吸附技術(shù)在水污染控制中的應(yīng)用研究
發(fā)布時間：2018-07-24 12:32
【摘要】：水是人類生存不可缺少的重要自然資源,是社會可持續(xù)發(fā)展的重要物質(zhì)保障。隨著我國工業(yè)和農(nóng)業(yè)的發(fā)展以及人口的增長,各行各業(yè)產(chǎn)生的大量廢棄物和生活垃圾排入到水環(huán)境中,我國水環(huán)境污染形勢十分嚴(yán)峻。根據(jù)2016年發(fā)布的《中國環(huán)境狀況公報(bào)》,我國967個地表水國控?cái)嗝?點(diǎn)位)水質(zhì)監(jiān)測結(jié)果顯示,Ⅳ-劣Ⅴ類水質(zhì)斷面有343個,占35.5%。近年來嚴(yán)重影響人民生活與經(jīng)濟(jì)生產(chǎn)的水環(huán)境污染事件頻頻發(fā)生,造成巨大的人民健康損害和經(jīng)濟(jì)損失,社會影響也十分惡劣。據(jù)統(tǒng)計(jì),我國在1996-2006年,共發(fā)生水污染公共衛(wèi)生事件271起,累計(jì)受影響人口超過700萬人,其中生物性污染、化學(xué)性污染和混合污染案例分別為171例、92例和8例,分別占63.1%、33.9%和3.0%。為了有效控制水環(huán)境的污染,國家先后制定了相關(guān)法律法規(guī)及標(biāo)準(zhǔn)等,同時大力開展水污染控制技術(shù)研究。當(dāng)前水污染控制方法主要有物理法、化學(xué)法、物理化學(xué)法和生物法等。吸附技術(shù)以其操作簡便、吸附材料可再生、便于控制與管理、對水質(zhì)水溫和水量變化具有較好的耐沖擊負(fù)荷等優(yōu)勢在水污染控制中得到廣泛的應(yīng)用,但是由于很多用于水質(zhì)處理的吸附材料存在吸附量不足、再生困難、對水質(zhì)要求高等缺點(diǎn),尚不能滿足越來越繁重的水污染控制的現(xiàn)實(shí)需求。本研究主要針對水環(huán)境中的有機(jī)物、重金屬和病毒污染等問題,利用吸附技術(shù)可吸附各種污染物的特點(diǎn),以第三代活性炭產(chǎn)品?活性炭纖維(Activated Carbon Fiber,ACF)和自制載陽電荷吸附材料為研究對象,分別開展ACF對水中有機(jī)污染物苯胺的吸附效率研究;利用表面改性技術(shù)增加ACF表面含氧酸性基團(tuán),進(jìn)行改性ACF吸附水中重金屬污染物鉛的研究;采用陽性電荷凝膠包被柱層層析硅膠的方法制備載陽電荷吸附材料用于吸附水中病毒,建立了一套富集大水樣中病毒的裝置及方法。1.ACF吸附水中苯胺:ACF是在碳纖維技術(shù)基礎(chǔ)上發(fā)展形成的一種理想高效吸附新材料。ACF的比表面積大,其內(nèi)部具有充足的微孔徑。ACF以其吸附容量大、吸附速度快、處理量大且使用時間長等特點(diǎn),在水質(zhì)凈化處理方面具有獨(dú)特的優(yōu)勢。ACF對苯胺的吸附等溫線符合弗蘭德(Freundlich)吸附模式,在相同的苯胺平衡濃度時,發(fā)現(xiàn)303K比293K時的ACF投加量要大。另外,ACF吸附苯胺受p H值影響較大,隨著溶液中p H值的升高,吸附效率呈明顯上升趨勢。在苯胺吸附過程中,應(yīng)保持吸附環(huán)境的最佳p H值控制在7-8,這樣可以充分發(fā)揮ACF對苯胺的吸附性能。2.表面改性ACF吸附水中重金屬鉛:利用硝酸對ACF進(jìn)行改性處理,可顯著提高ACF表面的羧基、內(nèi)酯基、酚羥基等含氧酸性基團(tuán)含量,含氧酸性基團(tuán)含量可增加到1.846mmol/g。尤其是將羧基含量從0.012mmol/g增至0.848mmol/g,其增加量占基團(tuán)總數(shù)增加量的78.87%。ACF表面酸性基團(tuán)的增加可以為ACF吸附金屬離子提供更多的吸附位點(diǎn),其實(shí)際意義遠(yuǎn)比提高比表面積更為重要,且使p Hpzc從4.47減少至2.43。隨著ACF表面酸性基團(tuán)的大量增加,改性ACF對Pb2+吸附效率從45%左右增加至95%以上,并且快速吸附階段的吸附速率提高了近3倍。3.載陽電荷吸附材料富集大水樣中病毒:采用在60-100目的柱層層析硅膠表面包被上帶陽性電荷的凝膠方法制備成載陽電荷吸附材料。掃描電鏡結(jié)果可以看出載陽電荷吸附材料是在硅膠表面上包被上了一層凝膠,其平均粒徑為271.59μm。將制備好的載陽電荷吸附材料裝入內(nèi)徑為84 mm,高為40 cm有機(jī)玻璃過濾柱中,最終載陽電荷吸附材料的高度約為30 cm,將含有濃度為102 PFU/m L大腸桿菌噬菌體f2的100 L水樣進(jìn)行過濾,載陽電荷吸附材料對大腸桿菌噬菌體f2的回收率達(dá)到90%以上。分別測試了3倍營養(yǎng)肉湯、3%牛肉粉、甘氨酸、甘氨酸復(fù)合3倍營養(yǎng)肉湯和甘氨酸復(fù)合3%牛肉粉等5種洗脫液對載陽電荷吸附材料上吸附病毒的洗脫效果,結(jié)果顯示只有甘氨酸回收率在60%左右,遠(yuǎn)低于其它4種洗脫液。通過分段檢測各第一次濃縮液中大腸桿菌噬菌體f2的含量,發(fā)現(xiàn)只有甘氨酸復(fù)合3倍營養(yǎng)肉湯為洗脫液不存在脫尾現(xiàn)象,因此確定甘氨酸復(fù)合3倍營養(yǎng)肉湯為該方法的洗脫液。通過富集方法中各項(xiàng)參數(shù)的測試,確定了富集過程中最佳流速為500 m L/min;水樣分別在p H值為5-9之間,溫度在4-30℃之間時大腸桿菌噬菌體f2的回收率均很穩(wěn)定,維持在90%以上;水中細(xì)菌濃度對大腸桿菌噬菌體f2影響較少。載陽電荷吸附材料富集方法與美國APHA推薦的1-MDS膜法比較具有對水質(zhì)要求低和回收率高的優(yōu)勢。通過測試不同水體中病毒富集效果,發(fā)現(xiàn)載陽電荷吸附材料對不同地域的自來水、地表水和醫(yī)院污水中的病毒均具有良好的富集去除效果。綜上所述,本研究以吸附技術(shù)為基礎(chǔ),利用ACF、表面改性ACF以及自制載陽電荷吸附材料分別對水中苯胺、鉛、病毒等典型污染物去除過程進(jìn)行了研究,均取得了良好的效果。其中,改性前后的ACF對苯胺和鉛均存在一個快速去除過程(5 min左右),達(dá)到平衡后的ACF對苯胺和鉛的去除效率均在80%以上。自制載陽電荷吸附材料對大體積水樣中的病毒具有較好的富集去除效果,當(dāng)洗脫液為甘氨酸復(fù)合3倍營養(yǎng)肉湯、流速為500 m L/min、p H值為5-9之間、溫度為4-30℃之間時,其回收率在90%以上。在下一步研究中將致力于把改性前后的ACF和載陽電荷吸附材料進(jìn)行高效集成,研制出可同時用于控制水環(huán)境中的有機(jī)物、重金屬和病毒的技術(shù)裝備,面對日益復(fù)雜的水質(zhì)污染狀況,使其在水污染控制研究領(lǐng)域具有更為廣泛的應(yīng)用前景。
[Abstract]:Water is an important natural resource for human survival and an important material guarantee for the sustainable development of the society. With the development of China's industry and agriculture and the growth of the population, a large amount of waste and domestic waste from all walks of life are discharged into the water environment. The pollution situation of the water environment in China is very severe. According to the "China" published in 2016, "China" The Environmental Status Bulletin, the water quality monitoring results of 967 surface water state control section (point position) in China showed that there were 343 water quality sections of class IV inferior V, accounting for the frequent occurrence of water environmental pollution which seriously affected people's living and economic production in recent years, resulting in the great people's health damage and economic loss, and the social influence was very bad. According to the data, the social influence was very bad. According to the 35.5%. In the past 1996-2006 years, 271 public health incidents of water pollution have occurred in China, with a cumulative impact of more than 7 million people, including 171 cases of biological, chemical and mixed pollution, 92 and 8, respectively, 63.1%, 33.9% and 3.0%. to effectively control the pollution of the water environment. The state has formulated relevant laws and regulations successively. The current water pollution control methods are mainly physical, chemical, physical and biological, and so on. The adsorption technology is easy to operate, the adsorptive material is renewable, easy to control and manage, and has better impact load on water temperature and water quantity, and the water pollution is better in water pollution. It has been widely used in dyeing control, but due to the lack of adsorption capacity, difficult regeneration and high requirements for water quality, many adsorbents used in water treatment are still unable to meet the practical needs of more and more heavy water pollution control. This study is mainly aimed at the problems of organic matter, heavy metals and virus pollution in water environment, and so on. Adsorption technology can adsorb the characteristics of various pollutants. The study on the adsorption efficiency of aniline by ACF on the third generation activated carbon products (Activated Carbon Fiber, ACF) and the self-made positive charge adsorption materials of the organic pollutants in water, and the use of surface modification technology to increase the oxygen containing acid group on the surface of ACF, The study on the adsorption of heavy metal contaminants in water by modified ACF was studied. The positive charge gel package was prepared by column layer chromatography with silica gel to adsorb virus in water. A set of equipment for enriching the virus in large water samples and the method of adsorption of aniline in water.1.ACF were established. ACF was developed on the basis of carbon fiber technology. The ideal high efficiency adsorption new material.ACF has large specific surface area, and its interior has sufficient micropore diameter.ACF with its large adsorption capacity, fast adsorption speed, large amount of treatment and long use time. The adsorption isotherm of.ACF to aniline is in accordance with the Flander (Freundlich) adsorption model in the water purification treatment. When the equilibrium concentration of aniline was balanced, the amount of ACF added to 303K was larger than that of 293K. In addition, the ACF adsorbed aniline was greatly influenced by the value of P H. With the increase of P H value in the solution, the adsorption efficiency showed an obvious upward trend. In the process of aniline adsorption, the optimum P H value of the adsorption environment should be kept at 7-8, so that the adsorption properties of ACF to aniline could be fully played. 2. surface modified ACF adsorbed heavy metal lead in water: using nitric acid to modify ACF, the content of carboxyl group, lactone group and phenol hydroxyl group on ACF surface can be increased significantly, and the content of oxygen containing acid group can be increased to 1.846mmol/g., especially the content of carboxyl group from 0.012mmol/ g to 0.848mmol/g, and the increase of the amount of group is increased. The increase of the surface acidic group of the amount of 78.87%.ACF can provide more adsorption sites for the adsorption of metal ions on ACF, which is more important than improving the surface area. And the decrease of P Hpzc from 4.47 to 2.43. increases with the increase of the acid group of ACF surface, and the adsorption efficiency of the modified ACF increases from about 45% to over 95%, and is faster. The adsorption rate of the fast adsorption phase increased by nearly 3 times the.3. carrier adsorption material to enrich the virus in the large water sample. The positive charge adsorption material was prepared by the gel method of the 60-100 column layer chromatography on the silica gel bread with the positive charge. The scanning electron microscope results showed that the positive charge adsorption material was coated on the surface of the silica gel. A layer of gel was applied to the average particle size of 271.59 mu m.. The prepared positive charge adsorption material was loaded into the inner diameter of 84 mm, and the 40 cm organic glass filter column was high. The height of the positive charge adsorption material was about 30 cm, and the 100 L water containing 102 PFU/m L coliphage F2 was filtered and the positive charge adsorption material was carried. The recovery rate of Escherichia coli F2 reached more than 90%. The elution effects of 5 kinds of eluent on the adsorbed virus on the positive charge adsorbents were tested 3 times of nutrient broth, 3% beef powder, glycine, 3 times glycine complex and 3% beef powder, and the results showed that only the recovery rate of glycine was about 60%, far low. In the other 4 eluates, the content of Escherichia coli F2 in the first concentration liquid was detected by segmenting. It was found that only 3 times the glycine compound broth was not the tail of the eluant, so the glycine compound 3 times nutrient broth was determined as the eluent of the method. The optimum flow rate was 500 m L/min, the water sample was 5-9 at P H, and the recovery rate of Escherichia coli phage F2 was more stable than 90% when the temperature was 4-30. The concentration of bacteria in the water was less affected by the Escherichia coli phage F2. The enrichment method of the positive charge adsorption material was compared with the 1-MDS membrane method recommended by American APHA. It has the advantages of low water quality and high recovery rate. By testing the effect of virus enrichment in different water bodies, it is found that the positive charge adsorption material has good enrichment and removal effect on the virus in the water, surface water and hospital sewage in different regions. In summary, the study is based on the adsorption technology, using ACF, surface modified ACF The removal process of typical pollutants, such as aniline, lead and virus in water, was studied by the self-made positive charge adsorption material, respectively, and good results were obtained. Among them, there was a rapid removal process of aniline and lead (about 5 min) before and after the modified ACF, and the removal efficiency of ACF to aniline and lead after the balance was above 80%. The positive charge adsorption material has a good enrichment and removal effect on the virus in large volume water. When the eluate is 3 times the glycine compound meat soup, the flow rate is 500 m L/min, the P H value is between 5-9 and the temperature is 4-30 degrees C, the recovery rate is above 90%. The next step will be devoted to the modified ACF and the charge positive charge. The adsorption materials are integrated efficiently, and the technology and equipment of heavy metals and viruses which can be used to control the water environment at the same time are more widely used in the field of water pollution control.
【學(xué)位授予單位】：中國人民解放軍軍事醫(yī)學(xué)科學(xué)院
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：X52;O647.3
本文編號：2141394
[Abstract]:Water is an important natural resource for human survival and an important material guarantee for the sustainable development of the society. With the development of China's industry and agriculture and the growth of the population, a large amount of waste and domestic waste from all walks of life are discharged into the water environment. The pollution situation of the water environment in China is very severe. According to the "China" published in 2016, "China" The Environmental Status Bulletin, the water quality monitoring results of 967 surface water state control section (point position) in China showed that there were 343 water quality sections of class IV inferior V, accounting for the frequent occurrence of water environmental pollution which seriously affected people's living and economic production in recent years, resulting in the great people's health damage and economic loss, and the social influence was very bad. According to the data, the social influence was very bad. According to the 35.5%. In the past 1996-2006 years, 271 public health incidents of water pollution have occurred in China, with a cumulative impact of more than 7 million people, including 171 cases of biological, chemical and mixed pollution, 92 and 8, respectively, 63.1%, 33.9% and 3.0%. to effectively control the pollution of the water environment. The state has formulated relevant laws and regulations successively. The current water pollution control methods are mainly physical, chemical, physical and biological, and so on. The adsorption technology is easy to operate, the adsorptive material is renewable, easy to control and manage, and has better impact load on water temperature and water quantity, and the water pollution is better in water pollution. It has been widely used in dyeing control, but due to the lack of adsorption capacity, difficult regeneration and high requirements for water quality, many adsorbents used in water treatment are still unable to meet the practical needs of more and more heavy water pollution control. This study is mainly aimed at the problems of organic matter, heavy metals and virus pollution in water environment, and so on. Adsorption technology can adsorb the characteristics of various pollutants. The study on the adsorption efficiency of aniline by ACF on the third generation activated carbon products (Activated Carbon Fiber, ACF) and the self-made positive charge adsorption materials of the organic pollutants in water, and the use of surface modification technology to increase the oxygen containing acid group on the surface of ACF, The study on the adsorption of heavy metal contaminants in water by modified ACF was studied. The positive charge gel package was prepared by column layer chromatography with silica gel to adsorb virus in water. A set of equipment for enriching the virus in large water samples and the method of adsorption of aniline in water.1.ACF were established. ACF was developed on the basis of carbon fiber technology. The ideal high efficiency adsorption new material.ACF has large specific surface area, and its interior has sufficient micropore diameter.ACF with its large adsorption capacity, fast adsorption speed, large amount of treatment and long use time. The adsorption isotherm of.ACF to aniline is in accordance with the Flander (Freundlich) adsorption model in the water purification treatment. When the equilibrium concentration of aniline was balanced, the amount of ACF added to 303K was larger than that of 293K. In addition, the ACF adsorbed aniline was greatly influenced by the value of P H. With the increase of P H value in the solution, the adsorption efficiency showed an obvious upward trend. In the process of aniline adsorption, the optimum P H value of the adsorption environment should be kept at 7-8, so that the adsorption properties of ACF to aniline could be fully played. 2. surface modified ACF adsorbed heavy metal lead in water: using nitric acid to modify ACF, the content of carboxyl group, lactone group and phenol hydroxyl group on ACF surface can be increased significantly, and the content of oxygen containing acid group can be increased to 1.846mmol/g., especially the content of carboxyl group from 0.012mmol/ g to 0.848mmol/g, and the increase of the amount of group is increased. The increase of the surface acidic group of the amount of 78.87%.ACF can provide more adsorption sites for the adsorption of metal ions on ACF, which is more important than improving the surface area. And the decrease of P Hpzc from 4.47 to 2.43. increases with the increase of the acid group of ACF surface, and the adsorption efficiency of the modified ACF increases from about 45% to over 95%, and is faster. The adsorption rate of the fast adsorption phase increased by nearly 3 times the.3. carrier adsorption material to enrich the virus in the large water sample. The positive charge adsorption material was prepared by the gel method of the 60-100 column layer chromatography on the silica gel bread with the positive charge. The scanning electron microscope results showed that the positive charge adsorption material was coated on the surface of the silica gel. A layer of gel was applied to the average particle size of 271.59 mu m.. The prepared positive charge adsorption material was loaded into the inner diameter of 84 mm, and the 40 cm organic glass filter column was high. The height of the positive charge adsorption material was about 30 cm, and the 100 L water containing 102 PFU/m L coliphage F2 was filtered and the positive charge adsorption material was carried. The recovery rate of Escherichia coli F2 reached more than 90%. The elution effects of 5 kinds of eluent on the adsorbed virus on the positive charge adsorbents were tested 3 times of nutrient broth, 3% beef powder, glycine, 3 times glycine complex and 3% beef powder, and the results showed that only the recovery rate of glycine was about 60%, far low. In the other 4 eluates, the content of Escherichia coli F2 in the first concentration liquid was detected by segmenting. It was found that only 3 times the glycine compound broth was not the tail of the eluant, so the glycine compound 3 times nutrient broth was determined as the eluent of the method. The optimum flow rate was 500 m L/min, the water sample was 5-9 at P H, and the recovery rate of Escherichia coli phage F2 was more stable than 90% when the temperature was 4-30. The concentration of bacteria in the water was less affected by the Escherichia coli phage F2. The enrichment method of the positive charge adsorption material was compared with the 1-MDS membrane method recommended by American APHA. It has the advantages of low water quality and high recovery rate. By testing the effect of virus enrichment in different water bodies, it is found that the positive charge adsorption material has good enrichment and removal effect on the virus in the water, surface water and hospital sewage in different regions. In summary, the study is based on the adsorption technology, using ACF, surface modified ACF The removal process of typical pollutants, such as aniline, lead and virus in water, was studied by the self-made positive charge adsorption material, respectively, and good results were obtained. Among them, there was a rapid removal process of aniline and lead (about 5 min) before and after the modified ACF, and the removal efficiency of ACF to aniline and lead after the balance was above 80%. The positive charge adsorption material has a good enrichment and removal effect on the virus in large volume water. When the eluate is 3 times the glycine compound meat soup, the flow rate is 500 m L/min, the P H value is between 5-9 and the temperature is 4-30 degrees C, the recovery rate is above 90%. The next step will be devoted to the modified ACF and the charge positive charge. The adsorption materials are integrated efficiently, and the technology and equipment of heavy metals and viruses which can be used to control the water environment at the same time are more widely used in the field of water pollution control.
【學(xué)位授予單位】：中國人民解放軍軍事醫(yī)學(xué)科學(xué)院
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：X52;O647.3
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9 張崇淼;劉永軍;王曉昌;薛小平;王春;;環(huán)境水體中腸道病毒濃縮方法的比較[J];中國給水排水;2007年07期
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