Reaction kettle sampler and hydrogenation reaction device

Abstract

The utility model relates to the field of reaction kettle sampling, and discloses a reaction kettle sampler and a hydrogenation reaction device. The reaction kettle sampler comprises a liquid phase valve 3, an inner sampling pipe 8, a filter 9, an outer sampling pipe 10, a needle valve 11 and a sampling bent pipe 12; one end of the inner sampling tube 8 is connected with the outer sampling tube 10 through the liquid phase valve 3, the other end of the inner sampling tube 8 is a free end capable of extending into a reaction kettle, and the free end is provided with a filter 9; and the outer sampling pipe 10 is connected with the sampling bent pipe 12 through the needle valve 11. The reaction kettle sampler meets the continuous sampling requirements of kinetic research on reaction material samples at different moments, accurately controls the sampling volume of each time, realizes quantitative sampling, provides reliable data for accurate analysis of reaction kinetic parameters, has good stability and reliability, and can meet the long-time and multi-time sampling requirements.

Description

Technical Field

[0001] This utility model relates to the field of reactor sampling, specifically to a reactor sampler and a hydrogenation reaction device. Background Technology

[0002] In scientific research and production processes across numerous fields such as petroleum, chemical engineering, and pharmaceuticals, reaction vessels are extremely important equipment, widely used in various chemical reactions including sulfidation, nitration, hydrogenation, hydrocarbonation, polymerization, and condensation. Particularly important for reactions involving kinetic studies is the continuous and accurate sampling and analysis of materials within a sealed, high-pressure reaction vessel at different reaction times to precisely obtain key kinetic parameters such as reaction rate and reactant concentration changes.

[0003] However, current reactor sampling methods typically involve disassembling the reactor or directly sampling through a liquid phase valve. Traditional disassembly sampling only allows for single, intermittent sampling, which fails to meet the need for continuous monitoring of the reaction process and cannot accurately reflect the true state of the materials at a specific moment. While direct sampling through a liquid phase valve seems convenient, in practice, the material inside the reactor is prone to splashing under high pressure, increasing the difficulty of sampling and potentially posing a serious threat to the safety of operators and the surrounding environment. Furthermore, this sampling method makes it difficult to precisely control the volume of each sample, thus affecting the accuracy and reliability of the sampling results.

[0004] In kinetic studies, existing sampling methods are insufficient to comprehensively and accurately capture the continuous changes in material composition and concentration over time during the reaction process, which in turn leads to certain deviations in the determination and analysis of reaction kinetic parameters.

[0005] Therefore, there is an urgent need to develop a new type of reactor sampling technology to solve the above problems. Utility Model Content

[0006] The purpose of this invention is to overcome the problems of non-continuous sampling and difficulty in quantitative sampling in the existing reactor sampling methods, and to provide a reactor sampler and hydrogenation reaction device. The reactor sampler can continuously sample and accurately control the volume of each sample to achieve quantitative sampling.

[0007] To achieve the above objectives, the first aspect of this utility model provides a reactor sampler, which includes a liquid phase valve 3, an inner sampling tube 8, a filter 9, an outer sampling tube 10, a needle valve 11, and a sampling bend 12.

[0008] One end of the inner sampling tube 8 is connected to the outer sampling tube 10 through the liquid phase valve 3, and the other end of the inner sampling tube 8 is a free end that can extend into the reaction vessel. The free end is equipped with a filter 9.

[0009] The external sampling tube 10 is connected to the sampling bend tube 12 via a needle valve 11.

[0010] The second aspect of this utility model provides a hydrogenation reaction apparatus, the apparatus comprising a reaction vessel, a gas supply device, and a reaction vessel sampler;

[0011] The gas supply device includes a hydrogen supply device, an inert atmosphere supply device, a gas phase valve 2, a pipeline 4, a three-way ball valve 5, and a three-way pipeline 6.

[0012] The hydrogen supply device and the inert atmosphere supply device are each independently connected to the inlet three-way ball valve 15 via pipelines to supply hydrogen and inert atmosphere to the reactor.

[0013] One end of the three-way pipe 6 is connected to the pipe 4 via the air exchange three-way ball valve 5, and the other end of the three-way pipe 6 is connected to the air intake three-way ball valve 15.

[0014] The pipeline 4 is connected to the reactor via the gas phase valve 2;

[0015] The reactor sampler includes a liquid phase valve 3, an inner sampling tube 8, a filter 9, an outer sampling tube 10, a needle valve 11, and a sampling bend 12;

[0016] One end of the inner sampling tube 8 is connected to the outer sampling tube 10 through the liquid phase valve 3, and the other end of the inner sampling tube 8 is a free end that can extend into the reaction vessel. The free end is equipped with a filter 9.

[0017] The external sampling tube 10 is connected to the sampling bend tube 12 via a needle valve 11.

[0018] Through the above technical solution, this utility model has the following beneficial effects:

[0019] (1) The reactor sampler provided by this utility model can perform sampling operations continuously according to the set time interval, solve the problem that traditional sampling methods cannot perform continuous sampling, meet the continuous sampling requirements of kinetic studies for reaction material samples at different times, and provide reliable data for accurate analysis of reaction kinetic parameters.

[0020] (2) The reactor sampler provided by this utility model can accurately control the volume of each sample by setting an external sampling tube, which is highly flexible and has a small error; it is equipped with "dual valves" for sampling, and the speed and size of material discharge can be effectively controlled by controlling the needle valve, avoiding material splashing and ensuring the safety of operators.

[0021] (3) The reactor sampler provided by this utility model has a filter at the end of the inner sampling tube to ensure that solid particles such as catalysts in the material will not flow out with the liquid during sampling, thus avoiding the material from clogging the inner sampling tube, the liquid phase valve and the outer sampling tube. The sampled material can be directly subjected to chromatographic analysis, which improves the accuracy of detection. In a preferred case, after sampling, the sampling tube is backwashed through a hydrogen pipeline to backwash the residual material in the sampling tube back into the reactor, thus avoiding the influence of the residual material in the sampling tube on the next sampling data, ensuring the real-time accuracy of each sampling data, and making the kinetic parameters calculated based on these sample data more reliable. Attached Figure Description

[0022] Figure 1 This is a schematic diagram of the hydrogenation reaction apparatus provided by this utility model;

[0023] Figure 2 These are the analysis results of hydrogenation rate and conversion rate of samples 1 to 18 in Embodiment 1 of this utility model;

[0024] Figure 3 These are the analytical results of the contents of 0H-NEC, 4H-NEC, 8H-NEC, and 12H-NEC in samples 1 to 18 of Example 1 of this utility model.

[0025] Explanation of reference numerals in the attached figures

[0026] 1. Reactor body 2. Gas phase valve 3. Liquid phase valve

[0027] 4. Pipeline; 5. Ventilation three-way ball valve; 6. Three-way pipeline

[0028] 7 Exhaust pipe 8 Internal sampling pipe 9 Filter

[0029] 10 External sampling tube 11 Needle valve 12 Sampling bend

[0030] 13 Sampling bottle 14 Second branch 15 Inlet three-way ball valve Detailed Implementation

[0031] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0032] In utility models, unless otherwise stated, directional terms such as "up," "down," "left," and "right" generally refer to the orientation shown in the accompanying drawings. "Inner" and "outer" refer to the inner and outer sides relative to the outline of each component itself.

[0033] The first aspect of this utility model provides a reactor sampler, which includes a liquid phase valve 3, an inner sampling tube 8, a filter 9, an outer sampling tube 10, a needle valve 11, and a sampling bend 12;

[0034] One end of the inner sampling tube 8 is connected to the outer sampling tube 10 through the liquid phase valve 3, and the other end of the inner sampling tube 8 is a free end that can extend into the reaction vessel. The free end is equipped with a filter 9.

[0035] The external sampling tube 10 is connected to the sampling bend tube 12 via a needle valve 11.

[0036] In this invention, the reactor sampler can continuously perform sampling operations at set time intervals, meeting the continuous sampling requirements of kinetic studies for reactant samples at different times, and providing reliable data for accurate analysis of reaction kinetic parameters. By setting an external sampling tube, the volume of each sample can be accurately controlled, offering high flexibility and keeping the error within a small range. The "dual-valve" sampling system effectively controls the speed and size of material discharge by controlling the needle valve, avoiding material splashing and ensuring operator safety. The filter at the end of the internal sampling tube ensures that solid particles such as catalysts in the material do not flow out with the liquid during sampling, improving detection accuracy.

[0037] According to a preferred embodiment of this invention, the reactor sampler further includes a hydrogen backflush tube, which is used to connect to the sampling bend 12 for backflushing after sampling. In this invention, by performing backflushing in this manner, the residual material in the outer sampling tube 10 and the inner sampling tube 8 is blown back into the reactor body 1 by the pressure difference to continue the reaction, avoiding the influence of residual material in the sampling tube on the next sampling data, ensuring the real-time accuracy of each sampling data, and also serving to replenish the pressure of the reactor.

[0038] According to a preferred embodiment of this invention, the filtration accuracy of the filter 9 is 2-45 μm, preferably 2-10 μm. In this invention, using the above-mentioned preferred filtration accuracy range is more conducive to preventing the material to be sampled from clogging the inner and outer sampling tubes, thereby further improving the accuracy of sampling.

[0039] According to a preferred embodiment of this utility model, the reactor sampler further includes a heating and temperature control device for controlling the temperature of the material in the external sampling tube 10. This utility model is suitable for sampling solidified materials, and can prevent the material in the reactor from solidifying during the process of entering the external sampling tube, thereby blocking the sampling tube and affecting the continuity and accuracy of sampling. The above embodiment is beneficial to improving the accuracy, continuity and safety of sampling, while extending the service life of the equipment.

[0040] In this invention, preferably, the heating and temperature control device is sleeved on the outside of the outer sampling tube 10. The type of heating and temperature control device in this invention is specifically limited; it only needs to perform the functions of heating and heat preservation, for example, it can be a heating jacket.

[0041] In this invention, the material of the inner sampling tube 8 has a wide range of selection; various high-temperature and high-pressure resistant materials commonly used in the art can be used in this invention. Preferably, the material of the inner sampling tube 8 is selected from stainless steel and / or alloys.

[0042] In this invention, the material of the external sampling tube 10 has a wide range of selection; various high-temperature and high-pressure resistant materials commonly used in the art can be used in this invention. The material of the external sampling tube 10 is selected from stainless steel and / or alloys.

[0043] In this invention, the inner diameter and length of the external sampling tube 10 are not particularly limited and need to be calculated based on the volume of the material to be sampled. Preferably, the volume of the external sampling tube 10 is the same as the volume of the material to be sampled. It should be noted that in practical applications, the actual volume of the external sampling tube 10 is slightly larger than the volume of the material to be sampled, but can be considered the same. The arrangement of the external sampling tube 10 in this invention allows for precise control of the volume of each sample by flexibly changing its length, offering high flexibility and minimal error.

[0044] In this invention, the material of the sampling bend 12 is not particularly limited, and each can be made of various high temperature and high pressure resistant materials commonly used in the field, such as stainless steel.

[0045] In this invention, the materials of the liquid phase valve 3, needle valve 11 and filter 9 are not particularly limited, and each can be made of various high temperature and high pressure resistant materials commonly used in the field, such as stainless steel.

[0046] The second aspect of this utility model provides a hydrogenation reaction apparatus, the apparatus comprising a reaction vessel, a gas supply device, and a reaction vessel sampler;

[0047] The gas supply device includes a hydrogen supply device, an inert atmosphere supply device, a gas phase valve 2, a pipeline 4, a three-way ball valve 5, and a three-way pipeline 6.

[0048] The hydrogen supply device and the inert atmosphere supply device are each independently connected to the inlet three-way ball valve 15 via pipelines to supply hydrogen and inert atmosphere to the reactor.

[0049] One end of the three-way pipe 6 is connected to the pipe 4 via the air exchange three-way ball valve 5, and the other end of the three-way pipe 6 is connected to the air intake three-way ball valve 15.

[0050] The pipeline 4 is connected to the reactor via the gas phase valve 2;

[0051] The reactor sampler includes a liquid phase valve 3, an inner sampling tube 8, a filter 9, an outer sampling tube 10, a needle valve 11, and a sampling bend 12;

[0052] One end of the inner sampling tube 8 is connected to the outer sampling tube 10 through the liquid phase valve 3, and the other end of the inner sampling tube 8 is a free end that can extend into the reaction vessel. The free end is equipped with a filter 9.

[0053] The external sampling tube 10 is connected to the sampling bend tube 12 via a needle valve 11.

[0054] The sampling device provided by this utility model, by rationally controlling the opening and closing sequence of each valve, can continuously perform sampling operations at set time intervals while ensuring uninterrupted reaction in the reactor, solving the problem of non-continuous sampling in traditional sampling methods. The external sampling tube allows for accurate control of the volume of each sample, offering high flexibility and minimal error. The "dual-valve" sampling system effectively controls the speed and amount of material discharge through the needle valve, preventing material splashing. Simultaneously, the three-way ball valve fully replaces the air in the reactor, preventing interference from oxygen and other components in the air and ensuring the reaction proceeds in a safe environment. The filter at the end of the internal sampling tube ensures that solid particles such as catalysts in the material do not flow out with the liquid during sampling, improving detection accuracy.

[0055] According to this invention, the specific types of the hydrogen supply device and the inert atmosphere supply device are not particularly limited. Conventional hydrogen supply devices and inert atmosphere supply devices in the art can be used in this invention, such as gas storage cylinders. The type of inert atmosphere in this invention is not particularly limited; for example, it can be nitrogen.

[0056] According to a preferred embodiment of this invention, the hydrogen supply device includes a first branch connected to the inlet three-way ball valve 15 and an optional second branch 14 connected to the sampling bend 12. The second branch 14 is used to connect to the sampling bend 12 for backwashing after sampling. In this invention, backwashing in this manner allows residual material to be blown back into the reactor body using the pressure difference to continue the reaction, avoiding the influence of residual material in the sampling tube on the next sampling data, ensuring the real-time accuracy of each sampling data, and also serving to pressurize the reactor.

[0057] According to a preferred embodiment of the present invention, the hydrogenation reactor further includes an exhaust fan connected to the exhaust gas pipe 7. In this invention, the exhaust fan discharges the air displaced in the reactor through the three-way ball valve 5 and the exhaust gas pipe 7, and into the exhaust gas collection device.

[0058] According to a preferred embodiment of this invention, the filtration accuracy of the filter 9 is 2-45 μm, preferably 2-10 μm. In this invention, using the above-mentioned preferred filtration accuracy range is more conducive to preventing the material to be sampled from clogging the inner and outer sampling tubes, thereby further improving the accuracy of sampling.

[0059] According to a preferred embodiment of this invention, the reactor sampler further includes a heating and temperature control device for controlling the temperature of the material in the external sampling tube 10. This invention is suitable for sampling solidified materials. The above-described embodiment helps improve the accuracy, continuity, and safety of sampling, while also extending the service life of the equipment.

[0060] According to some specific embodiments of this utility model, such as Figure 1 As shown, sampling is performed using the hydrogenation reaction apparatus shown. First, nitrogen is introduced into the reactor body 1 through the nitrogen supply device via the three-way pipe 6 (nitrogen pipe). The nitrogen then enters the reactor body 1 sequentially through the gas exchange three-way ball valve 5, pipe 4, and gas phase valve 2. A pressure holding test is conducted to check the airtightness of the apparatus.

[0061] After confirming no leaks, nitrogen gas is introduced into the reactor body 1 through the three-way ball valve 5 for air replacement. After the replacement is completed, the connection between the three-way ball valve 5 and the three-way pipeline 6 (nitrogen pipeline) and the tail gas discharge pipe 7 is closed to maintain a nitrogen atmosphere in the reactor body 1.

[0062] Open the three-way pipe 6 (hydrogen pipe), and the first branch of the hydrogen supply device will introduce hydrogen into the reactor body 1 through the three-way pipe 6 (hydrogen pipe) to carry out the reaction. After the reaction reaches the predetermined sampling time, close the gas phase valve 2 and the needle valve 11, and open the liquid phase valve 3 to take a sample. After the material is filtered by the filter 9, it enters the outer sampling pipe 10 through the inner sampling pipe 8. After the material fills the outer sampling pipe 10, close the liquid phase valve 3; open the needle valve 11, and the material in the outer sampling pipe 10 flows into the sampling bottle 13 through the sampling bend 12. After all the material in the outer sampling pipe 10 has flowed into the sampling bottle 13, close the needle valve 11 to complete the sampling.

[0063] After sampling, the second branch 14 of the hydrogen supply device is connected to the sampling bend 12 for reverse flushing. The needle valve 11 and the liquid phase valve 3 are opened to backflush the inner sampling tube 8 and the outer sampling tube 10. The residual material is backflushed back to the reactor body 1 by using the pressure difference. Then the liquid phase valve 3 is closed and the gas phase valve 2 is opened to wait for the next sampling.

[0064] The present invention will be described in detail below through embodiments.

[0065] Example 1

[0066] use Figure 1 The hydrogenation reaction apparatus shown is based on the NEC (N-ethylcarbazole) catalytic hydrogenation reaction experiment. A high-pressure reactor with a volume of 500 mL is selected as the reactor body. The reaction temperature is set at 180℃ and the reaction pressure is 4 MPa. The inner sampling tube is made of stainless steel, and the outer sampling tube is also made of stainless steel. The inner diameter of the outer sampling tube is 2 mm. Based on the required sampling volume of 0.5 mL, the calculated length of the outer sampling tube is approximately 15.9 cm (considering a certain margin, the actual value is 20 cm). A stainless steel filter with an accuracy of 5 μm is selected as the filter.

[0067] (1) Clean the reactor, add a certain amount of NEC and catalyst into the reactor, install the reactor, gas supply device and sampling device, and introduce nitrogen into the reactor through the three-way pipeline. Let the nitrogen enter the reactor tank through the gas exchange three-way ball valve and the gas phase valve in sequence. Conduct a pressure test to check the air tightness of the device.

[0068] After confirming there are no leaks, nitrogen gas at 2MPa is introduced into the reactor through the three-way ball valve for air replacement. The replacement operation is repeated 3 times. The replaced air is discharged into the connected exhaust pipe through the tail gas discharge pipe of the three-way ball valve.

[0069] (2) Start heating. After the temperature reaches the set reaction temperature (180°C), start the stirring device. The first branch of the hydrogen supply device introduces 4MPa of hydrogen into the reactor through the three-way pipe to start the reaction.

[0070] (3) When the reaction proceeds to 60 min, start sampling, close the gas phase valve and needle valve, slowly open the liquid phase valve, and the material fills the external sampling tube under the pressure inside the reactor. Close the liquid phase valve and slowly open the needle valve so that the material flows slowly into the sampling bottle through the sampling bend. After all the material in the external sampling tube has flowed into the sampling bottle, close the needle valve.

[0071] (4) After sampling, connect the second branch of the hydrogen supply device to the sampling bend, open the needle valve and the liquid phase valve, and backflush the sampling tube (inner sampling tube and outer sampling tube). The material in the sampling tube is backflushed back to the reactor under the action of pressure difference. Then close the liquid phase valve and the needle valve, open the gas phase valve, continue the reaction, and wait for the next sampling.

[0072] The sampling bottle was labeled as Sample 1, and its components and contents were analyzed by gas chromatography.

[0073] Following the above steps, the first sampling was conducted at 60 minutes of reaction, with a sampling interval of 10 minutes. The 18th sampling was completed at 240 minutes of reaction, yielding samples 2 through 18, which were then analyzed by gas chromatography. The hydrogenation rate and conversion rate analysis results for samples 1 through 18 are as follows: Figure 2 As shown, the analytical results of the contents of 0H-NEC, 4H-NEC, 8H-NEC, and 12H-NEC in samples 1 to 18 are as follows: Figure 3 As shown, by Figure 2 and Figure 3 It can be seen that the changes in material composition and content during the reaction process are consistent with the theory, and the concentration of substances in the sample is highly consistent with the actual situation inside the reactor.

[0074] The results above show that the reactor sampler provided by this invention can accurately obtain material samples at different stages of the reaction process, meeting the accuracy requirements of material composition analysis in reaction kinetics research. No material splashing occurred during the entire sampling process, and operators can operate in a safe environment. After multiple sampling operations, all components of the reactor and sampling device operated normally without leakage or blockage, demonstrating good stability and reliability, and can adapt to long-term and multiple sampling needs.

[0075] The preferred embodiments of this utility model have been described in detail above; however, this utility model is not limited thereto. Within the scope of the technical concept of this utility model, various simple modifications can be made to the technical solution of this utility model, including combining the various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed by this utility model and are all within the protection scope of this utility model.

Claims

1. A sampler for a reaction vessel, characterized in that, The reactor sampler includes a liquid phase valve (3), an inner sampling tube (8), a filter (9), an outer sampling tube (10), a needle valve (11), and a sampling bend (12); One end of the inner sampling tube (8) is connected to the outer sampling tube (10) through the liquid phase valve (3), and the other end of the inner sampling tube (8) is a free end that can be inserted into the reactor. The free end is equipped with a filter (9). The external sampling tube (10) is connected to the sampling bend (12) via a needle valve (11).

2. The reactor sampler according to claim 1, characterized in that, The reactor sampler also includes a hydrogen backflush tube, which is used to connect to the sampling bend (12) for reverse flushing after sampling is completed.

3. The reactor sampler according to claim 1, characterized in that, The filter (9) has a filtration accuracy of 2-45 μm.

4. The reactor sampler according to claim 1, characterized in that, The reactor sampler also includes a heating and temperature control device for controlling the temperature of the material in the external sampling tube (10).

5. The reactor sampler according to claim 1, characterized in that, The material of the inner sampling tube (8) is selected from stainless steel and / or alloy; The material of the external sampling tube (10) is selected from stainless steel and / or alloys.

6. A hydrogenation reaction apparatus, characterized in that, The device includes a reaction vessel, a gas supply device, and a reaction vessel sampler; The gas supply device includes a hydrogen supply device, an inert atmosphere supply device, a gas phase valve (2), a pipeline (4), a three-way ball valve for gas exchange (5), and a three-way pipeline (6); The hydrogen supply device and the inert atmosphere supply device are each independently connected to the inlet three-way ball valve (15) via pipelines to supply hydrogen and inert atmosphere to the reactor. One end of the three-way pipe (6) is connected to the pipe (4) through the ventilation three-way ball valve (5), and the other end of the three-way pipe (6) is connected to the intake three-way ball valve (15). The pipeline (4) is connected to the reactor via the gas phase valve (2); The reactor sampler includes a liquid phase valve (3), an inner sampling tube (8), a filter (9), an outer sampling tube (10), a needle valve (11), and a sampling bend (12); One end of the inner sampling tube (8) is connected to the outer sampling tube (10) through the liquid phase valve (3), and the other end of the inner sampling tube (8) is a free end that can be inserted into the reactor. The free end is equipped with a filter (9). The external sampling tube (10) is connected to the sampling bend (12) via a needle valve (11).

7. The hydrogenation reactor according to claim 6, characterized in that, The hydrogen supply device includes a first branch connected to the inlet three-way ball valve (15) and an optional second branch (14) connected to the sampling bend (12). The second branch (14) is used to connect to the sampling bend (12) for reverse rinsing after sampling is completed.

8. The hydrogenation reactor according to claim 6, characterized in that, The hydrogenation reaction device also includes a blower, which is connected to the exhaust pipe (7).

9. The hydrogenation reactor according to claim 6, characterized in that, The filter (9) has a filtration accuracy of 2-45 μm.

10. The hydrogenation reactor according to claim 6, characterized in that, The reactor sampler also includes a heating and temperature control device for controlling the temperature of the material in the external sampling tube (10).

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