CN118558719A - Biodegradation method and degradation device for oil-based drill cuttings deoiling tailings - Google Patents

Biodegradation method and degradation device for oil-based drill cuttings deoiling tailings Download PDF

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CN118558719A
CN118558719A CN202410553939.4A CN202410553939A CN118558719A CN 118558719 A CN118558719 A CN 118558719A CN 202410553939 A CN202410553939 A CN 202410553939A CN 118558719 A CN118558719 A CN 118558719A
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CN118558719B (en
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范例
甘伟
张晟
龚先河
宾灯辉
王健
袁胜
颜渝森
刘姜艳
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Chongqing Academy Of Eco-Environmental Sciences
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09BDISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/60Biochemical treatment, e.g. by using enzymes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09BDISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/30Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
    • B09B3/35Shredding, crushing or cutting
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09BDISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/30Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
    • B09B3/38Stirring or kneading
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09BDISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
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Abstract

本发明涉及含油固体废弃物微生物处理领域,具体涉及用于油基钻屑脱油尾渣的生物降解方法及其降解装置,试验方法如下:1)配置油基岩屑,2)准备降解菌群,3)在降解装置中建立降解体系,4)启动实验装置,降解周期定为60天,取样,测定样品重量以及样品中的石油烃浓度,最终计算降解率。实验装置主要包括降解桶,在降解桶的内部设有搅拌轴,在降解桶的内底部和桶壁设有曝气管,在搅拌轴上从上至下分别刚性连接着框式搅拌桨、强化搅拌桨和刮泥搅拌桨,该方法相对于三角瓶小试实验方法,能通过装置实现搅拌、降解体系控温、曝气等功能,从而规模化处理油基钻屑脱油尾渣,实现高效处理脱油后剩余尾渣,具有经济性、高效性、可持续性。

The present invention relates to the field of microbial treatment of oil-containing solid waste, and specifically to a biodegradation method and a degradation device for oil-based drill cuttings deoiling tailings. The test method is as follows: 1) configuring oil-based rock cuttings, 2) preparing degradation bacteria, 3) establishing a degradation system in a degradation device, 4) starting the experimental device, setting the degradation cycle to 60 days, taking samples, measuring the sample weight and the petroleum hydrocarbon concentration in the sample, and finally calculating the degradation rate. The experimental device mainly includes a degradation barrel, a stirring shaft is provided inside the degradation barrel, an aeration pipe is provided at the inner bottom and barrel wall of the degradation barrel, and a frame stirring paddle, a reinforced stirring paddle and a scraping stirring paddle are rigidly connected to the stirring shaft from top to bottom. Compared with the small-scale experimental method of a triangular flask, this method can realize stirring, degradation system temperature control, aeration and other functions through the device, thereby large-scale treatment of oil-based drill cuttings deoiling tailings, and efficient treatment of the remaining tailings after deoiling, which is economical, efficient and sustainable.

Description

用于油基钻屑脱油尾渣的生物降解方法及其降解装置Biodegradation method and degradation device for oil-based drill cuttings deoiling tailings

技术领域Technical Field

本发明涉及含油固体废弃物微生物处理领域,具体涉及一种用于油基钻屑脱油尾渣的生物降解方法及其降解装置。The invention relates to the field of microbial treatment of oil-containing solid waste, and in particular to a biodegradation method and a degradation device for oil-based drill cuttings deoiling tailings.

背景技术Background Art

油基泥浆具有抗高温、润滑性好、对油气层损害小等优点,被大规模地应用于页岩气钻采过程,但在该过程中会产生大量的油基泥浆钻井岩屑,其中包括反排油即柴油、白油、生物油、矿物油、合成油和各种油田化学剂等,具有体系异常稳定,污染物种类复杂、含油量高等特点,处理难度非常大。页岩气是地下页岩地层中附汲包裹着的气,页岩气勘探钻井过程中,为了获得更多的页岩气,常在钻达目的层位—页岩层位时要采取水平钻井。为了在水平层实现快速安全钻井,保护油气层,钻井过程中往往使用油基泥浆进行钻井,国内油基泥浆主要采用柴油或白油作为基础油加入其它添加剂配置而成。破碎的地下岩层岩屑粘附于油基泥浆,由此产生了油基钻屑。一个单井油基钻屑产生量约350m3左右,一个平台井组(一般5—7口单井)将产生2000—2500m3左右的油基钻屑,而油基钻屑含油率在15—20%,环境危害性大,处理难度高。Oil-based mud has the advantages of high temperature resistance, good lubricity, and little damage to oil and gas layers. It is widely used in the shale gas drilling process. However, a large amount of oil-based mud drilling cuttings will be generated in the process, including reverse oil, namely diesel, white oil, bio-oil, mineral oil, synthetic oil and various oilfield chemicals. It has the characteristics of abnormal stability of the system, complex types of pollutants, and high oil content, and is very difficult to handle. Shale gas is gas enclosed in underground shale formations. In the process of shale gas exploration and drilling, in order to obtain more shale gas, horizontal drilling is often used when drilling to the target layer - shale formation. In order to achieve fast and safe drilling in the horizontal layer and protect the oil and gas layer, oil-based mud is often used for drilling during the drilling process. Domestic oil-based mud is mainly made of diesel or white oil as the base oil and other additives. The broken underground rock formation cuttings adhere to the oil-based mud, thus producing oil-based drilling cuttings. A single well produces about 350m3 of oil-based drill cuttings, and a platform well group (usually 5-7 single wells) will produce about 2000-2500m3 of oil-based drill cuttings. The oil content of oil-based drill cuttings is 15-20%, which is highly harmful to the environment and difficult to handle.

油基钻屑直接排放将对环境的影响主要体现在以下几个方面:1、有机污染物污染地表水和地下水资源;2、石油类对植物的生长有毒害作用,长期滞留土壤抑制植物生长和土壤微生物繁殖;3、高浓度可溶性盐会造成周围土壤硬化,减少土壤肥力;4、油基钻屑中含有大量的铜、铅、铬等重金属离子,进入土壤后被作物吸收最终通过食物链作用进入人体,危害人体健康。因此,研究处理油基钻屑具有重要的实际意义。The direct discharge of oil-based drill cuttings will have the following impacts on the environment: 1. Organic pollutants pollute surface water and groundwater resources; 2. Petroleum is toxic to plant growth, and long-term retention in the soil inhibits plant growth and soil microbial reproduction; 3. High concentrations of soluble salts will cause the surrounding soil to harden and reduce soil fertility; 4. Oil-based drill cuttings contain a large amount of heavy metal ions such as copper, lead, and chromium, which enter the soil and are absorbed by crops and eventually enter the human body through the food chain, endangering human health. Therefore, research on the treatment of oil-based drill cuttings has important practical significance.

目前处理油基钻屑的方法主要分为物理处理法、化学处理法和生物降解法。其中物化处理技术是国内外如今普遍采用较成熟的方法,但上述方法对环境有较大污染隐患,设备能耗大、成本高、二次污染严重及普适性差等问题;生物降解法因具有处理成本低、对环境无二次污染等优点,被认为最经济和最具永续利用的环保型技术,现已得到较多应用。At present, the methods for treating oil-based drill cuttings are mainly divided into physical treatment, chemical treatment and biodegradation. Among them, physical and chemical treatment technology is a relatively mature method widely used at home and abroad, but the above methods have great pollution risks to the environment, high energy consumption of equipment, high cost, serious secondary pollution and poor universality. The biodegradation method has the advantages of low treatment cost and no secondary pollution to the environment. It is considered to be the most economical and sustainable environmentally friendly technology and has been widely used.

微生物降解技术是指在适宜环境下通过微生物各种代谢途径将污染物降解的技术。大量研究表明,在石油烃类污染的自然降解中,微生物降解起着重要的作用。向石油污染的水体或土壤中投加环境适应性强、降解效能高的菌种或菌群是提高石油降解效率的重要技术手段。微生物好氧代谢过程中能够降解大部分饱和脂肪烃和芳香烃,脂肪烃在单氧化酶和脱氢酶的作用下生成脂肪酸,而芳香烃则在氧化酶和水解酶的作用下转化成二氢二醇。经过实验证明,申请号为201911067322.7的发明专利,公开了一种多源页岩气油基钻屑高效降解复合菌的制备方法及其应用,公开了一种多源页岩气油基钻屑高效降解复合菌的制备方法及其应用,复合菌由红球菌FL-1(Rhodococcus baikonurensis)、红球菌NC-17(Rhodococcus pedocola)和迪茨氏菌WL-3(Dietzia maris)的培养液按照体积比为1:1:1比例混合而成。该复合菌可在不人为添加碳源的基础上,降解多井场来源的页岩气油基钻屑石油烃类污染物,对含油量5%以内的油基钻屑均有较好的降解效果,是一种对油基钻屑具备良好降解性能的耐油复合菌。实验证明这种菌群对于多源页岩气油基钻屑的高效降解具有关键作用,虽然阐述了降解条件和降解应用,但是没有具体阐述降解的方法和设备。Microbial degradation technology refers to the technology of degrading pollutants through various metabolic pathways of microorganisms under suitable environments. A large number of studies have shown that microbial degradation plays an important role in the natural degradation of petroleum hydrocarbon pollution. Adding bacteria or bacterial communities with strong environmental adaptability and high degradation efficiency to petroleum-contaminated water or soil is an important technical means to improve the efficiency of petroleum degradation. Microorganisms can degrade most saturated aliphatic hydrocarbons and aromatic hydrocarbons during aerobic metabolism. Aliphatic hydrocarbons are converted into fatty acids under the action of monooxygenases and dehydrogenases, while aromatic hydrocarbons are converted into dihydrodiols under the action of oxidases and hydrolases. Experimental results show that the invention patent with application number 201911067322.7 discloses a preparation method and application of a multi-source shale gas oil-based drill cuttings efficient degradation composite bacteria, and discloses a preparation method and application of a multi-source shale gas oil-based drill cuttings efficient degradation composite bacteria, the composite bacteria is a mixture of the culture solution of Rhodococcus baikonurensis FL-1 (Rhodococcus baikonurensis), Rhodococcus NC-17 (Rhodococcus pedocola) and Dietzia maris WL-3 (Dietzia maris) in a volume ratio of 1:1:1. The composite bacteria can degrade petroleum hydrocarbon pollutants in shale gas oil-based drill cuttings from multiple well sites without artificially adding carbon sources, and has a good degradation effect on oil-based drill cuttings with an oil content of less than 5%. It is an oil-resistant composite bacteria with good degradation performance for oil-based drill cuttings. Experiments have shown that this bacterial community plays a key role in the efficient degradation of multi-source shale gas and oil-based drill cuttings. Although the degradation conditions and degradation applications are explained, the degradation methods and equipment are not specifically explained.

基于以上情况,我们研发了一种小型设备(该设备可见申请号为CN202311592449.7,公开(公告)号为CN117619867A的发明专利),利用微生物降解技术和一种自动控制转速的设备通过控制转速、倾斜角度让油基钻屑与降解菌充分混匀,以便于确定最佳降解条件,这种通过实验设备与实验方法结合,模拟实际降解环境,确定降解实验内外界条件对降解效果的影响,实现高效处理脱油后剩余尾渣达到环保要求的效果。经过不断实验,该项技术具有显著效果,但是前述实验设备只能提供小规模试验,不便于大批量实验,提供的数据具有不稳定性,所以需要继续研发能够大量处理多源页岩气油基钻屑的设备,一步一步将该方法推向工业化。Based on the above situation, we have developed a small device (the device can be seen in the patent application number CN202311592449.7, and the public (announcement) number is CN117619867A). We use microbial degradation technology and an automatic speed control device to fully mix the oil-based drill cuttings with the degradation bacteria by controlling the speed and tilt angle to determine the optimal degradation conditions. This combines experimental equipment with experimental methods to simulate the actual degradation environment, determine the influence of external and internal conditions on the degradation effect in the degradation experiment, and achieve efficient treatment of the remaining tailings after deoiling to meet environmental protection requirements. After continuous experiments, this technology has significant effects, but the aforementioned experimental equipment can only provide small-scale experiments, which is not convenient for large-scale experiments, and the data provided is unstable, so it is necessary to continue to develop equipment that can process a large number of multi-source shale gas oil-based drill cuttings, and step by step promote this method to industrialization.

发明内容Summary of the invention

为解决上述技术问题,本发明的目的在于提供一种用于油基钻屑脱油尾渣的生物降解方法及其降解装置,In order to solve the above technical problems, the object of the present invention is to provide a biodegradation method and a degradation device for oil-based drill cuttings deoiling tailings.

为了实现上述目的,本发明的技术方案如下:In order to achieve the above object, the technical solution of the present invention is as follows:

用于油基钻屑脱油尾渣的生物降解方法,包含以下步骤:The biodegradation method for oil-based drill cuttings deoiling tailings comprises the following steps:

1)配置油基岩屑1) Configure oil-based cuttings

调整待降解油基岩屑的浓度,使得待降解油基岩屑的含油量小于2%浓度;Adjusting the concentration of the oil-based rock cuttings to be degraded so that the oil content of the oil-based rock cuttings to be degraded is less than 2% concentration;

2)准备降解菌群2) Prepare the degradation bacteria

将石油烃降解细菌红球菌FL-1(Rhodococcus baikonurensis)、红球菌NC-17(Rhodococcus pedocola)、迪茨氏菌WL-3(Dietzia maris)于LB培养基中培养至对数生长期,收集并用无机盐培养基洗涤后,调节菌液浓度,使OD600=1,以1:1:1的等比例混合各降解菌,获得降解菌群;Petroleum hydrocarbon degrading bacteria Rhodococcus baikonurensis, Rhodococcus pedocola, and Dietzia maris were cultured in LB medium until the logarithmic growth phase, collected and washed with inorganic salt medium, and then the concentration of the bacterial solution was adjusted to make OD600 = 1, and the degrading bacteria were mixed in an equal ratio of 1:1:1 to obtain a degrading bacterial population;

3)建立降解体系3) Establish a degradation system

准备降解装置,先加入培养基,再降解装置内加入步骤1)中的待降解油基岩屑和步骤2)中配制的降解菌群,油基岩屑:降解菌群的比例为1:5,得降解装置内的固液比维持在1:3-1:5,启动降解装置内的搅拌器,对内部固液体进行搅拌,搅拌转速为44rpm;Prepare a degradation device, first add a culture medium, then add the oil-based rock chips to be degraded in step 1) and the degradation bacteria prepared in step 2) into the degradation device, the ratio of oil-based rock chips to degradation bacteria is 1:5, the solid-liquid ratio in the degradation device is maintained at 1:3-1:5, start the agitator in the degradation device to stir the solid and liquid inside, and the stirring speed is 44 rpm;

在搅拌时利用降解桶内的曝气装置,对着固液内部进行曝气,曝气的进气量为67.5-135升/分钟;同时,在搅拌时调整好降解装置内的温度,温度保持在25℃-30℃之间;During stirring, the aeration device in the degradation tank is used to aerate the solid and liquid inside, and the aeration air intake is 67.5-135 liters/minute; at the same time, the temperature in the degradation device is adjusted during stirring, and the temperature is maintained between 25℃-30℃;

4)启动实验装置后制定降解周期,降解周期定为60天,期间测定无机N和P浓度,及时补充营养盐;于第0天、第10天、第20天、第30天、第40天、第50天和60天分别取固体样、液体样以及固液混合样,每个体系取3个平行样,设置对照组和测定组,对照组为第0天中的样品,测定组为10天及10天以上从降解体系中取的样品,测定样品重量以及样品中的石油烃浓度,最终计算降解率。4) After starting the experimental device, a degradation cycle was established, which was set at 60 days. During this period, the concentrations of inorganic N and P were measured, and nutrients were supplemented in time. Solid samples, liquid samples, and solid-liquid mixed samples were taken on the 0th, 10th, 20th, 30th, 40th, 50th, and 60th days, respectively. Three parallel samples were taken from each system, and a control group and a measurement group were set up. The control group was the sample on the 0th day, and the measurement group was the sample taken from the degradation system on the 10th day and above. The sample weight and the concentration of petroleum hydrocarbons in the sample were measured, and the degradation rate was finally calculated.

进一步的,培养基的制作方法取培养基的制作方法取磷酸二氢钾2g、磷酸氢二钠3g、氯化钾0.7g、硝酸钾2g、七水硫酸镁1.03g、氯化钠20g,溶解于1000ml蒸馏水,根据最佳降解条件优化实验结果,调整其pH至8,添加氯化钠至盐度为1%,加入微量元素0.5ml。共配制90-150L,用于制备菌剂的MSM培养基需进行121℃灭菌20min。Further, the method for preparing the culture medium is to take 2g of potassium dihydrogen phosphate, 3g of disodium hydrogen phosphate, 0.7g of potassium chloride, 2g of potassium nitrate, 1.03g of magnesium sulfate heptahydrate, and 20g of sodium chloride, and dissolve them in 1000ml of distilled water. According to the experimental results of the optimal degradation condition optimization, adjust the pH to 8, add sodium chloride to a salinity of 1%, and add 0.5ml of trace elements. A total of 90-150L is prepared, and the MSM culture medium used to prepare the bacterial agent needs to be sterilized at 121°C for 20min.

进一步的,石油烃的测定及降解率的计算方式为:用气相色谱仪进行测定样品中的石油烃,气相色谱条件为毛细管柱子,火焰离子检测器为FID,进样口温度为300℃,检测器温度为280℃,进样量为1ul,分流比为30:1,柱温为初始40℃,保持2min;以15℃/min增加至300℃,保持10min。Furthermore, the determination of petroleum hydrocarbons and calculation of degradation rate are as follows: petroleum hydrocarbons in samples are determined by gas chromatograph, gas chromatography conditions are capillary columns, flame ionization detector is FID, injection port temperature is 300°C, detector temperature is 280°C, injection volume is 1ul, split ratio is 30:1, column temperature is initially 40°C, maintained for 2min; increased to 300°C at 15°C/min, maintained for 10min.

进一步的,测定降解体系样品中石油烃,获得峰面积数据,并根据石油烃峰面积与浓度的标准曲线计算获得样品中的油浓度。以0天样品作为对照,计算降解率,并按照以下公式计算降解率:Furthermore, the petroleum hydrocarbons in the degradation system samples were measured to obtain peak area data, and the oil concentration in the samples was calculated based on the standard curve of petroleum hydrocarbon peak area and concentration. The degradation rate was calculated using the 0-day sample as a control, and the degradation rate was calculated according to the following formula:

降解率%=(总峰面积A对照-总峰面积A样品)/总峰面积A对照×100%Degradation rate % = (total peak area A control - total peak area A sample ) / total peak area A control × 100%

进一步的,测定组内取的固体样、液体样以及固液混合样的样品要随时检测石油烃浓度,以跟对照组形成对比,其中石油烃浓度测定之前需要做如下准备工作:Furthermore, the solid samples, liquid samples and solid-liquid mixed samples taken from the test group should be tested for petroleum hydrocarbon concentration at any time to form a comparison with the control group. The following preparations need to be made before the petroleum hydrocarbon concentration measurement:

先向固体样、液体样以及固液混合样中加入10-20ml正己烷,超声3min,转入分液漏斗;再向三角瓶中加入10ml正己烷洗涤三角瓶并合并到分液漏斗,强力振荡分液漏斗3min,静置10min,将上层正己烷滴入装有适量无水硫酸钠的漏斗过滤,滤液用旋转蒸发仪于45℃蒸干,之后用5ml正己烷溶解,溶液定容于5ml后,过0.45μm尼龙滤头,再进行数据测定。First, add 10-20 ml of n-hexane to the solid sample, liquid sample and solid-liquid mixed sample, ultrasonicate for 3 minutes, and transfer to a separatory funnel; then add 10 ml of n-hexane to the conical flask to wash the conical flask and combine it into the separatory funnel, vigorously shake the separatory funnel for 3 minutes, let it stand for 10 minutes, drop the upper layer of n-hexane into a funnel filled with an appropriate amount of anhydrous sodium sulfate and filter, evaporate the filtrate at 45°C using a rotary evaporator, then dissolve it with 5 ml of n-hexane, make the solution dilute to 5 ml, pass it through a 0.45μm nylon filter, and then perform data measurement.

为了以上降解方法能够更好的实现,我们设计了一种针对该方法的设备,具体结构如下:In order to better implement the above degradation method, we designed a device for this method. The specific structure is as follows:

用于油基钻屑脱油尾渣的生物降解装置,包括降解桶,在降解桶的顶部设有固定盖和活动盖,降解桶的下部设有出水口,在降解桶的内部设有搅拌轴,在降解桶内的底部和桶壁设有曝气管,底部曝气管安装在搅拌轴上并随之转动,桶壁曝气管固定分布在筒壁两侧。The biodegradation device for oil-based drill cuttings deoiling tailings comprises a degradation barrel, a fixed cover and a movable cover are arranged on the top of the degradation barrel, a water outlet is arranged at the bottom of the degradation barrel, a stirring shaft is arranged inside the degradation barrel, aeration pipes are arranged at the bottom and barrel wall of the degradation barrel, the bottom aeration pipe is installed on the stirring shaft and rotates therewith, and the barrel wall aeration pipes are fixedly distributed on both sides of the barrel wall.

在搅拌轴上从上至下分别刚性连接着框式搅拌桨、强化搅拌桨和刮泥搅拌桨,曝气管设置在在强化搅拌桨与框式搅拌桨中间,在曝气管上排布着两个及两个以上的单向阀曝气接头,The frame-type stirring paddle, the enhanced stirring paddle and the scraper stirring paddle are rigidly connected to the stirring shaft from top to bottom. The aeration pipe is arranged between the enhanced stirring paddle and the frame-type stirring paddle. Two or more one-way valve aeration joints are arranged on the aeration pipe.

所述搅拌轴为中空状,且与曝气管连通,搅拌轴的顶部延伸出固定盖之外,在降解桶的旁边设有压缩空气加热制冷器,压缩空气加热制冷器与搅拌轴顶部之间利用旋转接头和管道连通。The stirring shaft is hollow and connected to the aeration pipe. The top of the stirring shaft extends out of the fixed cover. A compressed air heating refrigerator is arranged next to the degradation barrel. The compressed air heating refrigerator is connected to the top of the stirring shaft by a rotary joint and a pipeline.

进一步的,所述框式搅拌桨为矩形状,在矩形框内正反交叉安装着破碎鳍。Furthermore, the frame-type stirring paddle is rectangular, and crushing fins are installed in a forward and reverse cross manner in the rectangular frame.

进一步的,在降解桶的外周设有水浴夹套,在降解桶的旁边还设有恒温水浴实验槽,水浴夹套以循环水的方式连接着恒温水浴实验槽,降解桶内部设有温度传感器,温度传感器通过继电器与恒温水浴实验槽连接着。Furthermore, a water bath jacket is provided on the outer periphery of the degradation barrel, and a constant temperature water bath test tank is provided next to the degradation barrel. The water bath jacket is connected to the constant temperature water bath test tank in a circulating water manner. A temperature sensor is provided inside the degradation barrel, and the temperature sensor is connected to the constant temperature water bath test tank through a relay.

进一步的,在降解桶的底部设有固体排放口,其中刮泥搅拌桨的刮泥面贴合固体排放口的上平面。Furthermore, a solid discharge port is provided at the bottom of the degradation barrel, wherein the scraping surface of the scraping stirring paddle fits in contact with the upper plane of the solid discharge port.

进一步的,其出水口位置高于刮泥搅拌桨的位置,并在出水口位置处接有可变液位高度排液阀。Furthermore, the water outlet is located higher than the scraper and agitator, and a variable liquid level height drain valve is connected to the water outlet.

本发明与现有技术相比的有益效果是:本降解试验方法相对于前期的三角瓶小试实验方法,能通过装置实现搅拌、降解体系控温、曝气等功能,能规模化的处理油基钻屑脱油尾渣,该中试试验方法和实验降解装置至少一次性能处理30kg的油基钻屑脱油尾渣,从而规模化处理油基钻屑脱油尾渣,实现高效处理脱油后剩余尾渣,具有经济性、高效性、可持续性。此中试的结果为后续多源页岩气油基钻屑的大量降解提供了可行性。这种规模化降解方法和设备可以为微生物降解技术的研发和应用提供科学依据,为进一步工业化降解油基钻屑脱油尾渣工作作出了创新。Compared with the prior art, the beneficial effects of the present invention are as follows: compared with the previous small-scale test method using a triangular flask, the degradation test method can realize stirring, temperature control of the degradation system, aeration and other functions through the device, and can process oil-based drill cuttings deoiling tailings on a large scale. The pilot test method and the experimental degradation device can process 30 kg of oil-based drill cuttings deoiling tailings at least once, thereby processing oil-based drill cuttings deoiling tailings on a large scale, and realizing efficient processing of the remaining tailings after deoiling, which is economical, efficient and sustainable. The results of this pilot test provide feasibility for the subsequent large-scale degradation of multi-source shale gas oil-based drill cuttings. This large-scale degradation method and equipment can provide a scientific basis for the research and development and application of microbial degradation technology, and make innovations for further industrial degradation of oil-based drill cuttings deoiling tailings.

附图说明BRIEF DESCRIPTION OF THE DRAWINGS

图1为本发明实验装置的主视结构视图;FIG1 is a front view of the structure of the experimental device of the present invention;

图2为本发明实验装置的立体结构示意图;FIG2 is a schematic diagram of the three-dimensional structure of the experimental device of the present invention;

图3为本发明实验装置降解桶内部结构的立体结构示意图。FIG. 3 is a schematic diagram of the three-dimensional structure of the internal structure of the degradation barrel of the experimental device of the present invention.

图4为强化搅拌桨和刮泥搅拌桨的立体结构图。FIG. 4 is a three-dimensional structural diagram of the enhanced stirring paddle and the scraping stirring paddle.

1、降解桶;11、固定盖;12、活动盖;13、固体排放口;14、可变液位高度排液阀;2、搅拌轴;3、曝气管;30、单向阀曝气接头;4、框式搅拌桨;40、破碎鳍;5、强化搅拌桨;6、刮泥搅拌桨;61、下刮泥板;62、鳍片;63、上刮泥板;7、压缩空气加热制冷器;8、恒温水浴实验槽;1. Degradation barrel; 11. Fixed cover; 12. Movable cover; 13. Solid discharge port; 14. Variable liquid level height drain valve; 2. Stirring shaft; 3. Aeration pipe; 30. One-way valve aeration joint; 4. Frame stirring paddle; 40. Crushing fin; 5. Strengthening stirring paddle; 6. Mud scraping stirring paddle; 61. Lower scraping plate; 62. Fin; 63. Upper scraping plate; 7. Compressed air heating refrigerator; 8. Constant temperature water bath test tank;

具体实施方式DETAILED DESCRIPTION

为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解,下面结合具体实施例进一步阐述本发明。In order to make the technical means, creative features, objectives and effects achieved by the present invention easy to understand, the present invention is further described below in conjunction with specific embodiments.

用于油基钻屑脱油尾渣的生物降解方法,包含以下步骤:The biodegradation method for oil-based drill cuttings deoiling tailings comprises the following steps:

1)配置油基岩屑,1) Configure oil-based cuttings,

调整待降解油基岩屑的浓度,使得待降解油基岩屑的含油量小于2%浓度;Adjusting the concentration of the oil-based rock cuttings to be degraded so that the oil content of the oil-based rock cuttings to be degraded is less than 2% concentration;

2)准备降解菌群2) Prepare the degradation bacteria

将石油烃降解细菌红球菌FL-1(Rhodococcus baikonurensis,保藏编号为CCTCCNO:2022454)、红球菌NC-17(Rhodococcus pedocola,保藏编号为CCTCC NO:M 2022453)、迪茨氏菌WL-3(Dietzia maris,保藏编号为CCTCC NO:2022455)于LB培养基中培养至对数生长期,收集并用无机盐培养基洗涤后,调节菌液浓度,使OD600=1,以1:1:1的等比例混合各降解菌,获得降解菌群。Petroleum hydrocarbon degrading bacteria Rhodococcus baikonurensis (CCTCC NO: 2022454), Rhodococcus pedocola (CCTCC NO: M 2022453), and Dietzia maris (CCTCC NO: 2022455) were cultured in LB medium to the logarithmic growth phase, collected and washed with an inorganic salt medium, and then the concentration of the bacterial solution was adjusted to make OD 600 = 1. The degrading bacteria were mixed in an equal ratio of 1:1:1 to obtain a degrading bacterial population.

其中,LB液体培养基:蛋白胨1g,酵母粉0.5g,NaCl 1g,加100ml蒸馏水溶解,121℃灭菌20min。LB liquid culture medium: 1 g of peptone, 0.5 g of yeast powder, 1 g of NaCl, dissolved in 100 ml of distilled water, and sterilized at 121°C for 20 min.

LB固体培养基:蛋白胨1g,酵母粉0.5g,NaCl 1g,琼脂粉1.5g,加100ml蒸馏水溶解,121℃灭菌20min,倒平板。LB solid medium: 1 g of peptone, 0.5 g of yeast powder, 1 g of NaCl, 1.5 g of agar powder, dissolve in 100 ml of distilled water, sterilize at 121°C for 20 min, and pour into a plate.

其中,无机盐培养基的制作方法取KH2PO4(磷酸二氢钾)2g、Na2HPO4(磷酸氢二钠)3g、KCl(氯化钾)0.7g、KNO3(硝酸钾)2g、MgSO4·7H2O(七水硫酸镁)1.03g、NaCl(氯化钠)20g,溶解于1000ml蒸馏水,根据最佳降解条件优化实验结果,调整其pH至8,添加NaCl至盐度为1%,加入微量元素0.5ml。共配制90-150L,用于制备菌剂的MSM培养基需进行121℃灭菌20min;Among them, the preparation method of inorganic salt culture medium is to take KH 2 PO 4 (potassium dihydrogen phosphate) 2g, Na 2 HPO 4 (sodium hydrogen phosphate) 3g, KCl (potassium chloride) 0.7g, KNO 3 (potassium nitrate) 2g, MgSO 4 ·7H 2 O (magnesium sulfate heptahydrate) 1.03g, NaCl (sodium chloride) 20g, dissolve in 1000ml distilled water, according to the results of the optimal degradation condition optimization experiment, adjust its pH to 8, add NaCl to a salinity of 1%, and add 0.5ml of trace elements. A total of 90-150L is prepared. The MSM culture medium used to prepare the bacterial agent needs to be sterilized at 121℃ for 20min;

细菌红球菌FL-1、红球菌NC-17、迪茨氏菌WL-3的形态图及降解菌群的制备方法可参考专利申请号为202310851248.8(公布号为CN 116948889 A)的发明专利。The morphological diagrams of bacteria Rhodococcus FL-1, Rhodococcus NC-17, and Dietrichia WL-3 and the preparation method of the degrading bacterial community can be referred to the invention patent with patent application number 202310851248.8 (publication number CN 116948889 A).

3)建立降解体系3) Establish a degradation system

准备降解装置,先加入培养基,再降解装置内加入步骤1)中的待降解油基岩屑和步骤2)中配制的降解菌群,油基岩屑:降解菌群的比例为1:5,得降解装置内的固液比维持在1:3-1:5,启动降解装置内的搅拌器,对内部固液体进行搅拌,搅拌转速为44rpm;Prepare a degradation device, first add a culture medium, then add the oil-based rock chips to be degraded in step 1) and the degradation bacteria prepared in step 2) into the degradation device, the ratio of oil-based rock chips to degradation bacteria is 1:5, the solid-liquid ratio in the degradation device is maintained at 1:3-1:5, start the agitator in the degradation device to stir the solid and liquid inside, and the stirring speed is 44 rpm;

在搅拌时利用降解桶内的曝气装置,对着固液内部进行曝气,曝气的进气量为67.5-135升/分钟;同时,在搅拌时调整好降解装置内的温度,温度保持在25±0.5℃之间;During stirring, use the aeration device in the degradation tank to aerate the solid and liquid inside, and the aeration air intake is 67.5-135 liters/minute; at the same time, adjust the temperature in the degradation device during stirring, and keep the temperature between 25±0.5℃;

4)启动实验装置后制定降解周期,降解周期定为60天,期间测定无机N和P浓度,及时补充营养盐;于第0天、第10天、第20天、第30天、第40天、第50天和60天分别取固体样、液体样以及固液混合样,每个体系取3个平行样,设置对照组和测定组,对照组为第0天中的样品,测定组为10天及10天以上从降解体系中取的样品,需要注意的是,针对取出来的固体样品,同时测定其含水率。4) After starting the experimental device, a degradation cycle is formulated, and the degradation cycle is set at 60 days. During this period, the concentrations of inorganic N and P are measured, and nutrients are supplemented in time; solid samples, liquid samples and solid-liquid mixed samples are taken on the 0th day, the 10th day, the 20th day, the 30th day, the 40th day, the 50th day and the 60th day, respectively. Three parallel samples are taken from each system, and a control group and a measurement group are set up. The control group is the sample on the 0th day, and the measurement group is the sample taken from the degradation system on 10 days and above. It should be noted that the water content of the solid samples taken is also measured at the same time.

测定组内取的固体样、液体样以及固液混合样的样品要随时检测石油烃浓度,以跟对照组形成对比,其中石油烃浓度测定之前需要做如下准备工作:The solid samples, liquid samples and solid-liquid mixed samples taken from the test group should be tested for petroleum hydrocarbon concentration at any time to form a comparison with the control group. The following preparations need to be made before the petroleum hydrocarbon concentration measurement:

先向固体样、液体样以及固液混合样中加入10-20ml正己烷,超声3min,转入分液漏斗;再向三角瓶中加入10ml正己烷洗涤三角瓶并合并到分液漏斗,强力振荡分液漏斗3min,静置10min(如果上下分层不明显,于5000g离心1min),将上层正己烷滴入装有适量无水硫酸钠的漏斗过滤,滤液用旋转蒸发仪于45℃蒸干,之后用5ml正己烷溶解,溶液定容于5ml后,过0.45μm尼龙滤头,再进行数据测定。First, add 10-20 ml of n-hexane to the solid sample, liquid sample and solid-liquid mixed sample, ultrasonicate for 3 minutes, and transfer to a separatory funnel; then add 10 ml of n-hexane to the conical flask to wash the conical flask and combine it into the separatory funnel, vigorously shake the separatory funnel for 3 minutes, let it stand for 10 minutes (if the upper and lower stratification is not obvious, centrifuge at 5000g for 1 minute), drop the upper layer of n-hexane into a funnel filled with an appropriate amount of anhydrous sodium sulfate and filter, evaporate the filtrate at 45°C using a rotary evaporator, then dissolve it with 5 ml of n-hexane, make the solution dilute to 5 ml, pass it through a 0.45μm nylon filter, and then perform data measurement.

根据以上方法测定每个取出来的样品重量以及样品中的石油烃浓度,最终计算降解率。The weight of each sample taken out and the concentration of petroleum hydrocarbons in the sample are determined according to the above method, and the degradation rate is finally calculated.

石油烃的测定及降解率的计算方式为:用气相色谱仪进行测定样品中的石油烃,气相色谱条件为毛细管柱子,火焰离子检测器为FID,进样口温度为300℃,检测器温度为280℃,进样量为1ul,分流比为30:1,柱温为初始40℃,保持2min;以15℃/min增加至300℃,保持10min。The determination of petroleum hydrocarbons and calculation of degradation rate are as follows: petroleum hydrocarbons in samples are determined by gas chromatograph, the gas chromatographic conditions are capillary columns, flame ionization detector is FID, injection port temperature is 300°C, detector temperature is 280°C, injection volume is 1ul, split ratio is 30:1, column temperature is initially 40°C, maintained for 2min; increase to 300°C at 15°C/min, maintained for 10min.

测定降解体系样品中石油烃,获得峰面积数据,并根据石油烃峰面积与浓度的标准曲线计算获得样品中的油浓度。以0天样品作为对照,计算降解率,并按照以下公式计算降解率:Determine the petroleum hydrocarbons in the degradation system samples, obtain the peak area data, and calculate the oil concentration in the samples based on the standard curve of petroleum hydrocarbon peak area and concentration. Take the 0-day sample as the control, calculate the degradation rate, and calculate the degradation rate according to the following formula:

降解率%=(总峰面积A对照-总峰面积A样品)/总峰面积A对照×100%Degradation rate % = (total peak area A control - total peak area A sample ) / total peak area A control × 100%

以30kg为例,该批油基钻屑样品石油烃含量为10.2%,为得到3%左右含油率的样品体系,目前样品组成为5kg油基钻屑+10kg河沙。Taking 30kg as an example, the petroleum hydrocarbon content of this batch of oil-based drill cuttings samples is 10.2%. In order to obtain a sample system with an oil content of about 3%, the current sample composition is 5kg of oil-based drill cuttings + 10kg of river sand.

如图1—图4所示,上述实验方法在实验时需要用到一种生物降解装置,包括降解桶1,在降解桶1的顶部设有固定盖11和活动盖12,在降解桶1的内部设有搅拌轴2,在降解桶1的内底部和桶壁设有曝气管3,底部曝气管3安装在搅拌轴2上并随之转动,桶壁曝气管3固定分布在筒壁的对称两侧。As shown in Figures 1 to 4, the above experimental method requires a biodegradation device during the experiment, including a degradation barrel 1, a fixed cover 11 and a movable cover 12 are provided on the top of the degradation barrel 1, a stirring shaft 2 is provided inside the degradation barrel 1, and aeration pipes 3 are provided on the inner bottom and barrel wall of the degradation barrel 1. The bottom aeration pipe 3 is installed on the stirring shaft 2 and rotates therewith, and the barrel wall aeration pipes 3 are fixedly distributed on both sides of the barrel wall.

在搅拌轴2上从上至下分别刚性连接着框式搅拌桨4、强化搅拌桨5和刮泥搅拌桨6,底部的曝气管3设置在在强化搅拌桨5与框式搅拌桨6中间,强化搅拌桨5和刮泥搅拌桨6呈十字交叉性安装,所述框式搅拌桨4为矩形形状,在矩形框内正反交叉安装着破碎鳍40,如图3所示,在一个矩形方框内,安装着四片破碎鳍10,破碎鳍10的截面呈弧形形状,四片破碎鳍10倾斜的角度不同,以便于在转动时更彻底的打碎油基钻屑脱油尾渣,使其充分与微生物降解物质发生反应,快速充分的分解油基钻屑脱油尾渣内的石油烃含量,降低废弃物的污染率,使得废弃物排放更环保。所述的强化搅拌5桨呈Z字形,在其表面上设有多个鳍片50。所述的刮泥搅拌桨6主要由7字形下刮泥板61、鳍片62和上刮泥板63,下刮泥板61和上刮泥板63平行安装,鳍片62为多个且等间距布置在下刮泥板61和上刮泥板63之间,当液体排出后,固体物质剩下,加厚的刮泥搅拌桨6能在面对固体物质的阻力时,顺畅的将固体物质从桶底挤压出去。The frame-type stirring paddle 4, the enhanced stirring paddle 5 and the scraper stirring paddle 6 are rigidly connected to the stirring shaft 2 from top to bottom. The aeration pipe 3 at the bottom is arranged between the enhanced stirring paddle 5 and the frame-type stirring paddle 6. The enhanced stirring paddle 5 and the scraper stirring paddle 6 are installed in a cross-shaped manner. The frame-type stirring paddle 4 is rectangular in shape, and the crushing fins 40 are installed in a positive and negative cross-shaped manner in the rectangular frame. As shown in FIG3 , four crushing fins 10 are installed in a rectangular frame. The cross-section of the crushing fin 10 is in an arc shape. The four crushing fins 10 are inclined at different angles, so as to more thoroughly break up the oil-based drill cuttings deoiling tailings during rotation, so that it can fully react with the microbial degradation substances, quickly and fully decompose the petroleum hydrocarbon content in the oil-based drill cuttings deoiling tailings, reduce the pollution rate of the waste, and make the waste discharge more environmentally friendly. The enhanced stirring paddle 5 is in a Z shape, and a plurality of fins 50 are arranged on its surface. The scraper and agitator paddle 6 mainly consists of a 7-shaped lower scraper plate 61, fins 62 and an upper scraper plate 63. The lower scraper plate 61 and the upper scraper plate 63 are installed in parallel. There are multiple fins 62 and they are arranged at equal intervals between the lower scraper plate 61 and the upper scraper plate 63. When the liquid is discharged, the solid matter remains. The thickened scraper and agitator paddle 6 can smoothly squeeze the solid matter out from the bottom of the barrel when facing the resistance of the solid matter.

在降解桶1的底部曝气管和桶壁的曝气管上排布着两个及两个以上的单向阀曝气接头30,底部的曝气管3上一边排布4个单向阀曝气接头30,其桶壁的曝气管上可排布四个及四个以上的单向阀曝气接头,可根据桶深度适当增加。Two or more one-way valve aeration joints 30 are arranged on the bottom aeration pipe and the aeration pipe on the barrel wall of the degradation barrel 1. Four one-way valve aeration joints 30 are arranged on one side of the bottom aeration pipe 3, and four or more one-way valve aeration joints can be arranged on the aeration pipe on the barrel wall, and the number can be appropriately increased according to the depth of the barrel.

所述搅拌轴2为中空状,且与曝气管3连通,搅拌轴2的顶部延伸出固定盖11之外,在降解桶1的旁边设有压缩空气加热制冷器7,压缩空气加热制冷器7与搅拌轴顶部之间利用旋转接头和管道连通。The stirring shaft 2 is hollow and connected to the aeration pipe 3. The top of the stirring shaft 2 extends out of the fixed cover 11. A compressed air heating refrigerator 7 is provided next to the degradation barrel 1. The compressed air heating refrigerator 7 is connected to the top of the stirring shaft by a rotary joint and a pipeline.

降解桶1的底部曝气管和桶壁的曝气管同时连通着压缩空气加热制冷器7,在压缩空气加热制冷器的作用下,对降解桶内定时定量进行强化曝气,在降解桶的外周设有水浴夹套,在降解桶的旁边还设有恒温水浴实验槽8,水浴夹套以循环水的方式连接着恒温水浴实验槽8,降解桶内部设有温度传感器,温度传感器通过继电器与恒温水浴实验槽连接着。空压机排出的空气经过加热制冷器加热进入桶内液体中,起到平衡反应环境中的温度,使其维持最佳降解环境温度。The bottom aeration pipe of the degradation barrel 1 and the aeration pipe of the barrel wall are connected to the compressed air heating refrigerator 7 at the same time. Under the action of the compressed air heating refrigerator, the degradation barrel is aerated regularly and quantitatively. A water bath jacket is provided on the periphery of the degradation barrel, and a constant temperature water bath test tank 8 is provided next to the degradation barrel. The water bath jacket is connected to the constant temperature water bath test tank 8 in the form of circulating water. A temperature sensor is provided inside the degradation barrel, and the temperature sensor is connected to the constant temperature water bath test tank through a relay. The air discharged from the air compressor is heated by the heating refrigerator and enters the liquid in the barrel, which balances the temperature in the reaction environment and maintains the optimal degradation environment temperature.

另外,为了在降解完成后,快速的将剩余的固体快速排出,以便于进行下一次微生物降解反应,在降解桶1的底部设有固体排放口13,其中刮泥搅拌桨的刮泥面贴合固体排放口的上平面。还在降解桶的下部设有出水口,其出水口位置高于刮泥搅拌桨的位置,并在出水口位置处接有可变液位高度排液阀14,先放液体,再放固体物质,液体可进行循环利用或者在再次环保处理后在进行排污。In addition, in order to quickly discharge the remaining solids after the degradation is completed so as to facilitate the next microbial degradation reaction, a solid discharge port 13 is provided at the bottom of the degradation barrel 1, wherein the scraping surface of the scraper and agitator fits the upper plane of the solid discharge port. A water outlet is also provided at the lower part of the degradation barrel, the water outlet position is higher than the position of the scraper and agitator, and a variable liquid level height drain valve 14 is connected at the water outlet position, the liquid is discharged first, and then the solid matter is discharged, and the liquid can be recycled or discharged after environmental protection treatment again.

为了防止搅拌电机和曝气电机过热,该装置在使用时,可通过控制系统实现自动启停,自定义连续工作时间与间歇时间,比如搅拌的时间和曝气的时间,一般搅拌的间歇时间是半小时曝气的间歇时间是半小时,为了使降解体系保持有氧环境,搅拌和曝气分别间歇,控制系统可实现远程系统修改。在降解桶的顶部先倒入30kg的油基钻屑脱油尾渣,然后倒入配制好的培养液和菌液,关闭翻转盖,调整好恒温水浴实验槽的温度,使得降解桶内的温度维持在25±0.5℃之间,以25℃为本实施例的控制温度,控温后,再进行搅拌,在搅拌的时候打开压缩空气加热制冷器,利用内部的多个单向阀曝气接头进行曝气,使得内部的微生物降解充分发生反应,根据反应的时间按照步骤4)中的方法取样品,以0天(即刚混合油基钻屑脱油尾渣和菌液)取用的样品为对照组,分别计算取出来样品的石油烃含量,石油烃含量越低,证明该降解体系效果越理想。In order to prevent the stirring motor and aeration motor from overheating, the device can be automatically started and stopped through the control system when in use, and the continuous working time and intermittent time can be customized, such as the stirring time and the aeration time. Generally, the stirring intermittent time is half an hour and the aeration intermittent time is half an hour. In order to keep the degradation system in an aerobic environment, the stirring and aeration are intermittent respectively. The control system can realize remote system modification. First, pour 30 kg of oil-based drill cuttings deoiled tailings on the top of the degradation barrel, then pour the prepared culture solution and bacterial solution, close the flip cover, adjust the temperature of the constant temperature water bath experimental tank, so that the temperature in the degradation barrel is maintained between 25±0.5°C, with 25°C as the control temperature of this embodiment. After temperature control, stir again, turn on the compressed air heating refrigerator during stirring, and use the multiple one-way valve aeration joints inside for aeration, so that the internal microbial degradation reacts fully, and take samples according to the method in step 4) according to the reaction time, take the sample taken on day 0 (i.e., just mixed with the oil-based drill cuttings deoiled tailings and bacterial solution) as the control group, and calculate the petroleum hydrocarbon content of the taken samples respectively. The lower the petroleum hydrocarbon content, the more ideal the degradation system effect is.

以上对本发明提供的用于油基钻屑脱油尾渣的生物降解方法及其降解装置进行了详细介绍。具体实施例的说明只是用于帮助理解本发明的方法及其核心思想,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以对本发明进行若干改进和修饰,这些改进和修饰也落入本发明权利要求的保护范围内。The above is a detailed introduction to the biodegradation method and degradation device for oil-based drill cuttings deoiling tailings provided by the present invention. The description of the specific embodiment is only used to help understand the method and its core idea of the present invention. It should be pointed out that for ordinary technicians in this technical field, without departing from the principle of the present invention, the present invention can also be improved and modified in several ways, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims (10)

1.用于油基钻屑脱油尾渣的生物降解方法,其特征在于,包含以下步骤:1. A biodegradation method for oil-based drill cuttings deoiling tailings, characterized in that it comprises the following steps: 1)配置油基岩屑1) Configure oil-based cuttings 调整待降解油基岩屑的浓度,使得待降解油基岩屑的含油量小于2%浓度;Adjusting the concentration of the oil-based rock cuttings to be degraded so that the oil content of the oil-based rock cuttings to be degraded is less than 2% concentration; 2)准备降解菌群2) Prepare the degradation bacteria 将石油烃降解细菌红球菌FL-1(Rhodococcus baikonurensis)、红球菌NC-17(Rhodococcus pedocola)、迪茨氏菌WL-3(Dietzia maris)于LB培养基中培养至对数生长期,收集并用无机盐培养基洗涤后,调节菌液浓度,使OD600=1,以1:1:1的等比例混合各降解菌,获得降解菌群;Petroleum hydrocarbon degrading bacteria Rhodococcus baikonurensis, Rhodococcus pedocola, and Dietzia maris were cultured in LB medium until the logarithmic growth phase, collected and washed with inorganic salt medium, and then the concentration of the bacterial solution was adjusted to make OD600 = 1, and the degrading bacteria were mixed in an equal ratio of 1:1:1 to obtain a degrading bacterial population; 3)建立降解体系3) Establish a degradation system 准备降解装置,先加入培养基,再降解装置内加入步骤1)中的待降解油基岩屑和步骤2)中配制的降解菌群,油基岩屑:降解菌群的比例为1:5,得降解装置内的固液比维持在1:3-1:5,启动降解装置内的搅拌器,对内部固液体进行搅拌,搅拌转速为44rpm;Prepare a degradation device, first add a culture medium, then add the oil-based rock chips to be degraded in step 1) and the degradation bacteria prepared in step 2) into the degradation device, the ratio of oil-based rock chips to degradation bacteria is 1:5, the solid-liquid ratio in the degradation device is maintained at 1:3-1:5, start the agitator in the degradation device to stir the solid and liquid inside, and the stirring speed is 44 rpm; 在搅拌时利用降解桶内的曝气装置,向固液内部进行曝气,曝气的进气量为67.5-135升/分钟;同时,在搅拌时调整好降解装置内的温度,温度保持在25±0.5℃;During stirring, the aeration device in the degradation tank is used to aerate the solid and liquid, and the aeration air intake is 67.5-135 liters/minute; at the same time, the temperature in the degradation device is adjusted during stirring, and the temperature is maintained at 25±0.5℃; 4)启动实验装置后制定降解周期,降解周期定为60天,期间测定无机N和P浓度,及时补充营养盐;于第0天、第10天、第20天、第30天、第40天、第50天和60天分别取固体样、液体样以及固液混合样,每个体系取3个平行样,设置对照组和测定组,对照组为第0天中的样品,测定组为10天及10天以上从降解体系中取的样品,测定样品重量以及样品中的石油烃浓度,最终计算降解率。4) After starting the experimental device, a degradation cycle was established, which was set at 60 days. During this period, the concentrations of inorganic N and P were measured, and nutrients were supplemented in time. Solid samples, liquid samples, and solid-liquid mixed samples were taken on the 0th, 10th, 20th, 30th, 40th, 50th, and 60th days, respectively. Three parallel samples were taken from each system, and a control group and a measurement group were set up. The control group was the sample on the 0th day, and the measurement group was the sample taken from the degradation system on the 10th day and above. The sample weight and the concentration of petroleum hydrocarbons in the sample were measured, and the degradation rate was finally calculated. 2.根据权利要求1所述的用于油基钻屑脱油尾渣的生物降解方法,其特征在于:培养基的制作方法取磷酸二氢钾2g、磷酸氢二钠3g、氯化钾0.7g、硝酸钾2g、七水硫酸镁1.03g、氯化钠20g,溶解于1000ml蒸馏水,根据最佳降解条件优化实验结果,调整其pH至8,添加氯化钠至盐度为1%,加入微量元素0.5ml。共配制90-150L,用于制备菌剂的MSM培养基需进行121℃灭菌20min。2. The biodegradation method for oil-based drill cuttings deoiling tailings according to claim 1 is characterized in that: the preparation method of the culture medium is to take 2g of potassium dihydrogen phosphate, 3g of disodium hydrogen phosphate, 0.7g of potassium chloride, 2g of potassium nitrate, 1.03g of magnesium sulfate heptahydrate, and 20g of sodium chloride, and dissolve them in 1000ml of distilled water. According to the experimental results of the optimal degradation conditions, adjust the pH to 8, add sodium chloride to a salinity of 1%, and add 0.5ml of trace elements. A total of 90-150L is prepared, and the MSM culture medium used to prepare the bacterial agent needs to be sterilized at 121°C for 20min. 3.根据权利要求1所述的用于油基钻屑脱油尾渣的生物降解方法,其特征在于:石油烃的测定及降解率的计算方式为:用气相色谱仪进行测定样品中的石油烃,气相色谱条件为毛细管柱子,火焰离子检测器为FID,进样口温度为300℃,检测器温度为280℃,进样量为1ul,分流比为30:1,柱温为初始40℃,保持2min;以15℃/min增加至300℃,保持10min。3. The biodegradation method for oil-based drill cuttings deoiling tailings according to claim 1 is characterized in that: the determination of petroleum hydrocarbons and the calculation of the degradation rate are as follows: the petroleum hydrocarbons in the sample are determined by a gas chromatograph, the gas chromatographic conditions are a capillary column, the flame ionization detector is FID, the injection port temperature is 300°C, the detector temperature is 280°C, the injection volume is 1ul, the split ratio is 30:1, the column temperature is initially 40°C, maintained for 2 minutes; increased to 300°C at 15°C/min, and maintained for 10 minutes. 4.根据权利要求3所述的用于油基钻屑脱油尾渣的生物降解方法,其特征在于:测定降解体系样品中石油烃,获得峰面积数据,并根据石油烃峰面积与浓度的标准曲线计算获得样品中的油浓度。以0天样品作为对照,计算降解率,并按照以下公式计算降解率:4. The biodegradation method for oil-based drill cuttings deoiling tailings according to claim 3 is characterized in that: the petroleum hydrocarbons in the degradation system sample are measured to obtain peak area data, and the oil concentration in the sample is calculated based on the standard curve of the peak area and concentration of the petroleum hydrocarbons. The degradation rate is calculated using the 0-day sample as a control, and the degradation rate is calculated according to the following formula: 降解率%=(总峰面积A对照-总峰面积A样品)/总峰面积A对照×100%Degradation rate % = (total peak area A control - total peak area A sample ) / total peak area A control × 100% 5.根据权利要求1所述的用于油基钻屑脱油尾渣的生物降解方法,其特征在于:测定组内取的固体样、液体样以及固液混合样的样品要随时检测石油烃浓度,以跟对照组形成对比,其中石油烃浓度测定之前需要做如下准备工作:5. The biodegradation method for oil-based drill cuttings deoiling tailings according to claim 1 is characterized in that: the solid samples, liquid samples and solid-liquid mixed samples taken in the determination group are tested for petroleum hydrocarbon concentration at any time to form a comparison with the control group, wherein the following preparations need to be done before the determination of petroleum hydrocarbon concentration: 先向固体样、液体样以及固液混合样中加入10-20ml正己烷,超声3min,转入分液漏斗;再向三角瓶中加入10ml正己烷洗涤三角瓶并合并到分液漏斗,强力振荡分液漏斗3min,静置10min,将上层正己烷滴入装有适量无水硫酸钠的漏斗过滤,滤液用旋转蒸发仪于45℃蒸干,之后用5ml正己烷溶解,溶液定容于5ml后,过0.45μm尼龙滤头,再进行数据测定。First, add 10-20 ml of n-hexane to the solid sample, liquid sample and solid-liquid mixed sample, ultrasonicate for 3 minutes, and transfer to a separatory funnel; then add 10 ml of n-hexane to the conical flask to wash the conical flask and combine it into the separatory funnel, vigorously shake the separatory funnel for 3 minutes, let it stand for 10 minutes, drop the upper layer of n-hexane into a funnel filled with an appropriate amount of anhydrous sodium sulfate and filter, evaporate the filtrate at 45°C using a rotary evaporator, then dissolve it with 5 ml of n-hexane, make the solution dilute to 5 ml, pass it through a 0.45μm nylon filter, and then perform data measurement. 6.用于油基钻屑脱油尾渣的生物降解装置,包括降解桶,在降解桶的顶部设有固定盖和活动盖,降解桶的下部设有出水口,在降解桶的内部设有搅拌轴,在降解桶的内底部和桶壁设有曝气管,底部曝气管安装在搅拌轴上并随之转动,桶壁曝气管固定分布在筒壁两侧,6. A biodegradation device for oil-based drill cuttings deoiling tailings, comprising a degradation barrel, a fixed cover and a movable cover are arranged on the top of the degradation barrel, a water outlet is arranged at the bottom of the degradation barrel, a stirring shaft is arranged inside the degradation barrel, aeration pipes are arranged at the inner bottom and barrel wall of the degradation barrel, the bottom aeration pipe is installed on the stirring shaft and rotates therewith, and the barrel wall aeration pipes are fixedly distributed on both sides of the barrel wall, 其特征在于:在搅拌轴上从上至下分别刚性连接着框式搅拌桨、强化搅拌桨和刮泥搅拌桨,曝气管设置在在强化搅拌桨与框式搅拌桨中间,在曝气管上排布着两个及两个以上的单向阀曝气接头,The invention is characterized in that: the frame-type stirring paddle, the enhanced stirring paddle and the scraper stirring paddle are rigidly connected to the stirring shaft from top to bottom, the aeration pipe is arranged between the enhanced stirring paddle and the frame-type stirring paddle, and two or more one-way valve aeration joints are arranged on the aeration pipe. 所述搅拌轴为中空状,且与曝气管连通,搅拌轴的顶部延伸出固定盖之外,在降解桶的旁边设有压缩空气加热制冷器,压缩空气加热制冷器与搅拌轴顶部之间利用旋转接头和管道连通。The stirring shaft is hollow and connected to the aeration pipe. The top of the stirring shaft extends out of the fixed cover. A compressed air heating refrigerator is arranged next to the degradation barrel. The compressed air heating refrigerator is connected to the top of the stirring shaft by a rotary joint and a pipeline. 7.根据权利要求6所述的用于油基钻屑脱油尾渣的生物降解装置,其特征在于:所述框式搅拌桨为矩形形状,在矩形框内正反交叉安装着破碎鳍。7. The biodegradation device for oil-based drill cuttings deoiling tailings according to claim 6 is characterized in that the frame-type stirring paddle is rectangular in shape, and the crushing fins are installed in a positive and negative cross manner in the rectangular frame. 8.根据权利要求6所述的用于油基钻屑脱油尾渣的生物降解装置,其特征在于:在降解桶的外周设有水浴夹套,在降解桶的旁边还设有恒温水浴实验槽,水浴夹套以循环水的方式连接着恒温水浴实验槽,降解桶内部设有温度传感器,温度传感器通过继电器与恒温水浴实验槽连接着。8. The biodegradation device for deoiling tailings of oil-based drill cuttings according to claim 6 is characterized in that a water bath jacket is provided on the periphery of the degradation barrel, a constant temperature water bath test tank is provided next to the degradation barrel, the water bath jacket is connected to the constant temperature water bath test tank in a circulating water manner, a temperature sensor is provided inside the degradation barrel, and the temperature sensor is connected to the constant temperature water bath test tank through a relay. 9.根据权利要求8所述的用于油基钻屑脱油尾渣的生物降解装置,其特征在于:在降解桶的底部设有固体排放口,其中刮泥搅拌桨的刮泥面贴合固体排放口的上平面。9. The biodegradation device for oil-based drill cuttings deoiling tailings according to claim 8 is characterized in that a solid discharge port is provided at the bottom of the degradation barrel, wherein the scraping surface of the scraping stirring paddle fits the upper plane of the solid discharge port. 10.根据权利要求9所述的用于油基钻屑脱油尾渣的生物降解装置,其特征在于:其出水口位置高于刮泥搅拌桨的位置,并在出水口位置处接有可变液位高度排液阀。10. The biodegradation device for oil-based drill cuttings deoiling tailings according to claim 9 is characterized in that the water outlet is located higher than the scraper and stirring paddle, and a variable liquid level height drain valve is connected at the water outlet.
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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08309327A (en) * 1995-05-22 1996-11-26 Mitsui Kushikino Kozan Kk Garbage processing equipment
JP2003033778A (en) * 2001-07-25 2003-02-04 Shinyo Sangyo Kk Agitating grease-trapping wastewater treatment device
CN103920694A (en) * 2014-04-08 2014-07-16 重庆大学 Method for rapidly passivating and coating phosphate tailings
CN207845258U (en) * 2017-12-29 2018-09-11 石家庄市源生园环保有限公司 A kind of biological contact oxidation pond
CN112077127A (en) * 2020-09-17 2020-12-15 杭州楠大环保科技有限公司 A large-scale kitchen waste phase change water degradation treatment system and its treatment method
CN112390413A (en) * 2020-11-07 2021-02-23 丁窒 Sewage precipitation device convenient to sludge treatment
CN115078577A (en) * 2022-06-14 2022-09-20 国网河北省电力有限公司电力科学研究院 Method for detecting petroleum hydrocarbon in soil
CN117264798A (en) * 2022-12-30 2023-12-22 重庆大学 Screening and application of a strain that efficiently degrades high-concentration shale gas oil-based drilling cuttings
CN117619867A (en) * 2023-11-27 2024-03-01 重庆大学 A multi-source shale gas oil-based drill cuttings degradation experimental method and device
CN220766963U (en) * 2023-09-08 2024-04-12 南京农业大学 Constant-temperature aerobic fermentation device for experiments
US20240240212A1 (en) * 2021-05-28 2024-07-18 Kimberly-Clark Worldwide, Inc. A Bioreactor and Process for Forming Polyhydroxybutyrate Directly from Depolymerized Polyhydroxybutyrate

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08309327A (en) * 1995-05-22 1996-11-26 Mitsui Kushikino Kozan Kk Garbage processing equipment
JP2003033778A (en) * 2001-07-25 2003-02-04 Shinyo Sangyo Kk Agitating grease-trapping wastewater treatment device
CN103920694A (en) * 2014-04-08 2014-07-16 重庆大学 Method for rapidly passivating and coating phosphate tailings
CN207845258U (en) * 2017-12-29 2018-09-11 石家庄市源生园环保有限公司 A kind of biological contact oxidation pond
CN112077127A (en) * 2020-09-17 2020-12-15 杭州楠大环保科技有限公司 A large-scale kitchen waste phase change water degradation treatment system and its treatment method
CN112390413A (en) * 2020-11-07 2021-02-23 丁窒 Sewage precipitation device convenient to sludge treatment
US20240240212A1 (en) * 2021-05-28 2024-07-18 Kimberly-Clark Worldwide, Inc. A Bioreactor and Process for Forming Polyhydroxybutyrate Directly from Depolymerized Polyhydroxybutyrate
CN115078577A (en) * 2022-06-14 2022-09-20 国网河北省电力有限公司电力科学研究院 Method for detecting petroleum hydrocarbon in soil
CN117264798A (en) * 2022-12-30 2023-12-22 重庆大学 Screening and application of a strain that efficiently degrades high-concentration shale gas oil-based drilling cuttings
CN220766963U (en) * 2023-09-08 2024-04-12 南京农业大学 Constant-temperature aerobic fermentation device for experiments
CN117619867A (en) * 2023-11-27 2024-03-01 重庆大学 A multi-source shale gas oil-based drill cuttings degradation experimental method and device

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