‘Emulsion locks’ for the containment of hydrocarbons during surfactant flushing

Reversible double water in oil in water (W/O/W) emulsions were developed to contain subsurface hydrocarbon spills during their remediation using surfactant flushing. Double emulsions were prepared by emulsifying CaCl₂ solutions in canola oil, and subsequently by emulsifying the W/O emulsions in aqueous sodium alginate solutions. The formation of double emulsions was confirmed with confocal and optical microscopy. The double emulsions reversed and gelled when mixed with the surfactants sodium dodecyl sulfate (SDS) and cocamidopropyl betaine (CPB). Gels can act as ‘emulsion locks’ to prevent spreading of the hydrocarbon plume from the areas treated with surfactant flushing, as shown in sand column tests. Shear rheology was used to quantify the viscoelastic moduli increase (gelation) upon mixing the double emulsion with SDS and CPB. SDS was more effective than CPB in gelling the double emulsions. CPB and SDS could adsorb at the interface between water and model hydrocarbons (toluene and motor oil), lowering the interfacial tension and rigidifying the interface (as shown with a Langmuir trough). Bottle tests and optical microscopy showed that SDS and CPB produced W/O and O/W emulsions, with either toluene or motor oil and water. The emulsification of motor oil and toluene in water with SDS and CPB facilitated their flow through sand columns and their recovery. Toluene recovery from sand columns was quantitated using Gas-Chromatography Mass-Spectroscopy (GC-MS). The data show that SDS and CPB can be used both for surfactant flushing and to trigger the gelation of ‘emulsion locks’. Ethanol also gelled the emulsions at 100 mL/L.     

Characterization of water-in-crude oil emulsions in oil spill response

The formation of water-in-crude oil emulsions occurs when crude oils are spired into sea. The water-in-crude oil emulsions significantly change the properties of the spilled crude oils and in turn influence the choices made relating to oil spill countermeasures. The water-in-crude oil emulsions were characterized using various techniques in this study. The environmental scanning dectron microscopy observation of water droplets in the emulsions is also presented. It is a powerful tool in emulsion observations.     

乳状液膜吸收有机废气的实验研究

为提高水吸收乙酸丁酯的净化效率,以石油醚作膜相,聚异丁烯单丁二酰亚胺(T151)、聚异丁烯多丁二酰亚胺(T155)作乳化剂,制备水相/油相(W/O)型乳状液,作为分散相加入水中形成水相/油相/水相(W/O/W)型乳状液膜,进行了吸收含乙酸丁酯模拟废气的研究.主要考察了制乳速度、乳水比、表面活性剂用量、废气中乙酸丁酯初始浓度等参数对液膜吸收效率的影响.结果表明,乳状液膜体系对乙酸丁酯的吸收效率较高,在搅拌转速为400r/min,V(石油醚)∶V(水)为1∶1,w(T151)和w(T155)分别为6%和4%,V(乳化剂)∶V(水)为1∶4条件下制备的乳状液膜稳定性较好,且对乙酸丁酯废气吸收效率最高,可达80%以上.      

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.     

Acceleration of floc-water separation and floc reduction with magnetic nanoparticles during demulsification of complex waste cutting emulsions

Waste cutting emulsions are difficult to treat efficiently owing to their complex composition and stable emulsified structure. As an important treatment method for emulsions, chemical demulsification is faced with challenges such as low flocs–water separation rates and high sludge production. Hence, in this study, Fe₃O₄ magnetic nanoparticles (MNPs) were used to enhance chemical demulsification performance for treating waste cutting emulsions under a magnetic field. The addition of MNPs significantly decreased the time required to attain sludge–water separation and sludge compression equilibrium, from 210 to 20 min. In addition, the volume percentage of sludge produced at the equilibrium state was reduced from 45% to 10%. This excellent flocculation–separation performance was stable over a pH range of 3–11. The magnetization of the flocculants and oil droplets to form a flocculant–MNP–oil droplet composite, and the magnetic transfer of the composite were two key processes that enhanced the separation of cutting emulsions. Specifically, the interactions among MNPs, flocculants, and oil droplets were important in the magnetization process, which was controlled by the structures and properties of the three components. Under the magnetic field, the magnetized flocculant–MNP–oil droplet composites were considerably accelerated and separated from water, and the sludge was simultaneously compressed. Thus, this study expands the applicability of magnetic separation techniques in the treatment of complex waste cutting emulsions.     

红球菌PR-1菌株破乳性能研究

利用乳化剂Span 80配制出一种稳定的煤油-水乳浊液作为模型乳浊液,进而从大港油田废水中筛选出1株破乳能力较强的红球菌PR-1.该菌株培养液在55℃下8h可以使模型乳浊液完全破乳,且在实验条件下比化学破乳剂DGF-01具有更强的破乳活性.研究发现,乳浊液的破乳为线性增长过程,冻融和高压灭菌对其破乳能力没有影响,菌体细胞是破乳的主要活性成分,经超声波破碎及有机溶剂处理后其破乳活性显著降低.菌体表面有很强的疏水性,其对烃的粘附率为84%,碳链长度范围在C₂₇～C₅₄的枝菌酸类物质是保持菌体细胞完整性和疏水性的关键,其对细胞的破乳活性也至关重要.PR-1菌株发酵液用于原油乳状液的破乳具有操作方便,破乳率高,应用面广,无毒无害等优点,且能完全脱出J9-19原油乳状液中的水,因此可作为原油乳状液或油田采出水的破乳剂.     

特稠油污水处理技术研究

采用自己研究的药剂对辽河油田稠油污水进行破乳和净水试验，找出了主要影响因素，确定了处理工艺的操作条件。结果表明，使用破乳剂DI，可使油的回收率大于99％；絮凝剂A中添加了收缩絮体的化学药剂和B之后作为净水剂，使积杂量小于5％（体积比）。同时，处理后的水完全达到辽河油田要求的指标，即油含量小于5mg/L，积杂量小于15mg/L。     

内交联型淀粉改性水性聚氨酯固沙剂的制备

文章以甲苯二异氰酸酯(TDI)、聚氧化丙烯二醇(PPG)为基本原料,二羟甲基丙酸(DMPA)为亲水化改性单体、三羟甲基丙烷(TMP)为扩链剂通过预聚体法制备了淀粉改性水性聚氨酯环保型固沙剂,研究了淀粉用量对固沙剂乳液及其所成胶膜性能的影响。研究结果表明:在扩链聚合时加入可溶性淀粉,可以得到稳定的聚氨酯乳液;随着可溶性淀粉用量的增加,乳液的粘度增加,粒径呈增大趋势,胶膜拉伸强度减小;动态热力学分析显示胶膜储能模量E’随着淀粉含量的增加而减小,而玻璃化转变温度升高;保水实验显示保水效果随淀粉含量的增加而提高。当可溶性淀粉与纯聚氨酯的质量比为10%时,胶膜的拉伸强度和断裂伸长率分别为16.7 MPa和662%,而应用此配比固沙液的沙土在测试条件下10 h的失水率仅为55.7%,达到固沙剂保水性和胶膜力学性能之间较好的平衡。     

Preparation of porous adsorbent via Pickering emulsion template for water treatment: A review

Porous materials as emerging potential adsorbents have received much more attention because they are capable of capturing various pollutants with fast adsorption rate, high adsorption capacity, good selectivity and excellent reusability. In order to prepare porous materials with decent porous structure, Pickering emulsion template method has been proved to be one of the most effective technologies to create pore structure. This paper reviewed comprehensively the latest research progress on the preparation of porous materials from various Pickering emulsions and their applications in the decontamination of pollutants (e.g., heavy metal ions, organic pollutants) and in the oil/water separation. It was expected that the summaries and discussions in this review will provide insights into the design and fabrication of new efficient porous adsorbents, and also give us a better understanding of the subject.     

Recouping the wastewater: a way forward for cleaner leather processing

Leather processing employs copious amounts of water. This leads to the generation of enormous amounts of liquid effluent. The high effluent volume requires huge investments for effluent treatment plants in order to meet the required specification for the discharge of liquid effluents to various water bodies. Increasingly therefore, water use minimization in leather processing assumes greater significance due to increased treatment costs. End-of-pipe treatment methods alone do not meet the requirements and hence, in-plant control measures are gaining importance. The new era of cleaner technology has begun in leather processing. Pre-tanning and tanning operations contribute about 57% of the water consumption in leather processing and the washings about 35%. The proper adoption of integrated cleaner technologies provides a viable solution to the conservation of water in leather processing. This paper presents an integrated approach for water use minimization through recycling and optimization in leather processing. The integrated approach provides considerable reduction in the use of process water.     

Reclamation treatment of the chrome leather scrap

ＩｎｔｒｏｄｕｃｔｉｏｎＣｈｒｏｍｅｌｅａｔｈｅｒｓｃｒａｐｉｓｔｈｅｓｏｌｉｄ ｗａｓｔｅｏｆｌｅａｔｈｅｒｉｎｄｕｓｔｒｙ .Ｉｔｓｍａｉｎｃｏｍｐｏｓｉｔｉｏｎｉｓｐｒｏｔｅｉｎ(ｍａｉｎｌｙｃｏｌｌａｇｅｎｐｒｏｔｅｉｎ ,ｇｌｏｂｕｌｉｎａｎｄａｌｂｕｍｉｎ) ,ｓｏｍｅＣｒｃｏｍｐｏｕｎｄｂｏｎｄｉｎｇｗｉｔｈｔｈｅｐｒｏｔｅｉｎ ,ａｌｉｔｔｌｅｃａｒｂｏｈｙｄｒａｔｅ ,ｆａｔａｎｄｓｏｍｅｉｎｏｒｇａｎｉｃｓ.Ｔｈｅｃｈｒｏｍｅｌｅａｔｈｅｒｓｃｒａｐｓｔａｃｋｅｄｗｉｌｌｐｕｔｒｉｄｇｒａ…     

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.     

Application of power ultrasound in leather processing: an eco-friendly approach

The paper analyses and reviews in detail the use of ultrasound as a tool to improve the cleanliness of leather production for each stage of leather processing, showing that ultrasound has the added advantages of improving the process efficiency, reducing the process time and improving the quality of leather produced. The rate of diffusion of chemicals such as dyes through the pores of the leather matrix can be enhanced by the use of power ultrasound. Thus the optimum amount of chemicals required can be employed to improve the % exhaustion of chemicals, thereby minimising the significant amount of unspent chemicals in the effluent and reducing pollution load to a large extent. Dyeing experiments carried out in the presence of ultrasound (150 W and 33 kHz) give an increase of about 40% in dye exhaustion and a decrease in dyeing time by about 55% compared with the process in the absence of ultrasound under stationary conditions. Compared with conventional drumming conditions, ultrasound increases dye exhaustion by about 28% and reduces dyeing time by 25%. Ultrasound can also function as a physical activator and reduce the use of conventional chemicals in some of the processing stages, such as soaking for cleaning the raw skin/hide, liming for loosening hair and degreasing for removing natural fat. Therefore, ultrasound can be employed effectively in leather processing to enjoy multifaceted benefits.     

Novel eco-friendly spherical porous adsorbent fabricated from Pickering middle internal phase emulsions for removal of Pb(II) and Cd (II)

Spherical porous materials prepared from the emulsion template used in the water treat-ment have displayed a vast prospect,as the high surface area,abundant porous structure,convenient operation and excellent adsorption performance.But the tedious fabrication process,high consumption of organic solvent and surfactant limited the application widely.Herein,a facile and eco-friendly spherical porous adsorbent (SPA) is fabricated from the green surfactant-free (corn oil)-in-water Pickering medium internal phase emulsions (Pick-ering MIPEs) via the convenient ion crosslinking procedure.The Pickering MIPEs synergis-tically stabilized with the semi-coke (SC),which is the natural particle produced from the shale oil distillation,and sodium alginate (SA) has excellent storage and anti-coalescence stability.The as-prepared porous adsorbent possessed the abundant pore structure,which provided favorable conditions for effective mass transfer in adsorption,and could be tuned by varying the SA dosage.The saturation adsorption capacities of Pb(Ⅱ) and Cd(Ⅱ) can be achieved with 460.54 and 278.77 mg/g within 45 min at 25℃,respectively.Overall,this study supplied a viable and eco-friendly route for fabricating the spherical porous adsorbent with a tunable porous structure for heavy metal ion wastewater.     

氨水精馏法制液氨工艺及其在污水汽提装置的应用

阐述了氨水精馏法制液氨工艺的技术经济特点，分析了炼厂生产液氨的质量问题，指出了采用“氨水精馏法制液氨工艺”是含硫含氨污水汽提装置提高经济效益、社会效益的有效途径     

乳化液膜法处理含氨基J酸工业废水中破乳的实验研究

针对当前乳化液膜法中关键步骤—破乳进行了实验性研究。对于煤油—LMA－1—NaOH膜体系,研究了化学法和交流低电压电破乳的可行性,重点研究了电破乳的方法及温度、液膜体系及电场强度对破乳的影响。结果表明：对本实验的膜体系,化学法破乳效果不佳,而低电压破乳效果较好,破乳后的LMA－1油相可重复使用,具有良好的工业化应用前景。     

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.     

Use of vegetable oil in water emulsion achieved through ultrasonic atomization as cutting fluids in micro-milling

Significant amount of work is reported on development of vegetable oil based metalworking fluids (MWFs). Many also report on development and performance evaluation of vegetable based oils. For many of these water-based MWFs with vegetable oils, much effort is focused on stable emulsification of vegetable oil in water using a variety of surfactants. It has been found that surfactant-free stable emulsification of oil in water is possible through ultrasonic vibration. However, emulsification through ultrasonic atomization has not yet been considered, and the feasibility of emulsified metalworking fluids through ultrasonic atomization has not been investigated. In this paper, stable emulsification of vegetable oil in water has been achieved through ultrasonic atomization without using any surfactant. The emulsified vegetable oil in water is directly used to investigate its effectiveness as MWF in milling operations. Lower cutting forces, chip thickness, and burr amount are observed with vegetable oil-in-water emulsion compared to conventional MWF. The experimental results show strong potential for vegetable oil-in-water emulsion obtained through ultrasonic atomization as an effective MWF.     

周集铁矿水包油型乳状钻井液破乳问题研究

钻井液的配方和特性对钻井液体系的稳定性与钻进能否顺利完成有着直接的关系。针对周集铁矿ZK1725井钻井液体系的破乳问题进行了试验研究。将OP-10、吐温-80、司盘-80分别加入皂化油中制成乳状钻井液,并测试其稳定性,结果发现含有OP-10、吐温-80的乳状液有防破乳的功效,同时测定这两个样品的润滑性,发现加入OP-10或吐温-80会使水包油型乳状钻井液的润滑性下降;后续试验中测试了加入皂化油和OP-10的某水基泥浆的性能,结果发现加入这两种药品使得该体系的黏度提高较少,而润滑性提高了67%,可见OP-10对于钻井液性能的影响微乎其微。     

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.