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1、FOOD INDUSTRY WASTEWATER TREATMENT食品工业污水处理Abstract The purpose of the present study is to assess the condition of wastewaters pertaining to the production of cooking oil and to develop an effective and low-cost method for purification of wastewaters and utilisation of other oil production-related wa
2、stes which would comply with environmental safety requirements. It was made a quality assessment in terms of content of polluting substances of cooking oil-production wastewater. For identification of fat content (phospholipids) of wastewaters, the thin-layer chromatography method was applied. The b
3、asis of the proposed method for purification of wastewaters was a preliminary separation of clarified and neutralized wastewater by dint of calcium carbonate, subsequently sodium hypochlorite for water clarification and its additional neutralization was used. The presented method allows reaching a h
4、igh degree of wastewater purification, being effective and low-cost.摘要 本研究的目的是评估生产食用油污水的情况和制定一个有效的、低成本的净化方法，在遵守环保安全要求的情况下利用其他含油污水和含油废弃物，旨在按照质量来评价烹调产生的油类污水。其中薄层色谱法应用于识别脂肪含量(磷脂)的污水。在该方法的基础上，对污水的净化是一个初步澄清分离污水中的碳酸钙，随后用次氯酸钠澄清水，再添加中和剂的过程。本文所提出的方法可以达到一个高度净化污水的目的，具有高效、低成本的特点。Keywords: Cooking oil production
5、 wastewater; phospholipids; thin-layer chromatography; wastewater purification; wastewater treatment关键词:食用油生产污水；磷脂；薄层色谱法；污水净化；污水处理One of the main tendencies of development of food industry in the 21st century is the creation of useful and healthy products, the so-called functional food products. A s
6、pecific feature of such products is that they contain ingredients which, besides their traditional nutrient and energys upplying function, also possess a range of specific physiological functions which help human organism to combat negative influence of civilisation.创造这种有用的、健康的叫做功能性食品的产品在二十一世纪成为一种食品
7、工业上的主要发展趋势。这种产品的特征是包含了某些材料，除了具有提供传统养分和能量的功能，还具有一系列独特的生理功能，有助于人体对抗负面影响。Food industry is one of the most resource-demanding branches of industry, therefore it is especially important to ensure rational usage of raw materials. In the processing sub-branches of agricultural complex where the net value o
8、f products is comprised of material and energy expenditures, it is increasingly crucial to decrease the consumption of materials. This can be achieved by dint of wide implementation of non-waste technologies, complex usage of raw materials and secondary(recycled) resources in combined industry. Anot
9、her important aspect of the subject problem is ensuring of ecological safety of plants where the food products are produced as well as elimination of the influence of the wastes upon the environment. One of the most important problems which the food industry enterprises face is the problem of wastew
10、ater treatment. In Ukraine, food-producing enterprises are mostly located in the West and the South-West which have a rich network of water bodies. This means that control over discharge of sewage water is to be exercised more strictly than usual and food-producing companies in these regions are to
11、be prevented from polluting the water reservoirs.食品企业是对资源要求最高的产业结构之一，因此确保原材料的合理使用显得尤为重要。农业加工行业的净价值由原材料和能量支出决定，而且越来越多的决定于原材料的消耗。这就可以实现无废物生产技术、反复使用的原材料技术和使用二次(再生)资源技术的联合工业。食品工厂在产品生产和去除环境中废物的过程中的主要问题的另一个重要方面是确保生态安全。其中一个最重要的问题是企业面临的食品工业污水处理的问题。在乌克兰, 食品生产企业主要分布在有丰富水体网络的西部和西南部。这意味着控制排放的污水要比平时更严格地执行来避免食品生产
12、公司在这些地区污染水库。Ukraine is one of the five main world producers of sunflower. Yearly output of sunflower amounted to more than 4 million tonnes in this year. Only Argentine (6.4 m tonnes) produced more.乌克兰是世界五个主要向日葵生产地之一。今年向日葵的年产量达400万多吨。比阿根廷(6.4万吨)所产生的多得多。In the latest years, Ukrainian vegetable oil ma
13、rket has become increasingly more integrated into the global vegetable oil market. This is due to the fact that processes of international division of labour get deepened and Ukraine is becoming one of the worlds leading producers of sunflower seeds, sunflower oil, and groats.最近几年，乌克兰的植物油市场日益融入全球植物油
14、市场。这是由于这样的事实，乌克兰在国际分工的过程中得到深化，已经成为世界领先的向日葵花种子、向日葵花油和燕麦的生产地。Therefore, we are facing a crucially important task which foresees a more detailed examination of peculiarities of such valuable product as sunflower oil, bringing this production closer to the ecologically clean technologies whilst minimisi
15、ng the wastes of production.因此,我们正在面临着一个重要的任务, 更详尽地预测如此有价值的向日葵花油的产品特性，促进清洁生产同时减少产生的废料。Sunflower oil, alongside other vegetable oils, possesses a number of useful properties which make its consumption a lot more preferable than consumption of animal fat.向日葵花油与其他植物油一样，拥有许多有益的特性，比很多动物脂肪消耗的更多。With the p
16、urpose of further study of ecological influence of production of the cooking oil, assessment of the condition of sewage water, we shall examine the technology of oil production. 我们进一步对生产食用油产生的生态影响的研究是为了评估污水情况,检查技术食用油的生产工艺。Extraction method is applied owing to the solubility of fat in organic ether,
17、hexane, and pentane. The fat which is produced in this manner must be cleansed of solvents and the fat is to be refined.提取方法是应用于溶解性脂肪如有机醚、环己烷和戊烷。这样产生的脂肪必须用溶剂清洗然后精炼浓缩。The oil produced by way of pressing may be refined or not refined. But given the increased usage of chemicals in the agriculture and t
18、he deterioration of the environment, the raw materials as well as the oil may contain pesticides, toxic metals, mycotoxins, and carcinogenic benzopyrene. Because of this, scientists and specialists deem it that all kinds of oil must necessarily be subject to refinement whilst raw material is to be s
19、ubject to sanitary and hygienic control, verifying the presence or absence of these substances.通过压榨产生的油可能是精炼的，也有可能不是。但是使用化学物质会使农业和环境恶化，原材料以及油中可能含有杀虫剂、有毒金属、毒素、致癌苯并芘。因此，科学家们和专家认为这种油必须在安全和卫生的控制下精制提纯，核实不存在这些物质。Oil refinement leads to full or partial removal of harmful substances. Depending upon the dept
20、h of purification, the following types of oil are produced:食用油的提纯导致全部或部分的有害物质的被去除。取决于纯化的深度，以下类型食用油被生产: non-refined (cleaned from mechanical admixtures) hydrated (cleaned from phosphatides) refined non-deodorised (cleaned from phosphatides, free fat acids, colouring agents) refined deodorised (refine
21、d oil cleaned from aromatic and flavouring substances, pesticides and carcinogens).After the non-refined oil is separated from the raw material, it is to be filtered or left to settle, so that peelings, particles of seed coats, pulp etc can be removed. The non-refined oil possesses colour, flavour,
22、and smell which are peculiar to its mother raw material as well as all the corresponding substances (including the biologically active ones) which are native to it.未精炼的(来自机械压榨)水合物(来自磷脂)精炼有臭味的(来自磷脂，游离脂肪酸、着色剂)精炼无臭味的(从香料和芳香物质,从杀虫剂和致癌物质清洗出来的精炼油)。未精炼的油从原料分离后，是过滤或沉淀下来，以便种皮,胚、果肉等可以去掉。有臭味的油具有的颜色、气味、味道都是独一无二
23、的,其原料以及所有类似的物质(包括生物活性物)都是土生土长的。Most of Ukrainian oil-producing enterprises do not provide for purification of industrial wastewaters, dumping thousands of tonnes of polluting substances into the water bodies. The purification facilities which exist in some places were constructed a long time ago and
24、 had been designed with regard to the requirements of domestic wastewater purification. Such facilities, at best, partially decrease the value of general BOD (biological oxygen demand) or simply let the wastewater flow through; whilst at worst, the wastewater is decomposing in these facilities and b
25、ecomes even more poisonous when dumped into water bodies. Such industrial wastewaters are mostly polluted, especially with organic substances; therefore the purification facilities which are currently in operation are unable to clean them in compliance with sanitary requirements. A significant ecolo
26、gical danger comes from the pollution of surface waters with organic substances which the wastewaters flowing from cooking oil-producing facilities contain. These substances, when dumped into water bodies, prompt the development of decomposition processes, infect water bodies with pathogenic bacteri
27、a, cause water efflorescence and have an overall negative influence over fauna and flora. For many enterprises of the subject branch, purification of wastewaters presents a serious problem.乌克兰大部分的食用油生产企业不能净化工业污水，排放成千上万吨的污染物质进入水体。一些存在净化设备的地方是很久以前建立的而且是为生活污水净化而设计的。这些设施即使在最好的情况下也只能减少部分BOD（生物需氧量）值或者仅仅是让
28、水通过；最坏的情况是这些污水在排入水体前腐蚀这些设备并增强毒性。这些工业污水大多受到污染，特别是有机物的污染；当前的净化设备不能达到卫生要求。这些受食用油生产企业产生的有机物污染的地表水成为重大的生态危机。这些物质排放到水体中促进了腐烂过程，病原菌污染了水体，导致水恶臭并且对动植物产生影响。对于许多企业，污水净化成为一个严峻的问题。The purpose of the present study is to assess the condition of wastewaters pertaining to the production of cooking oil and to develop
29、 an effective and low-cost method for purification of wastewaters and utilisation of other oil production-related wastes which would comply with environmental safety requirements.本研究的目的是评估食用油工业产生的污水情况和开发一种高效、低成本的方法来利用市面上其他油类污水，并且达到环保安全要求。As basis of our study, we have chosen the wastewaters dumped b
30、y those Ukrainian vegetable oil producing enterprises whose purification facilities are all but unused due to their technical deficiency. As a result of this, the polluted wastewaters, which do not correspond to the requirements of the Law of Ukraine “About protection of environment” and “Regulation
31、s for Protection of Surface Waters from Wastewater Pollution”, are dumped into open water bodies. As of today, the main problem of such facilities is the vast amount of wastewaters which are discharged in the process of production. These wastewaters flowing from extraction and refinement workshops a
32、re heavily polluted with organic substances (neutral fats, phospholipids, organic acids etc), both in dissolved condition and in the form of suspended solids and emulsion. It is not possible to dump such wastewaters into open water bodies without prior purification. The enterprise regarded it as eco
33、nomically unsound to neutralise discharges using sodium hydroxide because a lot of sodium hydroxide is needed while the water body would get even more polluted. Wastewaters are characterised by high degree of turbidity (dimness); the appearance of the substance resembles shaken emulsion of suspended
34、 substances in the form of tiny flakes having a sharp unpleasant smell of rancid fat exposed to rotting processes. 以研究为基础，我们通过乌克兰的植物油生产企业选择废弃的污水，那些企业的净化设施由于工艺缺陷几乎不用。因此，不符合乌克兰“关于保护环境”和“保护地表水污水污染条例”法律要求的污染污水排入开放的水体。从今天开始，主要问题是这些设备在生产过程中大量排放的污水。这些来自提纯和精炼的车间的污水含有大量的有机污染物(中性脂肪、磷脂、有机酸等)，以悬浮液和乳浊液的形式溶解。事先未经
35、净化的污水不可能排放在开放的水体中。企业出于经济问题的考虑不会中和排放的氢氧化钠，虽然水体会造成更严重的污染，但是氢氧化钠是必须的。污水特色是高度的浑浊(浑浊)；外表类似悬浮液摇动后的乳浊液，以微小的鳞片形式存在，并有腐败过程产生的难闻的腐臭气味。Experimental part实验部分In order to design a method for purification of the aforementioned wastewaters, we have conducted a series of experimental investigation. A quality assessm
36、ent (in terms of content of polluting substances) of cooking oil-production wastewater was made using physical and chemical methods of analysis. A degree of pollution of wastewater was determined in terms of the following indicators (Table 1).为了设计出一种净化上述污水的方法，我们已经进行了一系列的实验研究。烹饪产生的含油污水质量的评价(污染物质的指标)采
37、用物理和化学的分析方法。污水的污染程度取决于以下指标(表1)。Table 1. Quality indicators of wastewaters from the examined oil-producing facilities表1 从含油污水设备中检查出的质量指标No. Wastewater indicatorqualityMeasuring unitValues(de facto)Values(normal)1Iron (general)mg/dm1.620.32Ammoniamg/dm10.02.03Phosphatesmg/dm102.793.54Suspended substan
38、cesmg/dm104.4155Dry residuemg/dm1571.02006Synthetic surface substances (anionic)activemg/dm0.880.57Fatsmg/dm13.01.08Biological demand-5 (BOD-5)oxygenmg/dm36.5159pH valuemg/dm2.16.5-8.5编号污水指标品质计量单位实际值正常值1铁(总体)mg/dm1.620.32氨mg/dm10.02.03磷酸盐mg/dm102.793.54悬浮物mg/dm104.4155干残渣mg/dm1571.02006表面合成物质(阴离子)活性
39、的mg/dm0.880.57脂肪mg/dm13.01.08BOD-5氧mg/dm36.5159PH值mg/dm2.16.5-8.5In order to determine BOD-5, a neutralisation of the examined water sample was made and the water sample was dissolved using a specially prepared, oxygen-saturated water containing nutrients; incubation of the sample lasting a certain
40、period of time (5 days) at t = 201 without air and light access in an entirely filled and corked bottle; concentration of dissolved oxygen before and after the incubation period was determined by the method of voluminal iodometric titration; turbidity of the water sample was determined using the pho
41、tometric method of analysis (turbidimetric method).为了确定BOD-5, 制作经检测水样的中和液，然后倒入一种特别的准备好的、含饱和氧、含有机物的水；保持水样一段时间（5天）恒温201摄氏度，满满地放入完全隔绝空气、光照的用瓶塞塞住的瓶子；用碘量滴定的体积表示恒温培养期前后的浓度；水样的浊度用分光光度法（浊度滴定法）。For identification of fat content of wastewaters, the thin-layer chromatography method was applied with silica gel
42、“H” plates produced by Merk company, layer thickness = 0.3 mm. Chromatography was made in the following systems:为辨认污水中脂肪的含量，薄层色谱法应用默克公司生产的硅胶“H”板，厚度=0.3毫米。色谱分析法在下列溶液中:Direction 1: chloroform: methanol: 25 % aqueous solution of ammonium in the following proportions: 65-25-2.Direction 2: chloroform: me
43、thanol: acetic acid: water; proportions: 85-15-10-3.方法1：氯仿：甲醇：25%的硝酸铵水溶液：比例:65-25-2。方法2：氯仿：甲醇：醋酸：水；比例:85-15-10-3。After preliminary neutralisation and deposition of sulphates, the wastewater (qty = 50 mcL) was applied on the plate in right lower angle. After drying, the plate was inserted into the ch
44、romatographic chamber filled with a system of solvents for Direction 1. After the F1 Solvent Front was passed, the plate was removed and air-dried. Then it was turned over 90 clockwise compared to its initial placing, and again inserted into the chromatographic chamber filled with a system of solven
45、ts for Direction 2. After passing of F2 Solvent Front, the plate was removed and air-dried. Then it was developed in an exsiccator saturated with iodine steam for about 15 minutes. The phospholipids manifested themselves on the chromatogram in the form of yellow stains.经过初步硫酸盐中和和沉淀，污水（数量=50mcl）涂抹在感光
46、片右下角。经过干燥，感光片插入到装满方法1溶液的色谱仪内。在通过F1溶剂后，将感光片移开、风干。接着顺时针转90度和最初的进行比较，再一次插入到装满方法2溶液的色谱仪内。在通过F2溶剂后，将感光片再次移开、风干。然后放入碘蒸汽中15分钟显影。磷脂显示着各种黄色的色谱图。It was detected that oil production-related wastewaters contain the following phospholipids (Figure 1):这是市面上检测到的油制造行业污水所包含的磷脂(图1)：Figure 1. Chromatogram of phospholi
47、pids in oil production Wastewaters图1 油制造行业污水的磷脂气相色谱1 - neutral lipids;2 - phosphatidylethanolamine;3 - phosphatidyl-glycerol;4 - phosphatidyl inositol;5 - phosphatidic acids; 6,7 - lysophosphatidylcholine;8 - sphingomyelins9 - phosphatidylserine;10 - lysophosphatidylinositol;11,12 lysophosphatidylse
48、rine1 - 中性脂肪。2 - 磷脂酰乙醇胺;3 - 磷脂酰丙三醇;4 - 卵磷脂;5 - 磷脂酸;6、7 - 溶血卵磷脂;8 - 鞘磷脂9 - 磷脂酰丝氨酸;10 - 溶血磷脂纤维醇;11、12 - 溶血磷脂丝氨酸On the stage of primary water treatment, reagent methods were used, which included neutralisation of oil industrys wastewaters using calcium carbonate (chalk) which is a cheap and easily accessible material. The technology of water purification by chemical deposition presupposes its preliminary purification from colloidal-dispersed and sus