CN102974600A - Periodic-dosing oil-gas-liquid three-phase extraction device and method thereof for repairing petroleum-contaminated soil - Google Patents
Periodic-dosing oil-gas-liquid three-phase extraction device and method thereof for repairing petroleum-contaminated soil Download PDFInfo
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Abstract
本发明公开了属于石油污染环境原位修复技术领域的一种周期性加药油气液三相抽提装置及其修复石油污染土壤的方法。该装置中对周期性加药系统的操作是先用空气压缩机在压力0.2-0.7MPa条件下对气裂/加药井周围进行气动震裂3h,提高周围土壤的孔隙度,然后将营养元素和表面活性剂药品周期性地向注入井内注入,以促进土壤当地微生物的生长,促进土壤颗粒上污染物的分散和增溶,有利于石油污染物质的降解。本发明的装置和方法充分有效的利用所加药品,节省药品成本,周期性加药有利于药品与石油烃污染物充分作用,提高修复系统的效率,对土壤中石油污染物的抽吸总体积提高达20%-40%,抽吸率提高达50%-65%。
The invention discloses a periodic dosing oil-gas-liquid three-phase extraction device and a method for repairing oil-polluted soil, which belong to the technical field of in-situ restoration of oil-polluted environments. The operation of the periodic dosing system in this device is to use an air compressor to perform pneumatic shock cracking around the gas cracking/dosing well for 3 hours under the condition of a pressure of 0.2-0.7 MPa to increase the porosity of the surrounding soil, and then inject nutrients And surfactant drugs are periodically injected into the injection well to promote the growth of local microorganisms in the soil, promote the dispersion and solubilization of pollutants on soil particles, and facilitate the degradation of petroleum pollutants. The device and method of the present invention make full and effective use of the added drugs, save the cost of drugs, and periodically add drugs to facilitate the full interaction between the drugs and petroleum hydrocarbon pollutants, improve the efficiency of the repair system, and increase the total volume of petroleum pollutants in the soil. Up to 20%-40%, the suction rate increased by 50%-65%.
Description
技术领域 technical field
本发明属于石油污染环境原位修复技术领域,具体涉及一种周期性加药油气液三相抽提装置及其修复石油污染土壤的方法。The invention belongs to the technical field of in-situ remediation of petroleum-polluted environments, and in particular relates to a periodic dosing oil-gas-liquid three-phase extraction device and a method for remediating petroleum-contaminated soil.
背景技术 Background technique
过去几十年,受历史时期经济技术条件及人们认识水平等多种因素的制约,石油企业在为国家做出重大贡献的同时,也带来了一系列的环境问题:油气开采过程中的废水、废气、落地原油、废气钻井液等污染物排入环境会对水体、大气、土壤和生态环境造成影响。随着石油资源的广泛应用,环境中的石油污染越来越严重。在石油生产、贮运、炼制加工及使用过程中,也会有石油烃类的溢出和排放,造成油田和石化工厂周围水体和土壤严重的石油污染。当今世界上石油的总产量每年约有22亿t,其中17.5亿t是由陆地油田生产的。全世界每年有800万t进入环境,我国每年有近60万t进入环境,污染土壤、地下水、河流和海洋,每年新增污染土壤 1x105t。In the past few decades, restricted by various factors such as economic and technological conditions in the historical period and people's awareness level, while petroleum companies have made great contributions to the country, they have also brought a series of environmental problems: Waste water in the process of oil and gas extraction The discharge of pollutants such as waste gas, ground crude oil, and waste gas drilling fluid into the environment will affect the water body, atmosphere, soil and ecological environment. With the wide application of petroleum resources, petroleum pollution in the environment is becoming more and more serious. During the process of oil production, storage, transportation, refining, processing, and use, there will also be spillage and discharge of petroleum hydrocarbons, causing serious oil pollution to the water and soil around oil fields and petrochemical plants. The total oil production in the world today is about 2.2 billion tons per year, of which 1.75 billion tons are produced by land oil fields. In the world, 8 million tons enter the environment every year, and in China, nearly 600,000 tons enter the environment every year, polluting soil, groundwater, rivers and oceans, and adding 1x10 5 tons of polluted soil every year.
20世纪80年代以来,土壤的石油污染问题成为世界各国普遍关注的环境问题。应运而生的修复方法主要包括物理法、化学法和生物方法。一般来说,早期治理石油污染土壤的方法主要是传统的物理(蒸汽法、抽气法、有机溶剂法、水力冲洗法)和化学方法(氧化法、热处理法),这些方法所需时间短、见效快,但存在二次污染、处理费用高等弊端,不利于广泛的应用。生物修复是随着人们对土壤生态系统自身的动态净化能力研究的深入,产生的应用人工生物干预土壤生态系统净化污染能力的新技术,特别是添加生物表面活性剂或者生物表面活性剂产生菌能够大幅缩短修复时间、提高修复效率,并且能够保持良好的环境友好性。它以其独有的污染物降解彻底、不造成二次污染、操作较简单及整体费用低、适用不同类型(原位/异位)的修复处理方式和能同时恢复生态系统美化环境等优点,而成为最新、发展最快的治理技术。到目前为止,通过生物修复技术改良受石油污染得土壤,被认为是最有生命力,最具代表性的技术,它作为一种环境友好技术己成为了国际科研的热点。Since the 1980s, soil oil pollution has become an environmental issue of widespread concern around the world. The restoration methods that emerged at the historic moment mainly include physical methods, chemical methods and biological methods. Generally speaking, the early methods of treating oil-contaminated soil are mainly traditional physical (steam method, air pumping method, organic solvent method, hydraulic flushing method) and chemical methods (oxidation method, heat treatment method). The effect is quick, but there are disadvantages such as secondary pollution and high treatment costs, which are not conducive to wide application. Bioremediation is a new technology that uses artificial biology to intervene in the purification ability of soil ecosystem with the in-depth research on the dynamic purification ability of soil ecosystem itself, especially the addition of biosurfactant or biosurfactant-producing bacteria can The repair time is greatly shortened, the repair efficiency is improved, and good environmental friendliness can be maintained. It has the advantages of complete degradation of pollutants, no secondary pollution, simple operation and low overall cost, applicable to different types of (in-situ/ex-situ) restoration methods, and the ability to restore the ecosystem and beautify the environment at the same time. And become the latest and fastest-growing governance technology. So far, the improvement of oil-contaminated soil through bioremediation technology is considered to be the most vital and representative technology. As an environmentally friendly technology, it has become a hot spot in international scientific research.
分析认为,所谓污染土壤的生物修复是指利用植物和微生物及其它生物,将存在于土壤中的污染物移除或降解转化成为无害物质,使土壤中污染物浓度降低到可接受水平。发达国家对生物修复技术非常重视,先后投入了大量资金用于土壤污染的恢复研究和应用,大量研究机构和商业公司从事该项技术的研究工作。德国1995年用于净化土壤的投资约60亿美元,美国90年代用于土壤修复的投资额超过百亿美元,它们的研究证明,利用生物分解有毒有害物质的生物修复技术是治理大面积污染区域的一种有价值的方法。According to the analysis, the so-called bioremediation of contaminated soil refers to the use of plants, microorganisms and other organisms to remove or degrade the pollutants existing in the soil into harmless substances, so that the concentration of pollutants in the soil can be reduced to an acceptable level. Developed countries attach great importance to bioremediation technology, and have invested a lot of money in the research and application of soil pollution restoration. A large number of research institutions and commercial companies are engaged in the research of this technology. Germany invested about 6 billion US dollars in soil purification in 1995, and the United States invested more than 10 billion US dollars in soil remediation in the 1990s. Their research has proved that bioremediation technology that uses biological decomposition of toxic and harmful substances is an effective way to treat large-scale polluted areas. a valuable method.
在土壤修复中,水溶性是影响污染物去除的重要因素,很多污染物都是疏水性很强的物质,一般的水洗修复速度慢,而且效率低,近年来人们通过加入各种添加剂来增强修复效果,这些添加剂能够促进土壤颗粒上污染物的分散和增溶,从而达到缩短时间提高污染物去除率的效果。In soil remediation, water solubility is an important factor affecting the removal of pollutants. Many pollutants are highly hydrophobic substances. The general water washing repair speed is slow and the efficiency is low. In recent years, people have added various additives to enhance repair. As a result, these additives can promote the dispersion and solubilization of pollutants on soil particles, thereby achieving the effect of shortening the time and improving the removal rate of pollutants.
发明内容 Contents of the invention
本发明的目的在于提供一种周期性加药油气液三相抽提装置。The purpose of the present invention is to provide a periodic dosing oil-gas-liquid three-phase extraction device.
本发明的目的还在于提供基于周期性加药油气液三相抽提装置修复受石油污染土壤的方法。The purpose of the present invention is also to provide a method for remediating oil-contaminated soil based on a three-phase oil-gas-liquid extraction device with periodic dosing.
一种周期性加药油气液三相抽提装置,该装置由周期性加药系统和油气液三相抽提系统组成,周期性加药系统中空气压缩机1和周期性加药装置2分别与控制系统3相连,空气压缩机1与气裂管4相连,周期性加药装置2与加药管5相连,气裂管4和加药管5分别与气裂/加药井6相连;油气液三相抽提系统中抽吸泵7分别与气液分离装置8和抽吸管18相连,气液分离装置8分别与液环泵9和输送泵12相连,液环泵9、气体处理装置10、气体回收装置11依次相连,输送泵12与水油分离装置13相连,水油分离装置13分别与油相回收装置14和水相处理装置15相连,水相处理装置15与水相回灌装置16相连,抽吸管18与抽吸井17相连。A periodic dosing oil-gas-liquid three-phase extraction device, which is composed of a periodic dosing system and an oil-gas-liquid three-phase extraction system. In the periodic dosing system, the
基于上述的周期性加药油气液三相抽提装置修复石油污染土壤的方法,包括如下步骤:The method for remediating oil-contaminated soil based on the above-mentioned periodical dosing oil-gas-liquid three-phase extraction device comprises the following steps:
1)用空气压缩机1在压力为0.2-0.7MPa下对气裂/加药井6周围进行气动震裂3h;1) Use the
2)开启周期性加药装置2将营养元素和表面活性剂注入气裂/加药井6内,加药9h,,然后停止气裂和加药12h,此次操作为一周期;2) Turn on the
3)加药同时,开启抽吸泵7通过抽吸井17中的抽吸管18将石油污染物抽取到地表面,进入气液分离装置8;分离出的气相通入气体处理装置10,处理后通过气体回收装置11或排放;分离出的液相通入水油分离装置13分离为油相和水相,油相通入油相回收装置14处理,水相通入水相处理装置15处理后进入水相回灌装置16;3) At the same time as dosing, start the suction pump 7 to pump the petroleum pollutants to the ground surface through the
4)在开启油气液三相抽提系统的时候,重复步骤1)和2)进行周期性加药,实时监测抽吸井渗出液的pH、COD、石油烃含量,当pH值为6-9,COD小于100mg/L,石油烃含量小于10mg/L时停止加药。4) When the oil-gas-liquid three-phase extraction system is turned on, repeat steps 1) and 2) for periodic dosing, and monitor the pH, COD, and petroleum hydrocarbon content of the suction well exudate in real time. When the pH value is 6- 9. Stop dosing when the COD is less than 100mg/L and the petroleum hydrocarbon content is less than 10mg/L.
步骤2)所述的营养元素由氮、磷元素和微量元素组成,其中氮、磷添加强度为:土壤中的污染物的碳元素含量与氮、磷元素的重量比C:N:P为100: (4-7): (0.8-1.3);营养元素中的微量元素为镁、铁、钙、铜、钴、锰、锌、硼、钼和硒,碳元素微量元素的重量比为1:(10-8-10-3)。Step 2) The nutritional elements are composed of nitrogen, phosphorus and trace elements, wherein the addition intensity of nitrogen and phosphorus is: the weight ratio of the carbon content of pollutants in the soil to nitrogen and phosphorus elements C:N:P is 100 : (4-7): (0.8-1.3); the trace elements in the nutrients are magnesium, iron, calcium, copper, cobalt, manganese, zinc, boron, molybdenum and selenium, and the weight ratio of the trace elements of carbon is 1: ( 10-8-10-3 ) .
步骤2)所述的表面活性剂为常规表面活性剂,其质量为土壤中石油污染物总质量的0.005-0.02。The surfactant described in step 2) is a conventional surfactant, and its mass is 0.005-0.02 of the total mass of petroleum pollutants in the soil.
本发明的有益效果为:1)在抽吸过程中周期性加药,极大地提高了石油污染物以及重金属在土壤中的可降解性;2)水油混合物的抽吸、分离一体化,设备结构紧凑,操作简单,可靠性高;3)石油烃类有机污染物去除率在95%以上,一次性修复效果好;4)修复周期较短,修复时间减少10%-25%,不产生二次污染;5)添加NLBS后处理系统的抽吸总体积提高20%-40%,抽吸率提高50%-65%;6)在国内外有良好的推广潜力,对加油站、石油产品生产、化工产品生产等造成的石油污染有较好的处理效果,该发明具有广阔的市场前景。The beneficial effects of the present invention are: 1) Periodic dosing during the suction process greatly improves the degradability of petroleum pollutants and heavy metals in the soil; 2) The suction and separation of the water-oil mixture are integrated, and the equipment Compact structure, simple operation and high reliability; 3) The removal rate of petroleum hydrocarbon organic pollutants is above 95%, and the one-time repair effect is good; 4) The repair cycle is short, the repair time is reduced by 10%-25%, and no secondary secondary pollution; 5) The total suction volume of the post-treatment system after adding NLBS is increased by 20%-40%, and the suction rate is increased by 50%-65%; The oil pollution caused by the production of , chemical products, etc. has a good treatment effect, and the invention has broad market prospects.
附图说明 Description of drawings
图1 为周期性加药油气液三相抽提装置示意图;Figure 1 is a schematic diagram of a periodic dosing oil-gas-liquid three-phase extraction device;
图中,1-空气压缩机、2-周期性加药装置、3-控制系统、4-气裂管、5-加药管、6-气裂/加药井、7-抽吸泵、8-气液分离装置、9-液环泵、10-气体处理装置、11-气体回收、12-输送泵、13-水油分离装置、14-油相回收装置、15-水相处理装置、16-水相回灌装置、17-抽吸井、18-抽吸管。In the figure, 1-air compressor, 2-periodically dosing device, 3-control system, 4-gas cracking tube, 5-dosing tube, 6-gas cracking/dosing well, 7-suction pump, 8 -Gas-liquid separation device, 9-liquid ring pump, 10-gas treatment device, 11-gas recovery, 12-transport pump, 13-water oil separation device, 14-oil phase recovery device, 15-water phase treatment device, 16 -Aqueous phase recharge device, 17-suction well, 18-suction pipe.
图2抽提系统在无加药与周期性加药后的抽吸总体积对比结果。Fig. 2 Comparison results of the total suction volume of the extraction system after no drug addition and periodic drug addition.
图3抽提系统在无加药与周期性加药后的抽吸率对比结果。Fig. 3 The comparison results of the suction rate of the extraction system after no dosing and periodic dosing.
具体实施方式 Detailed ways
下面结合附图和具体实例对本发明做进一步说明:Below in conjunction with accompanying drawing and specific example the present invention will be further described:
如图1所示的周期性加药油气液三相抽提装置,该装置由周期性加药系统和油气液三相抽提系统组成,周期性加药系统中空气压缩机1和周期性加药装置2分别与控制系统3相连,空气压缩机1与气裂管4相连,周期性加药装置2与加药管5相连,气裂管4和加药管5分别与气裂/加药井6相连;油气液三相抽提系统中抽吸泵7分别与气液分离装置8和抽吸管18相连,气液分离装置8分别与液环泵9和输送泵12相连,液环泵9、气体处理装置10、气体回收装置11依次相连,输送泵12与水油分离装置13相连,水油分离装置13分别与油相回收装置14和水相处理装置15相连,水相处理装置15与水相回灌装置16相连,抽吸管18与抽吸井17相连。The periodic dosing oil-gas-liquid three-phase extraction device shown in Figure 1 is composed of a periodic dosing system and an oil-gas-liquid three-phase extraction system. In the periodic dosing system, the
图2和图3分别反映了中试实验中添加周期性加药系统前后,抽提系统抽吸总体积和抽吸率的对比,可看出周期性加药后整个抽提系统的去除率和抽吸效率有明显提高,其中抽吸总体积可提高20% - 40%,抽吸率提高50% - 65%。Figure 2 and Figure 3 respectively reflect the comparison of the total suction volume and suction rate of the extraction system before and after adding the periodic dosing system in the pilot test. It can be seen that the removal rate and The suction efficiency is significantly improved, in which the total suction volume can be increased by 20% - 40%, and the suction rate can be increased by 50% - 65%.
2010年在辽宁省盘锦市辽河油田建立了一套上述周期性加药油气液三相抽提装置,并利用上述装置原位修复受石油污染的土壤,步骤如下。In 2010, a set of the above-mentioned periodic dosing oil-gas-liquid three-phase extraction device was established in Liaohe Oilfield, Panjin City, Liaoning Province, and the above-mentioned device was used to repair oil-contaminated soil in situ. The steps are as follows.
1)用空气压缩机1在压力为0.2-0.7MPa下对气裂/加药井6周围进行气动震裂3h;1) Use the
2)开启周期性加药装置2将营养元素和表面活性剂注入气裂/加药井6内,加药9h,,然后停止气裂和加药12h,此次操作为一周期;2) Turn on the
3)加药同时,开启抽吸泵7通过抽吸井17中的抽吸管18将石油污染物抽取到地表面,进入气液分离装置8;分离出的气相通入气体处理装置10,处理后通过气体回收装置11或排放;分离出的液相通入水油分离装置13分离为油相和水相,油相通入油相回收装置14处理,水相通入水相处理装置15处理后进入水相回灌装置16;3) At the same time as dosing, start the suction pump 7 to pump the petroleum pollutants to the ground surface through the
4)在开启油气液三相抽提系统的时候,重复步骤1)和2)进行周期性加药,实时监测抽吸井渗出液的pH、COD、石油烃含量,当pH值为6-9,COD小于100mg/L,石油烃含量小于10mg/L时停止加药。4) When the oil-gas-liquid three-phase extraction system is turned on, repeat steps 1) and 2) for periodic dosing, and monitor the pH, COD, and petroleum hydrocarbon content of the suction well exudate in real time. When the pH value is 6- 9. Stop dosing when the COD is less than 100mg/L and the petroleum hydrocarbon content is less than 10mg/L.
步骤2)所述的营养元素由氮、磷元素和微量元素组成,其中氮、磷添加强度为:土壤中的污染物的碳元素含量与氮、磷元素的重量比C:N:P为100: (4-7): (0.8-1.3);营养元素中的微量元素为镁、铁、钙、铜、钴、锰、锌、硼、钼和硒,碳元素微量元素的重量比为1:(10-8-10-3)。Step 2) The nutritional elements are composed of nitrogen, phosphorus and trace elements, wherein the addition intensity of nitrogen and phosphorus is: the weight ratio of the carbon content of pollutants in the soil to nitrogen and phosphorus elements C:N:P is 100 : (4-7): (0.8-1.3); the trace elements in the nutrients are magnesium, iron, calcium, copper, cobalt, manganese, zinc, boron, molybdenum and selenium, and the weight ratio of the trace elements of carbon is 1: ( 10-8-10-3 ) .
步骤2)所述的表面活性剂为常规表面活性剂,其质量为土壤中石油污染物总质量的0.005-0.02。The surfactant described in step 2) is a conventional surfactant, and its mass is 0.005-0.02 of the total mass of petroleum pollutants in the soil.
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