Portable water surface oil spill sample rapid enrichment device and method

Abstract

The invention discloses a portable water surface oil spill sample rapid enrichment device and method. The portable water surface oil spill sample rapid enrichment device comprises a feeding unit, a first oil-water separation unit, a second oil-water separation unit, a concentration unit, a tail gas treatment unit, a finished product unit and a control unit. The feeding unit performs demulsification pretreatment on a sample through an ultrasonic generator, an extraction column of the first oil-water separation unit adsorbs spilled oil components and preliminarily separates water, and an elution reagent is injected into a reagent bottle to elute the spilled oil components into a collection bottle; an adsorption column of the second oil-water separation unit deeply removes water, and the concentration unit heats an evaporation bottle through a heating sleeve to remove an elution reagent; an activated carbon adsorption tank of the tail gas treatment unit purifies reagent steam, and the finished product unit realizes quantitative storage of samples. According to the method, through an integrated process of collection, pretreatment, adsorption, elution, water removal, concentration and storage, rapid enrichment and preparation of an oil spill sample are realized. The device is compact in structure and automatic in operation, the prepared sample can be directly matched with detection equipment, and the field monitoring efficiency of sea surface oil spill is improved.

Description

Technical Field

[0001] This invention relates to the field of rapid detection technology for oil spills on water surfaces, specifically to a portable device and method for rapid enrichment of oil spill samples on water surfaces. Background Technology

[0002] Oil spills can occur during offshore oil exploration and development, crude oil transportation by ships, and fuel oil use, causing serious marine environmental pollution. These accidents not only result in huge economic losses but also disrupt the balance of marine ecosystems, causing long-term damage to marine biodiversity and coastal ecosystems. After an oil spill, quickly identifying the source and determining liability are core requirements of marine environmental management, and achieving this goal relies on accurate and efficient oil spill component identification as technical support.

[0003] Currently, laboratory-level identification of oil spill components has matured, primarily employing instrumental analysis methods such as gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). With advancements in detection technology, portable GC and GC-MS instruments have become increasingly sophisticated, enabling direct on-site detection at oil spill sites. However, a key issue remains: the field of oil spill testing and identification lacks suitable on-site pretreatment and enrichment devices. Existing technologies cannot rapidly enrich, dehydrate, and purify seawater oil spill samples on-site, making portable detection equipment unusable directly. Samples either need to be taken back to the laboratory for pretreatment before testing, severely delaying emergency response time; or the sample's moisture and impurities may interfere with GC injection requirements, affecting the accuracy of the identification results. Therefore, developing a dedicated device that can operate directly at the oil spill site, rapidly enrich, dehydrate, and purify oil samples, and whose processed samples are directly compatible with GC detection, thus resolving the contradiction between mature on-site detection equipment and the lack of pretreatment technology, is a pressing issue that needs to be addressed. Summary of the Invention

[0004] To address the technical problems existing in the prior art, the first objective of this invention is to provide a portable device and method for rapid enrichment of oil spill samples from water surfaces, achieving integrated on-site sample enrichment and preparation. The device integrates feed pretreatment, two-stage oil-water separation, concentration and purification, exhaust gas purification, and finished product storage. It features a compact and modular structure, is portable, and can be carried to oil spill emergency sites by monitoring vehicles and vessels. The enriched samples can be directly adapted to portable gas chromatographs and other detection equipment, solving the problems of lacking on-site adaptable oil spill pretreatment devices and slow detection response in existing technologies.

[0005] The second objective of this invention is to provide a portable method for rapid enrichment of oil spill samples. Based on the aforementioned enrichment device, this method achieves efficient enrichment of oil spill components through an integrated process of sample collection, demulsification pretreatment, adsorption separation, elution transfer, deep dehydration, heating concentration, nitrogen blowing, and finished product storage. The method is highly automated, requiring no complex manual intervention, and can quickly complete sample pretreatment, shortening the on-site detection cycle and providing timely and accurate sample support for oil spill accident liability determination and emergency response.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: A portable device for rapid enrichment of oil spill samples on water surfaces, comprising: The upper feeding unit is used to collect and pre-process oil spill samples from the sea surface to be treated; The first oil-water separation unit located at the top includes an extraction column, a reagent bottle, a collection bottle, and a waste liquid tank. The input end of the extraction column is connected to the feeding unit and is used to adsorb oil spill components from the sea surface oil spill sample. The waste liquid tank is connected to the output end of the extraction column through a pipeline and is used to collect the water separated by the extraction column. The reagent bottle is connected to the input end of the extraction column through a pipeline and is used to inject elution reagent into the extraction column to elute the adsorbed oil spill components into the collection bottle. The second oil-water separation unit located at the top includes an adsorption column. The input end of the adsorption column is connected to the collection bottle for receiving the spilled oil components in the collection bottle. The adsorption column is filled with an adsorbent to adsorb the residual water in the spilled oil components. The concentration unit located at the bottom is connected to the output end of the adsorption column of the second oil-water separation unit. It is used to receive the oil spill components after water removal and to evaporate the eluent in the oil spill components by heating, so as to obtain the concentrated oil spill components. An exhaust gas treatment unit is connected to the exhaust end of the concentration unit and is used to collect and treat the reagent vapor generated by the evaporation of the concentration unit. The finished product unit is connected to the discharge end of the concentration unit and is used to receive and store the concentrated oil spill components. The control unit located at the bottom is electrically connected to the feeding unit, the first oil-water separation unit, the second oil-water separation unit and the concentration unit, respectively, and is used to control the working sequence, reagent addition amount and heating temperature of each unit.

[0007] According to one example, a purging unit is also included, located between the feed unit and the first oil-water separation unit. The purging unit has a nitrogen cylinder connected via pipelines to the extraction column and the concentration unit, respectively, for introducing nitrogen into the extraction column to dry residual moisture, or for introducing nitrogen into the concentration unit to promote the evaporation of the eluent.

[0008] According to one example, the feeding unit includes a housing with a rotating plate rotatably disposed on the top of the housing. The rotating plate is circumferentially provided with a plurality of sample slots for accommodating oil spill sample bottles to be treated. An ultrasonic generator is disposed at the bottom of the sample slots and is electrically connected to the control unit for demulsifying the oil spill sample to disperse the oil droplets.

[0009] According to one example, the extraction column and the adsorption column are arranged side by side along the width of the enrichment device, the collection bottle and the waste liquid tank are located below the extraction column, and the concentration unit is located below the adsorption column.

[0010] According to one example, the concentration unit includes an evaporation flask and a heating jacket disposed outside the evaporation flask. The input end of the evaporation flask is connected to the output end of the adsorption column for receiving the oil spill components after water removal. The heating jacket is used to heat the evaporation flask to evaporate the eluent in the oil spill components inside, thereby obtaining concentrated oil spill components.

[0011] According to one example, the exhaust gas treatment unit includes an activated carbon adsorption tank, the inlet of which is connected to the exhaust of the concentration unit, for adsorbing and purifying reagent vapors generated by evaporation.

[0012] According to one example, the finished product unit includes: The injection device includes a sleeve and a piston rod disposed at one end of the sleeve. The upper part of the sleeve is connected to the discharge end of the concentration unit through a pipeline to receive the concentrated oil spill components. The piston rod is used to quantitatively push the oil spill components and discharge them from the other end of the sleeve. A storage device includes a frame having a first plate and a second plate arranged vertically. A pipette is slidably disposed on the first plate, and a plurality of through holes for placing an ampoule are formed on the second plate. The upper end of the pipette is connected to the other end of a sleeve via a flexible conduit, and the lower end of the pipette extends to the top of the ampoule.

[0013] According to one example, the adsorbent is anhydrous sodium sulfate; the eluent includes one or more of n-hexane, dichloromethane, and petroleum ether.

[0014] A method for rapidly enriching marine oil spill samples using the aforementioned device includes the following steps: Oil spill samples from the sea surface are collected through the feeding unit; The pretreated sample is transported to the extraction column of the first oil-water separation unit, where the adsorbent in the extraction column adsorbs the oil spill components, and the separated water is discharged into the waste liquid tank through a pipeline. Elution reagent is injected into the extraction column through the reagent bottle to elute the adsorbed oil spill components into the collection bottle; The spilled oil components in the collection bottle are transported to the adsorption column of the second oil-water separation unit, where the adsorbent inside the adsorption column removes the residual moisture. The dehydrated oil spill components are fed into the concentration unit, where the eluent is evaporated by heating to obtain the concentrated oil spill components. The concentrated oil spill components are transferred to the finished product unit for storage, and the reagent vapor generated by evaporation is purified by adsorption through the tail gas treatment unit.

[0015] According to one example, after the adsorption of the extraction column is completed, gas is first introduced into the extraction column through the purge unit to dry the residual moisture in the extraction column before elution is performed; while the eluent is heated and evaporated in the concentration unit, gas is introduced into the concentration unit through the purge unit to promote the evaporation of the eluent.

[0016] The present invention has the following advantages: This invention achieves rapid enrichment, extraction, and standardized processing of oil spill samples by integrating fully automated modules for feed pretreatment, two-stage oil-water separation, concentration and purification, quantitative dispensing, and exhaust gas treatment. This overcomes the limitations of traditional oil spill detection methods that require samples to be taken back to the laboratory for complex pretreatment. The device can be used directly on-site with a portable chromatography detection system. Processed oil spill samples are dispensed into dedicated gas chromatography vials via the finished product unit, allowing for direct injection and analysis without secondary transfer. This truly enables on-site inspection and identification of oil spills, shortening the overall cycle from sample collection to results, and improving the efficiency and emergency response speed of oil spill monitoring and detection.

[0017] In practical applications, this device can separate and enrich characteristic oil fingerprint components such as alkanes and aromatics in oil spill samples. Combined with the rapid detection function of a portable chromatograph, it can quickly obtain the compositional characteristics and source information of the oil spill. Based on these accurate detection results, relevant departments can quickly identify the source of the oil spill, clarify the responsible party, and formulate a scientifically sound emergency response plan. Timely and targeted measures can be taken to control the spread of the oil spill, prevent the pollution from expanding, and effectively reduce the damage to the aquatic ecosystem caused by the oil spill. Simultaneously, the device's automated operation design reduces errors and sample loss caused by human intervention, ensuring the accuracy and reliability of the detection data. This provides strong technical support for tracing the source of oil spill pollution, assigning responsibility, and making emergency decisions, demonstrating both emergency monitoring value and practical environmental significance. Attached Figure Description

[0018] Figure 1 This is a three-dimensional structural schematic diagram of the portable marine oil spill sample rapid enrichment device of the present invention.

[0019] Figure 2 This is a three-dimensional cross-sectional view of the portable marine oil spill sample rapid enrichment device of the present invention.

[0020] Figure 3 This is a planar cross-sectional view of the portable marine oil spill sample rapid enrichment device of the present invention.

[0021] Figure 4 This is a three-dimensional structural diagram of the feeding unit of the present invention.

[0022] Figure 5 This is a three-dimensional structural diagram of the feeding unit and the first oil-water separation unit of the present invention.

[0023] Figure 6 This is a three-dimensional structural diagram of the first oil-water separation unit and the second oil-water separation unit of the present invention.

[0024] Figure 7 This is a three-dimensional structural diagram of the second oil-water separation unit, concentration unit, exhaust gas treatment unit, and finished product unit of the present invention.

[0025] Figure 8 This is a three-dimensional structural diagram of the concentration unit of the present invention.

[0026] Figure 9 This is a three-dimensional structural diagram of the finished product unit of the present invention.

[0027] Figure 10 This is a schematic diagram of the working process of the portable marine oil spill sample rapid enrichment device of the present invention.

[0028] Wherein, 1 is the feeding unit, 101 is the shell, 102 is the rotating plate, 102a is the sample tank, 103 is the sample bottle, 104 is the ultrasonic generator, 105 is the rotating shaft, 106 is the rotating motor, 2 is the first oil-water separation unit, 201 is the extraction column, 202 is the reagent bottle, 203 is the collection bottle, 204 is the waste liquid tank, 204a is the waste liquid outlet, 205 is the peristaltic pump, 206 is the first transfer pump, 2a is the first feeding pipeline, 2b is the first discharging pipeline, 2b1 is the first valve, 2c is the second feeding pipeline, and 2d is the second discharging pipeline. Piping: 2d1 is the second valve, 2e is the waste liquid pipeline, 2e1 is the third valve, 2f is the reagent feed pipeline, 2f1 is the fourth valve, 2g is the reagent discharge pipeline, 2h is the third discharge pipeline, 2h1 is the fifth valve, 3 is the second oil-water separation unit, 301 is the adsorption column, 302 is the second transfer pump, 3a is the third feed pipeline, 3b is the fourth discharge pipeline, 3b1 is the sixth valve, 4 is the concentration unit, 401 is the evaporation flask, 401a is the air blowing port, 401b is the feed port, 401c is the exhaust port, and 401d is the discharge port. 402 is the heating jacket, 402a is the heat medium inlet, 402b is the heat medium outlet, 4a is the steam exhaust pipe, 4a1 is the seventh valve, 4b is the fifth discharge pipe, 4b1 is the eighth valve, 5 is the finished product unit, 501 is the injection and push device, 501a is the sleeve, 501b is the piston rod, 501c is the injection and push motor, 502 is the storage device, 502a is the frame, 502b is the first plate, 502b1 is the chute, 502c is the second plate, 502c1 is the through hole, 503 is the ampoule, 504 is the pipette, 504a... 5a is the limit block, 6 is the sixth discharge pipe, 6 is the tail gas treatment unit, 601 is the activated carbon adsorption tank, 7 is the control unit, 701 is the controller, 702 is the power supply, 703 is the control panel, 8 is the purging unit, 801 is the nitrogen cylinder, 8a is the first purging pipe, 8b is the second purging pipe, 9 is the housing, 901 is the bottom plate, 902 is the side plate, 903 is the top plate, 904 is the first partition plate, 904a is the positioning block, 905 is the second partition plate, 906 is the caster wheel, 907 is the push-pull rod, 908 is the fan, and 909 is the maintenance door. Detailed Implementation

[0029] The present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments.

[0030] Reference Figure 1 and Figure 2This invention illustrates a specific embodiment of a portable rapid enrichment device for marine oil spill samples. The device employs an integrated layout with upper separation and lower concentration sections, featuring a compact, portable, and mobile structure that can be rapidly deployed to oil spill emergency sites via monitoring vehicles and vessels. Through the coordinated operation of the feeding unit 1, the first oil-water separation unit 2, the second oil-water separation unit 3, the concentration unit 4, the exhaust gas treatment unit 6, the finished product unit 5, the purging unit 8, and the control unit 7, the entire process of marine oil spill sample collection, pretreatment, adsorption separation, elution and transfer, deep dehydration, and concentration and storage is fully automated. The enriched samples can be directly adapted to portable gas chromatographs and other detection equipment, eliminating the need for secondary processing in a laboratory. This significantly improves the efficiency and accuracy of on-site oil spill monitoring, providing timely technical support for oil spill accident liability determination and emergency response.

[0031] Reference Figure 1 and Figure 2 Each unit is integrated within a rectangular housing 9, which includes a horizontally arranged base plate 901. Four side plates 902 extend vertically upwards from the base plate 901, and a top plate 903 covers the top of each side plate 902. The base plate 901, the four side plates 902, and the top plate 903 together form a sealed space accommodating each unit. A first partition plate 904 and a second partition plate 905 are arranged vertically along the height of the housing 9 to divide the sealed space into an upper, middle, and lower region. The feeding unit 1, the first oil-water separation unit 2, and the second oil-water separation unit 3 are horizontally integrated along the upper part of the housing 9 and located in the upper and middle regions. The concentration unit 4, the exhaust gas treatment unit 6, the finished product unit 5, and the control unit 7 are correspondingly arranged in the lower part of the housing 9, i.e., the lower region. The purging unit 8 is modularly assembled in the area between the feeding unit 1 and the first oil-water separation unit 2, forming a compact and rationally laid-out integrated device.

[0032] The bottom of the housing 9 is equipped with multiple lockable casters 906, allowing operators to quickly move the device to the vicinity of the sampling source and fix it in position. Push-pull rods 907 are located on the two outer end walls of the housing 9 to facilitate movement of the housing 9. Each unit has an inspection door 909 on its corresponding side panel 902, allowing for direct maintenance, component replacement, or reagent replenishment of that individual unit. Furthermore, multiple fans 908 are installed on the side walls of the housing 9 for ventilation and heat dissipation of each unit.

[0033] Reference Figures 2-4The feeding unit 1 is used to collect and pre-process oil spill samples from the sea surface to be processed. The feeding unit 1 includes a housing 101, which is fixed in the central region. A rotating plate 102 is rotatably provided on the top of the housing 101. Multiple sample slots 102a are formed along the rotating plate 102. The sample slots 102a contain oil spill sample bottles 103 to be processed. The oil spill can be collected on-site by operators and directly injected into the sample bottles 103, or it can be connected to an external pipeline through an interface on the side wall of the housing 101, and then pumped into the sample bottles 103 by an external pump.

[0034] Continue to refer to Figure 4 A rotating shaft 105 is vertically inserted through the middle of the rotating plate 102. The upper end of the rotating shaft 105 is fixed to the rotating plate 102, and the lower end of the rotating shaft 105 extends towards the bottom of the housing 101 and is equipped with a rotating motor 106. The rotating plate 102 can be rotated by the rotating motor 106, realizing the sequential switching of multiple sample tanks 102a, which facilitates continuous sample processing. At the same time, an ultrasonic generator 104 is correspondingly installed at the bottom of each sample tank 102a. The ultrasonic generator 104 is fixed to the lower part of the housing 101 and is electrically connected to the control unit 7. It starts working under the command of the control unit 7 and uses high-frequency ultrasonic waves to demulsify the oil spill sample on the sea surface, effectively breaking the oil-water emulsion system, so that the oil droplets wrapped in the aqueous phase are fully dispersed, thereby improving the adsorption efficiency of oil spill components in the subsequent first oil-water separation unit 2.

[0035] Reference Figure 2 , 3 5. The first oil-water separation unit 2 is used for the preliminary separation of oil spill components. It includes an extraction column 201, a reagent bottle 202, a collection bottle 203, and a waste liquid tank 204. The collection bottle 203 and the waste liquid tank 204 are located below the extraction column 201. The extraction column 201 has a cylindrical structure and the top of the extraction column 201 is open. Its interior is filled with an adsorption medium for selectively adsorbing the oil phase components in the sea surface oil spill sample. The adsorption medium can be a special adsorption material such as C18 silica gel. The upstream of the extraction column 201 is connected to the sample bottle 103 of the feeding unit 1 through a pipeline. Specifically, the input end of the top of the extraction column 201 is connected to a second feed line 2c. The input end of the second feed line 2c is connected to a first discharge line 2b and a reagent feed line 2f via a three-way valve. The input end of the first discharge line 2b is connected to the output end of the peristaltic pump 205. The input end of the peristaltic pump 205 is connected to the sample vial 103 via the first feed line 2a. The first feed line 2a and the sample vial 103 are magnetically connected to facilitate quick switching between different sample vials 103. Simultaneously, a first valve 2b1 is also installed on the first discharge line 2b to control the opening and closing of the sample delivery path.

[0036] The bottom of the extraction column 201 has two branches at its output end: a waste liquid pipeline 2e and a second discharge pipeline 2d. The output end of the waste liquid pipeline 2e is connected to the waste liquid tank 204, and a third valve 2e1 is installed on the waste liquid pipeline 2e to guide the aqueous phase components separated by the extraction column 201 into the waste liquid tank 204 for collection. The side wall of the waste liquid tank 204 is also provided with a waste liquid outlet 204a for convenient subsequent centralized discharge of waste liquid. The output end of the second discharge pipeline 2d is connected to the top of the collection bottle 203, and a second valve 2d1 is installed on the second discharge pipeline 2d to transport the eluted oil spill components to the collection bottle 203 for temporary storage.

[0037] Reagent bottle 202 is used to store eluents and is connected to extraction column 201 via a reagent delivery pipeline. Specifically, the outlet of reagent bottle 202 is connected to the input of first delivery pump 206 via reagent discharge pipeline 2g, and the output of first delivery pump 206 is connected to a three-way valve via reagent feed pipeline 2f. A fourth valve 2f1 is configured on reagent feed pipeline 2f. The start and stop of first delivery pump 206 and fourth valve 2f1 are controlled by control unit 7 to control the injection volume and timing of eluents, ensuring that the oil spillage adsorbed on extraction column 201 is fully eluted and transferred to collection bottle 203. Multiple reagent bottles 202 are configured, such as 3, 4, 5, etc., each independently storing different types of eluents, including one or more commonly used organic solvents such as n-hexane, dichloromethane, and petroleum ether. Multiple reagent bottles 202 are rotatably mounted on the second partition plate 905 via a turntable, allowing for switching between different reagent bottles 202 and the reagent discharge pipeline 2g connection states.

[0038] Reference Figure 2 , 5 6. The second oil-water separation unit 3 is used to remove residual water from the sample after elution by the first oil-water separation unit 2, ensuring the efficiency of the subsequent concentration process and the purity of the final sample. It includes an adsorption column 301, which has a cylindrical structure and is roughly the same as the structure of the extraction column 201. The extraction column 201 and the adsorption column 301 are detachable and arranged side by side on the first partition plate 904. The first partition plate 904 has mounting holes adapted to the outer diameter of the extraction column 201 and the adsorption column 301. Multiple positioning blocks 904a are provided on the circumferential wall of the mounting holes. When the extraction column 201 and the adsorption column 301 are inserted into the mounting holes from top to bottom, the positioning blocks 904a are close to the top outer wall of the extraction column 201 and the adsorption column 301 to achieve rapid positioning and fixation, preventing them from shifting during device movement or operation.

[0039] A third discharge pipe 2h is connected to the top of the collection bottle 203. The input end of the third discharge pipe 2h extends to the bottom of the collection bottle 203 to completely drain the oil-containing eluent temporarily stored in the bottle. A fifth valve 2h1 is installed on the third discharge pipe 2h to control the flow of the pipe. The output end of the third discharge pipe 2h is connected to the input end of the second transfer pump 302, which is fixed on the bottom plate 901 of the housing 9. The output end of the second transfer pump 302 is connected to the input end of the top of the adsorption column 301 through the third feed pipe 3a. Powered by the second transfer pump 302, the sample in the collection bottle 203 is transported to the adsorption column 301. The adsorption column 301 is filled with anhydrous sodium sulfate adsorbent, which has strong water absorption and does not react with oil phase components. When the spilled oil sample containing residual water flows through the adsorbent layer, the water is adsorbed and retained, while the oil phase components pass through smoothly, achieving deep water removal. The output end at the bottom of the adsorption column 301 is connected to the concentration unit 4 through the fourth discharge pipe 3b. The fourth discharge pipe 3b is equipped with a sixth valve 3b1. After the water removal is completed, the control unit 7 opens the sixth valve 3b1, and the oil phase sample after deep water removal is transported to the concentration unit 4 for further processing.

[0040] Reference Figure 2 , 7 Concentration unit 4 is used to receive the dehydrated oil spill components and evaporate the eluent in the oil spill components through heating and nitrogen blowing to obtain concentrated oil spill components. Concentration unit 4 is located below adsorption column 301 and is connected to the output end of adsorption column 301 of second oil-water separation unit 3 through a pipeline. Concentration unit 4 includes evaporation flask 401 and heating jacket 402 disposed outside evaporation flask 401. Evaporation flask 401 is made of high temperature resistant glass material, and its top has a feed port 401b, an exhaust port 401c and a discharge port 401d. Heating jacket 402 is a cylindrical sleeve structure with a resistance wire wound inside as a heating source. Heating jacket 402 is filled with heat transfer oil. The heat transfer oil is heated by the resistance wire and then the heat transfer oil heats the evaporation flask 401 through heat conduction. The side wall of heating jacket 402 is provided with heat medium inlet 402a and heat medium outlet 402b respectively. Of course, thermal oil can be replaced with other thermal media, such as silicone oil, mineral oil, glycerin, or solid thermal paste.

[0041] The inlet 401b of the evaporating flask 401 is connected to the output end of the bottom of the adsorption column 301 via the fifth outlet pipe 4b, for receiving the deep-dehydrated oil spill components containing eluent. An eighth valve 4b1 is installed on the fifth outlet pipe 4b, and its opening and closing are controlled by the control unit 7. The vent 401c of the evaporating flask 401 is connected to the tail gas treatment unit 6 via the steam discharge pipe 4a, which is equipped with a seventh valve 4a1 to discharge reagent vapor during the heating and evaporation process. The outlet 401d of the evaporating flask 401 is connected to the finished product unit 5 via the fifth outlet pipe 4b, for transporting the concentrated oil spill components to the storage device 502.

[0042] Reference Figure 2 and Figure 3 The housing 101 also includes a purging unit 8, located between the feeding unit 1 and the first oil-water separation unit 2. The purging unit 8 has a nitrogen cylinder 801, which is connected to the top of the extraction column 201 and the evaporation flask 401 via pipelines. The nitrogen cylinder 801 is used to introduce nitrogen gas into the extraction column 201 to dry residual moisture, or to introduce nitrogen gas into the evaporation flask 401 to promote the evaporation of the eluent. Specifically, the nitrogen cylinder 801 is connected to the top of the extraction column 201 via a first purging pipeline 8a, and to the top of the evaporation flask 401 via a second purging pipeline 8b. The top of the evaporation flask 401 has a purging port 401a, which is connected to the outlet of the second purging pipeline 8b. After the first oil-water separation unit 2 completes the discharge of the aqueous phase, the control unit 7 opens the valve on the first purge line 8a. High-pressure nitrogen gas released from the nitrogen cylinder 801 is introduced into the extraction column 201 through the first purge line 8a. The nitrogen gas flows down the extraction column 201 through the adsorption medium, blowing off the trace amounts of water remaining in the pores of the medium to prevent water from mixing with the subsequent eluent. The water after blowing off flows downward with the airflow and is finally collected in the waste liquid tank 204 through the waste liquid line 2e. During the heating and evaporation process in the concentration unit 4, the control unit 7 opens the valve on the second purge line 8b. Nitrogen gas is blown into the evaporation flask 401 from the air outlet 401a at the top of the evaporation flask 401 through the second purge line 8b. The nitrogen gas accelerates the escape of the eluent vapor.

[0043] Reference Figure 2 and Figure 7 The exhaust gas treatment unit 6 is connected to the exhaust end of the concentration unit 4 and is used to collect and treat the reagent vapor generated by the evaporation of the concentration unit 4, so as to avoid the direct emission of volatile organic reagents and pollution to the on-site environment. The exhaust gas treatment unit 6 includes an activated carbon adsorption tank 601. The inlet end of the activated carbon adsorption tank 601 is connected to the vapor discharge pipeline 4a of the concentration unit 4, and the seventh valve 4a1 on the pipeline is linked to the adsorption tank for control.

[0044] Reference Figure 2 and Figure 9The finished product unit 5 is connected to the discharge end of the concentration unit 4 and is used to receive and store the concentrated oil spill components. The finished product unit 5 includes an injection and pushing device 501 and a storage device 502. The injection and pushing device 501 includes a sleeve 501a, the upper part of which is connected to the discharge port 401d of the evaporation flask 401 via a fifth discharge pipe 4b to receive the concentrated oil spill components. A piston rod 501b is mounted at one end of the sleeve 501a, and an injection and pushing motor 501c is connected to the end of the piston rod 501b. The motor's stroke is controlled by a control unit 7 to achieve quantitative pushing of the oil spill components. The pushed sample is output from the other end of the sleeve 501a via a sixth discharge pipe 5a.

[0045] The storage device 502 includes a vertical frame 502a, on which a first plate 502b and a second plate 502c arranged parallel to each other are fixed. A transverse groove 502b1 is provided on the first plate 502b, and a pipette 504 is slidably mounted within the groove 502b1. The upper end of the pipette 504 is connected to the output end of a sleeve 501a via a sixth discharge pipe 5a, which is a flexible pipe. The lower end of the pipette 504 has a pointed tip structure, allowing it to be inserted into the mouth of an ampoule 503. A limiting block 504a is also provided on the outer wall of the upper end of the pipette 504 to engage the pipette 504 within the groove 502b1. The second plate 502c has multiple through holes 502c1, the diameter of which matches the outer diameter of the standard gas chromatography ampoule 503 for placement. The position of the through holes 502c1 corresponds to the sliding trajectory of the pipette 504, ensuring the pipette 504 is aligned with different ampoules 503 for orderly sample dispensing. The finished product unit 5 can directly dispense the concentrated oil spill components into the gas chromatography detection ampoule 503 without secondary transfer, simplifying the process from processing to detection.

[0046] In an embodiment not shown, a stepper motor is mounted above the first plate, with its output shaft connected to the upper sidewall of the pipette 504, and the axis of the output shaft parallel to the slide groove 502b1. When the control unit 7 issues a shift command, the stepper motor drives the output shaft to rotate in the forward or reverse direction, thereby driving the pipette 504 to slide linearly along the slide groove 502b1. When the lower tip of the pipette 504 moves directly above the mouth of the target ampoule 503, the sensor sends a feedback signal to the control unit 7, and the motor immediately stops operating, completing the alignment.

[0047] Return to reference Figure 2 and Figure 3The control unit 7 is electrically connected to the feeding unit 1, the first oil-water separation unit 2, the second oil-water separation unit 3, and the concentration unit 4, respectively, and is used to control the working sequence, reagent addition amount, and heating temperature of each unit. The control unit 7 mainly includes a power supply 702, a controller 701, a control panel 703, and multiple sensors. The power supply 702 provides power to the motors, valves, heating jackets 402, and other equipment in each unit. The controller 701 has a preset processing program that can adjust the operating parameters of each actuator in real time based on the signals such as liquid level, temperature, and pressure fed back by the sensors. The control panel 703 is located on the outer wall of the housing 9 and has a touch screen that can display the real-time process status. Operators can complete program selection, parameter setting, and manual intervention through the touch screen.

[0048] In an embodiment not shown, the controller 701 employs an STM32F407ZGT6 microcontroller, capable of simultaneously receiving signal inputs from multiple sensors such as liquid level, temperature, and weight. It precisely controls the start-stop sequence of actuators such as the peristaltic pump 205, rotary motor 106, and injection / push motor 501c via I / O ports. The controller 701 communicates with the touchscreen of the control panel 703 via a UART serial port for parameter setting and status feedback. The power supply 702 uses a Mean Well RQ-120B-24 switching power supply with an input voltage range of 90-264VAC, an output DC voltage of 24V, and a rated output current of 5A, capable of simultaneously powering high-power equipment such as the heating jacket 402, stepper motor, and transfer pump.

[0049] In an embodiment not shown, the feeding unit 1 is equipped with a liquid level sensor, specifically installed at the bottom of the sample tank 102a, to monitor the liquid level in the sample bottle 103. The first oil-water separation unit 2 is equipped with a flow sensor, specifically installed in the first discharge pipe 2b, to monitor the sample delivery flow rate. The second oil-water separation unit 3 is equipped with a humidity sensor, specifically embedded in the adsorbent layer of the adsorption column 301, to determine whether the water removal meets the standard. The concentration unit 4 is equipped with a temperature sensor, specifically built into the heating jacket 402 and the evaporation flask 401, to monitor the heating temperature in real time, and is also equipped with a weight sensor, specifically installed at the bottom of the evaporation flask 401, to determine the concentration endpoint through weight changes. The finished product unit 5 is equipped with a displacement sensor, which is linked to the piston rod 501b of the injection and pushing device 501 to control the pushing volume.

[0050] Reference Figure 10 A method for rapidly enriching marine oil spill samples using the aforementioned device includes the following steps: Oil spill samples are collected from the sea surface through the feeding unit 1. If the oil contains emulsified oil, the ultrasonic generator 104 is activated to demulsify the sample, dispersing the oil droplets. Operators can directly inject the collected oil spill samples into sample bottles 103 and place them into sample slots 102a of the rotating plate 102. For automated batch sampling, an external delivery pipeline can be connected via an interface pre-reserved on the side wall of the housing, allowing an external pump to directly pump the oil spill samples into the sample bottles 103. The control unit 7 starts the rotating motor 106 according to a preset program. The motor drives the top rotating plate 102 to rotate via the rotating shaft 105, causing multiple sample slots 102a to sequentially switch to the positions that connect with the first feeding pipeline 2a. When the target sample bottle 103 rotates to the designated position, the rotating motor 106 stops working, and the magnetic interface automatically completes the rapid connection between the first feeding pipeline 2a and the sample bottle 103. After the sample bottle 103 is positioned, the control unit 7 synchronously activates the ultrasonic generator 104 corresponding to the bottom of the sample tank 102a. The high-frequency ultrasonic waves emitted by the generator are transmitted into the spilled oil sample through the bottom of the sample bottle 103. The mechanical vibration generated by the ultrasonic waves breaks the oil-water emulsion system, causing the tiny oil droplets originally wrapped in the aqueous phase to be fully dispersed and aggregated, thereby improving the adsorption efficiency of the extraction column 201 in the first oil-water separation unit 2 for oil phase components.

[0051] The pretreated sample is transported to the extraction column 201 of the first oil-water separation unit 2. The adsorbent within the extraction column 201 adsorbs the spilled oil components, and the separated water is discharged into the waste liquid tank 204 through a pipeline. Elution reagent is injected into the extraction column 201 through the reagent bottle 202, eluting the adsorbed spilled oil components into the collection bottle 203. The control unit 7 starts the peristaltic pump 205 and opens the first valve 2b1, while closing the third valve 2e1, the second valve 2d1, and the fourth valve 2f1. The pretreated spilled oil sample from the feeding unit 1 is continuously transported to the extraction column 201 through the first feed pipeline 2a, the peristaltic pump 205, the first discharge pipeline 2b, and the second feed pipeline 2c. The sample slowly flows through the adsorption medium within the extraction column 201. The oil phase components are selectively adsorbed onto the surface of the medium, while the aqueous phase components flow downwards along the column. After the adsorption process is complete, control unit 7 closes the first valve 2b1 and peristaltic pump 205, and opens the third valve 2e1. The aqueous phase separated in the extraction column 201 is collected in the waste liquid tank 204 through waste liquid pipeline 2e. After the water is completely drained, control unit 7 closes the third valve 2e1, starts the first transfer pump 206 and opens the fourth valve 2f1. The eluent in reagent bottle 202 is injected into the extraction column 201 through reagent discharge pipeline 2g, the first transfer pump 206, reagent inlet pipeline 2f and the second inlet pipeline 2c. The eluent flows through the adsorption medium, fully dissolving and carrying the adsorbed oil phase component downwards. Control unit 7 opens the second valve 2d1, and the eluent containing the oil phase component is transported to the collection bottle 203 for temporary storage through the second discharge pipeline 2d.

[0052] The spilled oil components in collection bottle 203 are transported to the adsorption column 301 of the second oil-water separation unit 3, where residual water is removed using anhydrous sodium sulfate adsorbent. When the eluent spilled oil components temporarily stored in collection bottle 203 reach a preset volume, control unit 7 starts the second delivery pump 302, simultaneously opening the fifth valve 2h1 on the third discharge pipeline 2h and closing the sixth valve 3b1 on the fourth discharge pipeline 3b. At this time, the sample in collection bottle 203 is discharged through the third discharge pipeline 2h under the power of the second delivery pump 302, and transported into the adsorption column 301 through the second delivery pump 302 and the third feed pipeline 3a. After entering the adsorption column 301, the sample flows down the column from top to bottom through the anhydrous sodium sulfate adsorbent layer inside. Because anhydrous sodium sulfate has a very strong selective adsorption capacity for water and does not react with the oil phase components, the trace amounts of residual water in the sample are efficiently retained by the adsorbent, while the oil phase components remain dissolved and continue to flow downwards, achieving deep separation of oil and water. After the sample in the adsorption column 301 has completely flowed through the adsorbent layer, the control unit 7 opens the sixth valve 3b1 on the fourth discharge pipe 3b, and the clean oil phase component after deep dehydration is transported to the concentration unit 4 through the fourth discharge pipe 3b.

[0053] The dehydrated oil spill is fed into concentration unit 4, where the eluent is evaporated by heating, resulting in concentrated oil spill. After the second oil-water separation unit 3 completes deep dehydration, control unit 7 opens the sixth valve 3b1 on the fourth discharge pipe 3b, while simultaneously closing the seventh valve 4a1 on the steam discharge pipe 4a and the eighth valve 4b1 at the outlet 401d of the evaporation flask 401. The dehydrated oil spill flows into the evaporation flask 401 through the fourth discharge pipe 3b from the inlet 401b until the preset liquid level is reached, after which control unit 7 closes the sixth valve 3b1. After sample introduction, control unit 7 activates the resistance wire of the heating jacket 402, which heats the heat-conducting oil inside the heating jacket 402, transferring heat to the evaporation flask 401 via heat conduction, gradually increasing the sample temperature inside the flask. The eluent evaporates into vapor upon heating, gradually separating from the oil spill, which, due to its higher boiling point, remains in the evaporation flask 401. As evaporation proceeds, the steam pressure inside the evaporation flask 401 gradually increases. The control unit 7 opens the seventh valve 4a1, and the steam enters the steam discharge pipe 4a through the exhaust port 401c. It is then continuously introduced into the activated carbon adsorption tank 601 for adsorption and purification. After entering the adsorption tank, the reagent steam slowly permeates along the pores between the activated carbon particles. The organic components in the steam are adsorbed and retained by the micropores on the surface of the activated carbon due to intermolecular attraction, achieving separation from the air. The exhaust gas purified by activated carbon adsorption is discharged from the exhaust port 401c.

[0054] Control unit 7 determines the concentration endpoint by real-time monitoring of heating time or weight change of evaporation flask 401. After the endpoint is reached, control unit 7 turns off the power supply 702 of heating jacket 402 and the seventh valve 4a1. After evaporation flask 401 cools naturally to room temperature, the eighth valve 4b1 is opened. The concentrated high-concentration overflow oil component is transported to the finished product unit 5 through the fifth discharge pipe 4b, completing the concentration process.

[0055] The concentrated oil spill is transferred to the finished product unit 5 for storage, and the reagent vapor generated by evaporation is purified by adsorption in the tail gas treatment unit 6. After the concentration unit 4 completes the evaporation process, the control unit 7 opens the eighth valve 4b1 on the fifth discharge pipe 4b, and the concentrated oil spill is pumped into the sleeve 501a of the injection device 501 until the preset volume is reached. Then, the eighth valve 4b1 is closed, and the sample is received. According to the preset dispensing volume, the control unit 7 sends a command to the injection motor 501c. The injection motor 501c drives the piston rod 501b to move to the initial calibration position, and the lower end of the pipette 504 is manually aligned with the mouth of the target ampoule 503 on the second plate 502c. The control unit 7 starts the injection motor 501c, which drives the piston rod 501b to move forward, injecting a fixed amount of oil spill from the sleeve 501a into the corresponding ampoule 503 through the sixth discharge pipe 5a and the pipette 504. After loading, the operator can directly remove the ampoule 503 containing the sample and place it directly into the gas chromatograph for detection.

[0056] In addition, a purging step is included. After adsorption is completed in the extraction column 201, gas is first introduced into the extraction column 201 through the purging unit 8 to dry the residual moisture in the extraction column 201 before elution. After the first oil-water separation unit 2 completes the adsorption of oil spill components and the discharge of water phase, the first purging of the purging unit 8 is started. The control unit 7 opens the main valve of the nitrogen cylinder 801 and the valve on the first purging pipeline 8a. High-pressure nitrogen gas is introduced into the top of the extraction column 201 through the first purging pipeline 8a. The nitrogen gas penetrates the adsorption medium from top to bottom along the axial direction of the extraction column 201. The airflow carries away the trace amount of moisture remaining in the pores of the medium and completely blows it off. The water vapor mixture generated by the blow-off is discharged into the waste liquid tank 204 through the waste liquid pipeline 2e at the bottom of the extraction column 201. The valve of the first purging pipeline 8a is closed, and then the elution operation is started again.

[0057] While the eluent is heated and evaporated in the concentration unit 4, gas is introduced into the concentration unit 4 through the purge unit 8 to promote the evaporation of the eluent. During the heating process of the sample in the evaporation flask 401 by the heating mantle 402 in the concentration unit 4, the second purge of the purge unit 8 is activated. The control unit 7 opens the valve on the second purge line 8b, and nitrogen gas is blown into the evaporation flask 401 through the purge port 401a at the top of the evaporation flask 401. The nitrogen gas flow accelerates the eluent vapor within the evaporation flask 401, causing it to detach from the liquid phase surface and move towards the exhaust port 401c.

[0058] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention should be considered equivalent substitutions and are included within the protection scope of the present invention. The embodiments described in this disclosure are intended as non-limiting examples, and other embodiments may take various and alternative forms. Furthermore, the drawings are not necessarily to scale and may present simplified expressions of various features of the present disclosure, including, for example, specific dimensions, orientations, positions, and shapes. Details associated with such features will be determined in part by the intended application and usage environment of the described embodiments.

[0059] The detailed description and accompanying drawings are supporting and descriptive of this teaching, but the scope of this teaching is defined only by the claims. While the best mode and some other embodiments for carrying out this teaching have been described in detail, various alternative designs and embodiments exist for practicing the teaching as defined in the appended claims. Furthermore, this disclosure expressly includes combinations and sub-combinations of the elements and features set forth above and below.

Claims

1. A portable device for rapid enrichment of oil spill samples from water surfaces, characterized in that, include: The upper feeding unit is used to collect and pre-process oil spill samples from the sea surface to be treated; The first oil-water separation unit located at the top includes an extraction column, a reagent bottle, a collection bottle, and a waste liquid tank. The input end of the extraction column is connected to the feeding unit and is used to adsorb oil spill components from the sea surface oil spill sample. The waste liquid tank is connected to the output end of the extraction column through a pipeline and is used to collect the water separated by the extraction column. The reagent bottle is connected to the input end of the extraction column through a pipeline and is used to inject elution reagent into the extraction column to elute the adsorbed oil spill components into the collection bottle. The second oil-water separation unit located at the top includes an adsorption column. The input end of the adsorption column is connected to the collection bottle for receiving the spilled oil components in the collection bottle. The adsorption column is filled with an adsorbent to adsorb the residual water in the spilled oil components. The concentration unit located at the bottom is connected to the output end of the adsorption column of the second oil-water separation unit. It is used to receive the oil spill components after water removal and to evaporate the eluent in the oil spill components by heating, so as to obtain the concentrated oil spill components. An exhaust gas treatment unit is connected to the exhaust end of the concentration unit and is used to collect and treat the reagent vapor generated by the evaporation of the concentration unit. The finished product unit is connected to the discharge end of the concentration unit and is used to receive and store the concentrated oil spill components. The control unit located at the bottom is electrically connected to the feeding unit, the first oil-water separation unit, the second oil-water separation unit and the concentration unit, respectively, and is used to control the working sequence, reagent addition amount and heating temperature of each unit.

2. The enrichment device according to claim 1, characterized in that, It also includes a purging unit located between the feeding unit and the first oil-water separation unit. The purging unit has a nitrogen cylinder, which is connected to the extraction column and the concentration unit via pipelines. It is used to introduce nitrogen into the extraction column to dry the residual moisture, or to introduce nitrogen into the concentration unit to promote the evaporation of the eluent.

3. The enrichment device according to claim 1, characterized in that, The feeding unit includes a housing, and a rotating plate is rotatably provided on the top of the housing. The rotating plate is circumferentially provided with multiple sample slots for accommodating oil spill sample bottles to be treated. An ultrasonic generator is provided at the bottom of the sample slots. The ultrasonic generator is electrically connected to the control unit and is used to demulsify the oil spill sample to disperse the oil droplets.

4. The enrichment device according to claim 1, characterized in that, The extraction column and the adsorption column are arranged side by side along the width of the enrichment device, the collection bottle and the waste liquid tank are located below the extraction column, and the concentration unit is located below the adsorption column.

5. The enrichment device according to claim 1, characterized in that, The concentration unit includes an evaporation flask and a heating jacket disposed outside the evaporation flask. The input end of the evaporation flask is connected to the output end of the adsorption column and is used to receive the oil spill components after water removal. The heating jacket is used to heat the evaporation flask to evaporate the eluent in the oil spill components inside, thereby obtaining concentrated oil spill components.

6. The enrichment device according to claim 1, characterized in that, The exhaust gas treatment unit includes an activated carbon adsorption tank, the inlet of which is connected to the exhaust of the concentration unit, for adsorbing and purifying reagent vapors generated by evaporation.

7. The enrichment device according to claim 1, characterized in that, The finished product unit includes: The injection device includes a sleeve and a piston rod disposed at one end of the sleeve. The upper part of the sleeve is connected to the discharge end of the concentration unit through a pipeline to receive the concentrated oil spill components. The piston rod is used to quantitatively push the oil spill components and discharge them from the other end of the sleeve. A storage device includes a frame having a first plate and a second plate arranged vertically. A pipette is slidably disposed on the first plate, and a plurality of through holes for placing an ampoule are formed on the second plate. The upper end of the pipette is connected to the other end of a sleeve via a flexible conduit, and the lower end of the pipette extends to the top of the ampoule.

8. The enrichment device according to claim 1, characterized in that, The adsorbent is anhydrous sodium sulfate; the elution reagent includes one or more of n-hexane, dichloromethane, and petroleum ether.

9. A method for rapidly enriching marine oil spill samples using the portable oil spill sample collection device as described in any one of claims 1-8, characterized in that, Includes the following steps: Oil spill samples from the sea surface are collected through the feeding unit; The pretreated sample is transported to the extraction column of the first oil-water separation unit, where the adsorbent in the extraction column adsorbs the oil spill components, and the separated water is discharged into the waste liquid tank through a pipeline. Elution reagent is injected into the extraction column through the reagent bottle to elute the adsorbed oil spill components into the collection bottle; The spilled oil components in the collection bottle are transported to the adsorption column of the second oil-water separation unit, where the adsorbent inside the adsorption column removes the residual moisture. The dehydrated oil spill components are fed into the concentration unit, where the eluent is evaporated by heating to obtain the concentrated oil spill components. The concentrated oil spill components are transferred to the finished product unit for storage, and the reagent vapor generated by evaporation is purified by adsorption through the tail gas treatment unit.

10. The enrichment method according to claim 9, characterized in that, After the adsorption in the extraction column is completed, gas is first introduced into the extraction column through the purge unit to dry the residual moisture in the extraction column before elution. While the eluent is heated and evaporated in the concentration unit, gas is introduced into the concentration unit through the purge unit to promote the evaporation of the eluent.

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