Electrochemical treatment device for delayed coking coke cooling water

Abstract

The utility model belongs to the technical field of petrochemical engineering, and discloses a delayed coking coke cooling water electrochemical treatment device which is mainly used for solving the problem that coke cooling water generated in the production process of a delayed coking process contains a large amount of corrosive ions and organic compounds. According to the utility model, an electrochemical treatment mode of combining electrocatalytic oxidation and electro-adsorption desalination is adopted, the electrocatalytic oxidation device can oxidize and degrade organic matters in the coke cooling water to remove toxicity until the coke cooling water is completely mineralized, and the electro-adsorption desalination device can reduce the concentration of inorganic salts in the coke cooling water, so that the water quality of the coke cooling water is improved. By combining the two methods, the degradation of corrosive ions and organic compounds in the coke cooling water is realized, and the problems of corrosion and pollution are solved; besides, the device is driven by adopting green and low-carbon electric power resources, and power supply output can be controlled by adopting a computer program according to the degradation condition of pollutants in the coke cooling water, so that the operation energy consumption cost of the device is greatly reduced.

Description

Technical Field

[0001] This utility model belongs to the field of petrochemical technology, and more specifically, relates to an electrochemical treatment device for delayed coking cold coke water. Background Technology

[0002] Delayed coking is a secondary petroleum processing technology that uses hydrogen-poor heavy oil as feedstock and involves deep thermal cracking and condensation reactions at high temperatures (approximately 500°C) to produce rich gas, crude gasoline, diesel, wax oil, and coke. It is one of the world's main methods for deep processing of residual oil, accounting for one-third of the world's residual oil processing capacity. The term "delayed" refers to the rapid heating of the coking oil (feedstock and circulating oil) to the coking reaction temperature in a furnace, preventing coking within the furnace tubes and allowing it to proceed to the coking tower for further coking. This delayed process is called delayed coking technology. Typically, it involves one furnace (heater) and two or four coking towers, with continuous feeding to the furnace and alternating operation of the coking towers, making it a semi-continuous process. The feedstock oil (vacuum residue or other heavy oils such as deoiled asphalt, clarified oil, or even sludge) is heated to 495℃~505℃ and then enters the coking tower. The hot feedstock oil undergoes a coking reaction inside the coking tower. The resulting light products exit from the top and enter the fractionation tower, where rich gas, crude gasoline, diesel, and heavy distillate are separated. The coke produced adheres to the inner wall of the coking tower. Once the coke content in the coking tower reaches a certain level, the hot feedstock oil is transferred to another coking tower. Then, the coke remaining in the coking tower is removed by hydraulic decoking.

[0003] During hydraulic decoking, pollutants such as dust, wastewater, and exhaust gas are inevitably generated during the cooling and coke removal processes. Particularly during the large feedwater cooling, coke soaking, and overflow processes, oily and sulfur-containing wastewater at around 100°C is produced, known as cold coke water. Research and analysis have revealed that cold coke water contains a large number of corrosive ions, such as SO42-. 2- Cl - F - Ca 2+ Fe 3+ These ions can corrode metal equipment and pipes; moreover, cold coke water contains a large amount of organic compounds, which are easily enriched during continuous circulation. During the cooling process of coke water, the volatilized organic chemicals can easily pollute the surrounding environment.

[0004] Therefore, how to rationally treat the cold coke water produced by the delayed coking unit is an urgent problem to be solved. Utility Model Content

[0005] The purpose of this invention is to provide an electrochemical treatment device for cold coke water generated during delayed coking, which aims to solve the problem that the cold coke water produced during the delayed coking process contains a large number of corrosive ions and organic compounds.

[0006] To achieve the above objectives, this utility model provides the following technical solution:

[0007] An electrochemical treatment device for delayed coking cold coke water is characterized by comprising a first electrocatalytic oxidation device, a second electrocatalytic oxidation device, an electroadsorption desalination device, and a power supply. The inlet of the first electrocatalytic oxidation device is the cold coke water input port, the outlet of the first electrocatalytic oxidation device is connected to the inlet of the second electrocatalytic oxidation device, the outlet of the second electrocatalytic oxidation device is connected to the inlet of the electroadsorption desalination device, and the electroadsorption desalination device is provided with a fresh water output port and a concentrated water output port. The power supply is electrically connected to the first electrocatalytic oxidation device, the second electrocatalytic oxidation device, and the electroadsorption desalination device.

[0008] As a further preferred embodiment of this technical solution, the first electrocatalytic oxidation device, the second electrocatalytic oxidation device, the electroadsorption desalination device, and the power supply are integrated and installed by a mounting frame. The mounting frame has a stacked structure, and the first electrocatalytic oxidation device, the second electrocatalytic oxidation device, and the electroadsorption desalination device are installed horizontally from top to bottom.

[0009] As a further preferred embodiment of this technical solution, the power supply is installed on the top layer of the mounting bracket.

[0010] As a further preferred embodiment of this technical solution, the power supply is a computer-programmable DC power supply, which is provided with three sets of interfaces, which are respectively electrically connected to the corresponding interfaces of the first electrocatalytic oxidation device, the second electrocatalytic oxidation device, and the electroadsorption desalination device.

[0011] As a further preferred embodiment of this technical solution, a first COD sensor and a first conductivity meter are installed at the inlet end of the first electrocatalytic oxidation device; a second COD sensor and a second conductivity meter are installed on the connecting pipeline between the first and second electrocatalytic oxidation devices; and a third COD sensor and a third conductivity meter are installed at the outlet end of the second electrocatalytic oxidation device. The device also includes a controller, which is electrically connected to the first COD sensor, the first conductivity meter, the second COD sensor, the second conductivity meter, the third COD sensor, the third conductivity meter, and a power supply.

[0012] As a further preferred embodiment of this technical solution, it also includes a water inlet tank, which is connected to the water inlet of the first electrocatalytic oxidation device via a pipeline, and a first drive pump is installed on the connecting pipeline between the water inlet tank and the first electrocatalytic oxidation device.

[0013] As a further preferred embodiment of this technical solution, a desalination buffer tank is also included. The desalination buffer tank is disposed between the connecting pipeline of the second electrocatalytic oxidation device and the electroadsorption desalination device. The desalination buffer tank is connected to the outlet of the second electrocatalytic oxidation device and the inlet of the electroadsorption desalination device through pipelines respectively. A second drive pump is installed on the connecting pipeline between the desalination buffer tank and the electroadsorption desalination device.

[0014] As a further preferred embodiment of this technical solution, it also includes a freshwater tank and a concentrated water tank. The freshwater tank and the concentrated water tank are respectively connected to the freshwater outlet and the concentrated water outlet of the electro-adsorption desalination device through pipelines, and a switch valve is installed on both of the two connecting pipelines of the freshwater tank, the concentrated water tank and the electro-adsorption desalination device.

[0015] As a further preferred embodiment of this technical solution, the first electrocatalytic oxidation device and / or the second electrocatalytic oxidation device include an electrocatalytic reaction chamber, in which a plurality of anode plates and cathode plates are installed. The anode plates and cathode plates are respectively fixedly connected to the upper and lower walls of the electrocatalytic reaction chamber and are arranged alternately.

[0016] As a further preferred embodiment of this technical solution, the electro-adsorption desalination device includes an electro-adsorption reaction chamber, on which cation exchange membranes are respectively disposed on the upper and lower walls, and an anion exchange membrane is disposed between the two cation exchange membranes.

[0017] Compared with the prior art, the beneficial effects of this utility model are:

[0018] This invention employs an electrochemical treatment method combining electrocatalytic oxidation and electroadsorption desalination. The electrocatalytic oxidation device oxidizes and degrades organic matter in the cold coke water, removing its toxicity and achieving complete mineralization. The electroadsorption desalination device reduces the inorganic salt concentration in the cold coke water, thus desalinating it. The combination of these two methods effectively removes corrosive ions and degrades organic compounds in the cold coke water, solving corrosion and pollution problems. Furthermore, this invention is powered by green and low-carbon electricity, and the power supply current output can be controlled by a computer-programmable power supply based on the degradation of pollutants, significantly reducing operating energy costs. The electrochemical treatment method operates under mild reaction conditions, is less affected by external forces, and offers higher safety and reliability. The electrochemical reaction process can be controlled by adjusting the power supply current and voltage, providing strong controllability. Since the electrochemical reaction primarily involves electrons, no external oxidizing or reducing agents are required, effectively avoiding secondary pollution. Attached Figure Description

[0019] The accompanying drawings are provided to further illustrate the present invention and form part of the specification. They are used together with the embodiments of the present invention to explain the present invention, but do not constitute a limitation thereof. In the drawings:

[0020] Figure 1 This is a schematic diagram of the overall structure of this utility model;

[0021] Among them, 1-first electrocatalytic oxidation device, 2-second electrocatalytic oxidation device, 3-electroadsorption desalination device, 4-power supply, 5-mounting frame, 6-inlet tank, 7-first drive pump, 8-desalination buffer tank, 9-second drive pump, 10-fresh water tank, 11-concentrated water tank, 12-switch valve, 13-electrocatalytic reaction chamber, 14-anode plate, 15-cathode plate, 16-electroadsorption reaction chamber, 17-cation exchange membrane, 18-anion exchange membrane. Detailed Implementation

[0022] The technical solutions of the present utility model will be clearly and completely described below with reference to the accompanying drawings of the embodiments. Obviously, the described embodiments are only some embodiments of the present utility model, and not all embodiments. Based on the embodiments of the present utility model, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the protection scope of the present utility model.

[0023] Example 1

[0024] like Figure 1 An electrochemical treatment device for delayed coking cold coke water is shown, comprising a first electrocatalytic oxidation device 1, a second electrocatalytic oxidation device 2, an electroadsorption desalination device 3, and a power supply 4. The inlet of the first electrocatalytic oxidation device 1 is the cold coke water input port, and the outlet of the first electrocatalytic oxidation device 1 is connected to the inlet of the second electrocatalytic oxidation device 2. The outlet of the second electrocatalytic oxidation device 2 is connected to the inlet of the electroadsorption desalination device 3. The electroadsorption desalination device 3 is provided with a fresh water output port and a concentrated water output port. The power supply 4 is electrically connected to the first electrocatalytic oxidation device 1, the second electrocatalytic oxidation device 2, and the electroadsorption desalination device 3.

[0025] More specifically, the first electrocatalytic oxidation device 1 and the second electrocatalytic oxidation device 2 include an electrocatalytic reaction chamber 13, in which a plurality of anode plates 14 and cathode plates 15 are installed. The anode plates 14 and cathode plates 15 are respectively fixedly connected to the upper and lower walls of the electrocatalytic reaction chamber 13 and are arranged alternately. The electroadsorption desalination device 3 includes an electroadsorption reaction chamber 16, in which cation exchange membranes 17 are respectively disposed on the upper and lower walls of the electroadsorption reaction chamber 16, and an anion exchange membrane 18 is disposed between the two cation exchange membranes 17.

[0026] This embodiment employs two electrocatalytic oxidation devices, which can significantly improve the degradation efficiency of organic matter in cold coke water. Specifically, the anode plate 14 of the first electrocatalytic oxidation device 1 uses a titanium-based metal oxide coated electrode, and the cathode plate 15 uses a titanium electrode. The anode plate 14 of the second electrocatalytic oxidation device 2 uses a boron-doped diamond electrode, and the cathode plate 15 uses a titanium electrode. It should be noted that the electrode plate materials of the first electrocatalytic oxidation device 1 and the second electrocatalytic oxidation device 2 are selected based on the overall equipment cost, operating cost, and maintenance cost of the device. Because the untreated cold coke water solution contains calcium and magnesium ions, which are easily enriched on the electrode plates, thereby reducing the oxidation effect of the electrode plates or even damaging the electrode plates, the electrode plates of the first electrocatalytic oxidation device 1 are usually made of electrode materials with lower cost and moderate oxidation capacity, while the electrode materials of the second electrocatalytic oxidation device 2 are selected with higher cost and better oxidation effect. This allows the first electrocatalytic oxidation device 1 to play a certain protective role for the second electrocatalytic oxidation device 2, while also reducing the overall equipment cost, operating cost, and maintenance cost of the device.

[0027] It should be noted that the materials of the electrocatalytic reaction chamber 13 and the electroadsorption reaction chamber 16 must have good corrosion resistance and sealing properties to ensure the stability and safety of the reaction process.

[0028] Furthermore, those skilled in the art should understand that the working principle of the first electrocatalytic oxidation device 1 and the second electrocatalytic oxidation device 2 is as follows: by directly losing electrons on the electrode surface through cold coke water or by using an electric field to generate hydroxyl radicals or other active substances with strong oxidizing capabilities, organic matter that is difficult to remove by ordinary biological methods is oxidized and degraded, thereby removing its toxicity until it is completely mineralized; the working principle of the electroadsorption desalination device 3 is as follows: by applying an external voltage to form an electrostatic field, ions are forced to move towards the electrode with the opposite charge, so that the ions are enriched in the double layer, greatly reducing the concentration of the solution, thereby achieving desalination of the aqueous solution.

[0029] This embodiment employs an electrochemical treatment method combining electrocatalytic oxidation and electroadsorption desalination. The cold coke water undergoes two electrocatalytic oxidation reactions followed by electroadsorption desalination. The entire process is driven by green and low-carbon electricity, significantly reducing operating energy costs. Furthermore, the electrochemical treatment method of electrocatalytic oxidation + electroadsorption desalination operates under relatively mild reaction conditions, is less affected by external forces, and has higher safety and reliability. Simultaneously, the electrochemical reaction process in this embodiment can be adjusted by regulating the supply current and voltage of power supply 4, offering strong controllability. Since the electrochemical reaction primarily involves electrons, no external oxidizing or reducing agents are required, effectively avoiding secondary pollution. Additionally, special electrodes can be selected to provide flocculation and sterilization functions. When the cold coke water contains metal ions, the cathode and anode can operate simultaneously, thereby improving treatment efficiency.

[0030] In addition, in this embodiment, a first COD sensor and a first conductivity meter are installed at the inlet end of the first electrocatalytic oxidation device 1, a second COD sensor and a second conductivity meter are installed on the connecting pipe between the first electrocatalytic oxidation device 1 and the second electrocatalytic oxidation device 2, and a third COD sensor and a third conductivity meter are installed at the outlet end of the second electrocatalytic oxidation device 2; it also includes a controller, which is electrically connected to the first COD sensor, the first conductivity meter, the second COD sensor, the second conductivity meter, the third COD sensor, the third conductivity meter, and the power supply 4 (not shown in the figure).

[0031] The aforementioned first COD sensor, first conductivity meter, second COD sensor, second conductivity meter, third COD sensor, and third conductivity meter are used to monitor the COD value and conductivity of the cold coke water at both ends of the first electrocatalytic oxidation device 1 and the second electrocatalytic oxidation device 2. The controller is used to receive the detection data from the aforementioned detection devices and control the output power of the power supply based on the difference in detection values ​​between the front and rear ends of the first electrocatalytic oxidation device 1 and the second electrocatalytic oxidation device 2. The reason for the above configuration is that the driving current of traditional electrocatalytic oxidation devices is a constant output. If the output is still based on a constant current after the concentration of the substance to be removed decreases, it will cause a lot of energy waste. Therefore, this embodiment can dynamically adjust the output of the power supply 4 according to the degradation of the substance to be removed and the conductivity of the solution, which is beneficial to improving resource utilization and reducing waste.

[0032] Example 2

[0033] This embodiment is a further supplement to embodiment 1. In order to improve the integration of the delayed cold coke water treatment device, the first electrocatalytic oxidation device 1, the second electrocatalytic oxidation device 2, the electroadsorption desalination device 3 and the power supply 4 in this embodiment are all integrated and installed by the mounting frame 5. The mounting frame 5 has a stacked structure, and the first electrocatalytic oxidation device 1, the second electrocatalytic oxidation device 2 and the electroadsorption desalination device 3 are installed horizontally from top to bottom.

[0034] The advantages of stacking the first electrocatalytic oxidation device 1, the second electrocatalytic oxidation device 2, and the electroadsorption desalination device 3 on the mounting frame 5 are: 1. The solution flow between each device can be completed by its own gravity, without the need for additional drive equipment, which can reduce production costs accordingly; 2. The overall device has a high degree of integration, does not require on-site installation, and is conducive to product standardization; 3. The integrated installation structure is more conducive to movement, and the transfer of the overall device is faster.

[0035] Specifically, the power supply 4 is installed on the top layer of the mounting frame 5; and the power supply 4 is a computer-programmable DC power supply, equipped with three sets of interfaces, which are electrically connected to the corresponding interfaces of the first electrocatalytic oxidation device 1, the second electrocatalytic oxidation device 2, and the electroadsorption desalination device 3, respectively. The computer-programmable DC power supply can set and stably output the required current density and voltage according to actual needs and the degradation of pollutants, thereby achieving precise control of the electrocatalytic oxidation process. By changing the current density, its impact on COD removal rate and unit energy consumption can be studied, providing important basis for optimizing process parameters.

[0036] Furthermore, it also includes a water inlet tank 6, which is used to store cold coke water. The water inlet tank 6 is connected to the water inlet of the first electrocatalytic oxidation device 1 through a pipeline, and a first drive pump 7 is installed on the connecting pipeline between the water inlet tank 6 and the first electrocatalytic oxidation device 1.

[0037] Furthermore, it also includes a desalination buffer tank 8, which is used for sedimentation and buffering of the cold coke water after the oxidation reaction. The desalination buffer tank 8 is set between the connecting pipeline of the second electrocatalytic oxidation device 2 and the electro-adsorption desalination device 3. The desalination buffer tank 8 is connected to the outlet of the second electrocatalytic oxidation device 2 and the inlet of the electro-adsorption desalination device 3 through pipelines respectively. A second drive pump 9 is installed on the connecting pipeline of the desalination buffer tank 8 and the electro-adsorption desalination device 3.

[0038] In this embodiment, both the first drive pump 7 and the second drive pump 8 are peristaltic pumps, which have the advantages of being leak-free and easy to maintain. By precisely adjusting the rotational speed of the peristaltic pump, the flow rate of the liquid in the reaction chamber can be precisely controlled, further controlling the contact time and mass transfer efficiency between the reactants and the electrodes, and adjusting the COD removal effect and unit energy consumption. Of course, those skilled in the art can also select other types of drive pump equipment according to actual needs.

[0039] Furthermore, it also includes a freshwater tank 10 and a concentrated water tank 11. The freshwater tank 10 and the concentrated water tank 11 are respectively connected to the freshwater outlet and the concentrated water outlet of the electro-adsorption desalination device 3 through pipes. A switch valve 12 is installed on both of the two connecting pipes between the freshwater tank 10, the concentrated water tank 11 and the electro-adsorption desalination device 3.

[0040] From the perspective of the overall installation, the inlet tank 6, desalination buffer tank 8, freshwater tank 10, and concentrated water tank 11 are located on the same horizontal plane as the mounting frame 2. The working principle of this embodiment is as follows: the cold coke water in the inlet tank 6 is input into the first electrocatalytic oxidation device 1 through the first drive pump 7 for the first electrocatalytic oxidation reaction. Then, under its own gravity, it flows into the second electrocatalytic oxidation device 2 for the second electrocatalytic oxidation reaction. Then, under its own gravity, it flows into the desalination buffer tank 8. The cold coke water after the oxidation reaction is subjected to sedimentation and buffering in the desalination buffer tank 8 for a period of time. Then, it is input into the electro-adsorption desalination device 3 through the second drive pump 9 for desalination. After desalination, the cold coke water is output as freshwater and concentrated water through the outlet of the electro-adsorption desalination device 3, and flows into the freshwater tank 10 and concentrated water tank 11 respectively for rational utilization.

[0041] Finally, it should be noted that the above description is merely a preferred embodiment of this utility model and is not intended to limit the utility model. Although the utility model has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this utility model should be included within the protection scope of this utility model.

Claims

1. An electrochemical treatment device for water from delayed coking cold coke, characterized in that, The device includes a first electrocatalytic oxidation device (1), a second electrocatalytic oxidation device (2), an electro-adsorption desalination device (3), and a power supply (4). The inlet of the first electrocatalytic oxidation device (1) is a cold coke water inlet. The outlet of the first electrocatalytic oxidation device (1) is connected to the inlet of the second electrocatalytic oxidation device (2). The outlet of the second electrocatalytic oxidation device (2) is connected to the inlet of the electro-adsorption desalination device (3). The electro-adsorption desalination device (3) is provided with a fresh water outlet and a concentrated water outlet. The power supply (4) is electrically connected to the first electrocatalytic oxidation device (1), the second electrocatalytic oxidation device (2), and the electro-adsorption desalination device (3).

2. The electrochemical treatment device for delayed coking cold coke water according to claim 1, characterized in that, The first electrocatalytic oxidation device (1), the second electrocatalytic oxidation device (2), the electroadsorption desalination device (3) and the power supply (4) are integrated and installed by a mounting frame (5). The mounting frame (5) has a stacked structure, and the first electrocatalytic oxidation device (1), the second electrocatalytic oxidation device (2) and the electroadsorption desalination device (3) are installed horizontally from top to bottom.

3. The electrochemical treatment device for delayed coking cold coke water according to claim 2, characterized in that, The power supply (4) is installed on the top layer of the mounting bracket (5).

4. The electrochemical treatment device for delayed coking cold coke water according to claim 3, characterized in that, The power supply (4) is a computer programmable DC power supply. Three sets of interfaces are provided on the power supply (4). The three sets of interfaces are electrically connected to the corresponding interfaces of the first electrocatalytic oxidation device (1), the second electrocatalytic oxidation device (2), and the electroadsorption desalination device (3), respectively.

5. The electrochemical treatment device for delayed coking cold coke water according to claim 4, characterized in that, A first COD sensor and a first conductivity meter are installed at the inlet end of the first electrocatalytic oxidation device (1). A second COD sensor and a second conductivity meter are installed on the connecting pipe between the first electrocatalytic oxidation device (1) and the second electrocatalytic oxidation device (2). A third COD sensor and a third conductivity meter are installed at the outlet end of the second electrocatalytic oxidation device (2). The device also includes a controller, which is electrically connected to the first COD sensor, the first conductivity meter, the second COD sensor, the second conductivity meter, the third COD sensor, the third conductivity meter, and a power supply (4).

6. The electrochemical treatment device for delayed coking cold coke water according to claim 2, characterized in that, It also includes a water inlet tank (6), which is connected to the water inlet of the first electrocatalytic oxidation device (1) through a pipeline, and a first drive pump (7) is installed on the connecting pipeline between the water inlet tank (6) and the first electrocatalytic oxidation device (1).

7. The electrochemical treatment device for delayed coking cold coke water according to claim 2, characterized in that, It also includes a desalination buffer tank (8), which is located between the connecting pipeline of the second electrocatalytic oxidation device (2) and the electro-adsorption desalination device (3). The desalination buffer tank (8) is connected to the outlet of the second electrocatalytic oxidation device (2) and the inlet of the electro-adsorption desalination device (3) through pipelines. A second drive pump (9) is installed on the connecting pipeline between the desalination buffer tank (8) and the electro-adsorption desalination device (3).

8. The electrochemical treatment device for delayed coking cold coke water according to claim 2, characterized in that, It also includes a fresh water tank (10) and a concentrated water tank (11). The fresh water tank (10) and the concentrated water tank (11) are respectively connected to the fresh water outlet and the concentrated water outlet of the electro-adsorption desalination device (3) through pipelines. Switch valves (12) are installed on both the fresh water tank (10), the concentrated water tank (11) and the two connecting pipelines of the electro-adsorption desalination device (3).

9. The electrochemical treatment apparatus for delayed coking cold coke water according to any one of claims 1 to 8, characterized in that, The first electrocatalytic oxidation device (1) and / or the second electrocatalytic oxidation device (2) include an electrocatalytic reaction chamber (13), in which a plurality of anode plates (14) and cathode plates (15) are installed. The anode plates (14) and cathode plates (15) are respectively fixedly connected to the upper and lower walls of the electrocatalytic reaction chamber (13) and are arranged alternately.

10. The electrochemical treatment apparatus for delayed coking cold coke water according to any one of claims 1 to 8, characterized in that, The electro-adsorption desalination device (3) includes an electro-adsorption reaction chamber (16), on which cation exchange membranes (17) are respectively provided on the upper and lower walls, and an anion exchange membrane (18) is provided in the middle of the two cation exchange membranes (17).

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