High pressure solids laden media on-line sampling system and method

Abstract

The present application relates to the technical field of online sampling, and discloses a high-pressure solid-containing medium online sampling system and method. The system comprises a liquid feeding unit, a gas feeding unit, a reaction unit, an online sampling unit, a product collecting unit and a pressure control unit; the outlets of the liquid feeding unit and the gas feeding unit are respectively communicated with the inlet of the reaction unit; the outlet of the reaction unit is respectively communicated with the inlet of the online sampling unit and the inlet of the product collecting unit; the pressure control unit is used for controlling the pressure of the system; the outlet of the product collecting unit is communicated with the inlet of the reaction unit; the online sampling unit comprises a sampling device and at least two three-way pneumatic valves connected in series. The system can realize high-pressure solid-containing medium online sampling, and the sampling analysis process can be completed without stopping work during the sampling process, thereby achieving the purpose of online sampling analysis, and the sampling product has good reproducibility.

Description

Technical Field

[0001] This invention relates to the technical field of online sampling, and specifically to an online sampling system and method for high-pressure solid-containing media. Background Technology

[0002] In the design of small and medium-sized experimental equipment, collecting representative reaction products and analyzing their composition is a key aspect of the design process. For continuous reaction equipment where reaction products contain solid particles, intermediate products need to be collected online, or the system pressure is high, the complexity and difficulty of the experimental equipment design are significantly increased. For example, in the design of microchannel reactors, solid catalysts are uniformly mixed with liquid raw materials before entering the reaction system, and the solid-containing products after the reaction in the microreactor need to be collected and analyzed online in real time.

[0003] Patent application CN105092294A discloses an online sampling system and a method for online sampling using this system. This method uses a miniature sampling canister to collect products. The products enter a pressure-reducing device through the sampling port at the bottom of the miniature sampling canister for pressure reduction. The depressurized products are then supplied to a vaporization tank for vaporization. The vaporized products are then discharged through the outlet of the vaporization tank and, via the pressure-reducing device, into an analytical instrument for analysis. This method is only suitable for collecting gas-liquid two-phase reaction products. When the reaction products contain solid particles, these particles cannot flow through the pressure-reducing device, and their accumulation over time can clog the pipeline. Furthermore, the reaction products in the miniature sampling canister are in a static state, resulting in uneven mixing and making the collected and analyzed products less representative.

[0004] Patent application CN106556525A discloses an online sampling system for polymer slurry. In this system, the bottom of the reactor is connected to the sampling system via a bottom valve. When the bottom valve is opened, the reaction product flows into the sampling tube. Then, when the bottom valve is closed, a metering pump pushes the reaction product and solvent together into the sampling device for analysis. This method is only applicable to batch reactors. During each start-up and shutdown of the bottom valve for sampling, the pressure inside the polymerization reactor fluctuates significantly, affecting the degree of reaction within the reactor. Summary of the Invention

[0005] The purpose of this invention is to overcome the problems of difficulty in continuous sampling and poor reproducibility of high-pressure solid-containing media in the prior art, and to provide a high-pressure solid-containing online sampling system and method. This system can achieve online sampling of high-pressure solid-containing media simply and quickly, without stopping the operation during the sampling process, thereby achieving the purpose of online sampling and analysis, and the sampled products have good reproducibility.

[0006] To achieve the above objectives, the first aspect of the present invention provides a high-pressure online sampling system for solid media, wherein the system includes: a liquid feeding unit, a gas feeding unit, a reaction unit, an online sampling unit, a product collection unit, and a pressure control unit;

[0007] The outlets of the liquid feeding unit and the gas feeding unit are respectively connected to the inlet of the reaction unit;

[0008] The outlet of the reaction unit is connected to the inlet of the online sampling unit and the inlet of the product collection unit, respectively.

[0009] The pressure control unit is used to control the pressure of the system.

[0010] The outlet of the product collection unit is connected to the inlet of the reaction unit;

[0011] The online sampling unit includes a sampling device and at least two three-way pneumatic valves connected in series.

[0012] The three-way pneumatic valve includes a first three-way valve and a second three-way valve. The common terminal COM of the first three-way valve is connected to the outlet of the reaction unit, the normally closed terminal NC of the first three-way valve is connected to the common terminal COM of the second three-way valve, and the normally closed terminal of the second three-way valve is connected to the inlet of the sampling device.

[0013] A second aspect of the present invention provides a method for online sampling of high-pressure solid-containing media, wherein the method is performed in the online sampling system for high-pressure solid-containing media described in the first aspect.

[0014] Preferably, the method includes:

[0015] S1, Reaction Stage: Gas and liquid reactants are introduced into the reaction unit and mixed to obtain a solid-containing mixed product. At this time, the first three-way valve, the second three-way valve and the third three-way valve are all de-energized. The solid-containing mixed product flows through the first three-way valve and the third three-way valve into the collection tank.

[0016] S2, Sampling stage: The first three-way valve and the third three-way valve are energized, and the second three-way valve is de-energized. The solid-containing mixed product flows through the first three-way valve, the sampling tank, and the second three-way valve, and enters the collection tank from the common terminal COM of the third three-way valve. During this stage, the sampling tank is filled with the product to be collected and analyzed.

[0017] S3. Sampling stage: The first three-way valve and the third three-way valve are de-energized, and the second three-way valve is energized. The solid mixture flows through the first three-way valve and the third three-way valve into the collection tank. At the same time, the product to be collected and analyzed stored in the sampling tank in step S2 flows through the second three-way valve into the sampling device under its own weight and / or gas pressure.

[0018] Compared with existing technologies, the method provided by this invention has the following advantages:

[0019] In this invention, multiple three-way pneumatic valve groups are used in conjunction to achieve precise and automatic online sampling. No throttling points are set during the sampling process, resulting in minimal pressure fluctuations and a low risk of pipeline blockage. This invention is particularly suitable for online sampling of products containing solids mixtures.

[0020] In a preferred embodiment, the system provided by the present invention does not have any diversion structure. During the sampling process, all solid-containing mixed products flow through the sampling tank rapidly, resulting in fast replacement speed, no residual products, and the collected products to be analyzed have excellent reproducibility.

[0021] In a preferred embodiment, the system provided by the present invention is equipped with online and offline sampling functions. The online sampling time, number of samplings, and sampling tank volume can all be set by the user, making the sampling highly flexible and providing strong support for studying the overall reaction product distribution and the degree, mechanism, and product distribution of the reaction at different time periods. Attached Figure Description

[0022] Figure 1 These are schematic diagrams of the sampling systems in Embodiments 1 and 2 of the present invention;

[0023] Figure 2 This is a schematic diagram of the reaction stage of the sampling system in Embodiments 1 and 2 of the present invention;

[0024] Figure 3 This is a schematic diagram of the sampling stage of the sampling system in Embodiments 1 and 2 of the present invention;

[0025] Figure 4 This is a schematic diagram of the sampling stage of the sampling system in Embodiments 1 and 2 of the present invention;

[0026] Figure 5 This is a schematic diagram of the sampling system of Comparative Example 1 of the present invention.

[0027] Explanation of reference numerals in the attached figures:

[0028] 1-Raw material tank 2-Agitator

[0029] 3-Raw material gas cylinder 4-Pressure reducing device

[0030] 5-Feed pump 6-Gas feed valve

[0031] 7-Heat exchange device 8-Reaction device

[0032] 9-First three-way valve 10-Third three-way valve

[0033] 11-Sampling container 12-Second three-way valve

[0034] 13-Sampling device 14-Collection container

[0035] 15-Discharge valve 16-Pressure measuring device

[0036] 17-Switching valve 18-Back pressure device

[0037] 19-Gas emission device 20-Gas outlet

[0038] 21-Throttle valve Detailed Implementation

[0039] 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.

[0040] In this invention, unless otherwise specified, all components in the system are connected by pipelines.

[0041] The first aspect of this invention provides a high-pressure online sampling system for solid-containing media, such as... Figure 1 As shown, the system includes: a liquid feeding unit, a gas feeding unit, a reaction unit, an online sampling unit, a product collection unit, and a pressure control unit;

[0042] The outlets of the liquid feeding unit and the gas feeding unit are respectively connected to the inlet of the reaction unit;

[0043] The outlet of the reaction unit is connected to the inlet of the online sampling unit and the inlet of the product collection unit, respectively.

[0044] The pressure control unit is used to control the pressure of the system.

[0045] The outlet of the product collection unit is connected to the inlet of the reaction unit;

[0046] The online sampling unit includes a sampling device 13 and at least two three-way pneumatic valves connected in series.

[0047] The three-way pneumatic valve includes a first three-way valve 9 and a second three-way valve 12. The common end COM of the first three-way valve 9 is connected to the outlet of the reaction unit, the normally closed end NC of the first three-way valve 9 is connected to the common end COM of the second three-way valve 12, and the normally closed end NC of the second three-way valve 12 is connected to the inlet of the sampling device 13.

[0048] The system provided by this invention enables online sampling and analysis of solid-containing mixed products without interrupting operations, thus saving costs. Using the system of this invention, the sampling process has a fast replacement speed and a low risk of pipeline blockage, which can effectively avoid pipeline blockage and thus make the analyzed products have good reproducibility. It is especially suitable for the evaluation of medium and small-sized devices containing solid-containing mixed products.

[0049] In a preferred embodiment, the liquid feeding unit is used to provide liquid reaction raw materials to the reaction unit, and the liquid feeding unit includes a raw material tank 1 and a feed pump 5 connected in the direction of liquid reaction raw material flow.

[0050] In this invention, it is understood that the solid medium can be placed in the liquid feeding unit or in the reaction unit, preferably in the liquid feeding unit.

[0051] In this invention, the type of solid medium is not specifically limited; for example, it can be catalyst particles, which are illustrated schematically in this invention. The type of catalyst is not particularly limited in this invention and can be selected according to the specific reaction; for example, it can be a hydrogenation catalyst.

[0052] In a preferred embodiment, the raw material tank 1 is equipped with a stirring device 2. In this invention, the raw material tank is used to store liquid reaction raw materials, and the stirring device can accelerate the mixing of the liquid reaction raw materials and the solid medium.

[0053] In a preferred embodiment, the gas feeding unit is used to supply gas to the reaction unit.

[0054] In this invention, it is understood that the gas can be a gas that participates in the reaction or a gas that does not participate in the reaction, preferably an inert gas, which is used to establish system pressure or to purge the system.

[0055] In this invention, there are no particular limitations on the specific structure and composition of the gas feeding unit. Preferably, the gas feeding unit includes a raw material gas cylinder 3 connected in the gas direction, a pressure reducing device 4, and a gas feeding valve 6.

[0056] In a preferred embodiment, the reaction unit is used to react liquid reactants and gas to obtain a solid-containing mixed product.

[0057] In this invention, the specific structure and composition of the reaction unit are not particularly limited. Preferably, the reaction unit includes a heat exchange device 7 and a reaction device 8. In this invention, the solid-containing mixed product obtained from the reaction unit enters the online sampling unit and / or product collection unit.

[0058] In this invention, preferably, the heat exchange device 7 is used to exchange heat with the reaction device 8. There are no particular limitations on the connection method between the heat exchange device and the reaction device; they can be connected in parallel or in series, but parallel connection is preferred.

[0059] In a preferred embodiment, the online sampling unit is used to perform online sampling and analysis of solid-containing mixed products.

[0060] In this invention, the specific structure of the online sampling unit is not particularly limited. Preferably, the online sampling unit further includes a sampling tank 11, which is disposed between the first three-way valve 9 and the second three-way valve 12. In this invention, by setting up the sampling tank, the product to be analyzed is temporarily stored in the sampling tank during the online sampling process of the solid mixture, and enters the next stage under its own weight or gas power.

[0061] In this invention, there is no particular limitation on the specific shape of the sampling container. It can be can-shaped or tubular. In this invention, the can shape is used for illustrative purposes.

[0062] In this invention, there are no particular limitations on the connection relationship between the sampling tank and other components, as long as the connection between the various components can be achieved. Preferably, the inlet of the sampling tank 11 is connected to the normally closed end NC of the first three-way valve 9, and the outlet of the sampling tank 11 is connected to the common end COM of the second three-way valve 12.

[0063] In this invention, there is no particular limitation on the volume of the sampling container, and those skilled in the art can select it according to actual needs. Preferably, the volume of the sampling container 11 is 1-10 mL, and more preferably 1-5 mL.

[0064] In a preferred embodiment, both the first three-way valve 9 and the second three-way valve 12 are ball valves without throttling points. The advantages of this preferred embodiment are that the ball valve structure is simple, the fluid resistance is low, and when the reaction products contain solid particles, the risk of pipeline and valve blockage can be reduced.

[0065] In a preferred embodiment, the first three-way valve 9 is vertically connected to the sampling tank 11 and / or the second three-way valve 12. The advantage of this preferred embodiment is that the reaction products can flow directly into the sampling device under the influence of gravity and gas pressure.

[0066] In a preferred embodiment, the sampling container 11 is vertically connected to the sampling device 13. The advantage of this preferred embodiment is that the reaction products flow into the sampling device under the influence of gravity and gas pressure, especially when the amount of reaction gas is small, it can be achieved directly by its own weight.

[0067] In a preferred embodiment, the distance between the second three-way valve 12 and the sampling device 13 is 0-0.005m, preferably 0-0.001m. The advantage of this preferred embodiment is that the shorter the distance between them, the less residual sample remains in the pipeline, and the more representative the sample is.

[0068] In a preferred embodiment, the product collection unit is used to collect a mixture of solids-containing products.

[0069] In this invention, there is no particular limitation on the specific structure of the product collection unit. Preferably, the product collection unit includes a collection tank 14 and a discharge valve 15 disposed at the outlet of the collection tank 14.

[0070] In this invention, there is no particular limitation on the volume of the collection tank, and those skilled in the art can select it according to actual needs. Preferably, the volume of the collection tank 14 is 1000-10000mL, and more preferably 1000-5000mL.

[0071] In a preferred embodiment, the discharge valve 15 is a ball valve structure without a throttling point. The advantage of this preferred embodiment is that the collection tank 14 contains accumulated samples, and the catalyst particles are deposited at the bottom of the collection tank. Using a ball valve with low flow resistance reduces the risk of clogging.

[0072] In a preferred embodiment, the system further includes a third three-way valve 10 disposed between the first three-way valve 9 and the product collection unit.

[0073] In a preferred embodiment, the normally open terminal NO of the third three-way valve 10 is connected to the normally open terminal NO of the first three-way valve 9, the normally closed terminal NC of the third three-way valve 10 is connected to the normally open terminal NO of the second three-way valve 12, and the common terminal COM of the third three-way valve 10 is connected to the inlet of the product collection unit. The advantage of this preferred embodiment is that online sample collection can be achieved by switching the three solenoid valves.

[0074] In a preferred embodiment, the pressure control unit is disposed on the connecting pipeline between the gas outlet 20 of the product collection unit and the inlet of the reaction unit.

[0075] In this invention, the specific structure of the pressure control unit is not particularly limited. Preferably, the pressure control unit includes a back pressure device 18 and a gas discharge device 19 connected in series. The outlet of the back pressure device 18 is connected to the gas outlet 20 of the product collection unit, and the inlet of the back pressure device 18 is connected to the inlet of the reaction unit. In this invention, the back pressure device is used to regulate the system pressure, enabling the system to quickly establish a pressure system before operation, and simultaneously preventing insufficient gas generation during operation that could lead to a drop in reaction pressure, thereby ensuring the reaction pressure.

[0076] In a preferred embodiment, the pressure control unit further includes a pressure measuring device 16 disposed between the back pressure device 18 and the gas outlet 20 of the product collection unit for measuring the reaction pressure of the system.

[0077] In a preferred embodiment, the system further includes a switching valve 17, which is disposed on the connecting pipeline between the outlet of the pressure reducing device 4 and the pressure control unit. The switching valve 17 is used to switch gases. In this invention, the switching valve 17 is a three-way ball valve. The advantage of this preferred embodiment is that when the reaction gas products cannot establish system pressure, the common end of the switching valve can be connected to the gas feed unit to supplement gas; when the back pressure device malfunctions or requires emergency pressure relief, the common end can be connected to the venting pipeline for rapid venting and gas release.

[0078] In this invention, it is understood that the control of system pressure includes the following two situations: first, establishing system pressure through a back pressure device before system operation; second, regulating system pressure through a pressure control unit during system operation. During system operation, the pressure control unit is used, on the one hand, to introduce gas (preferably nitrogen) to supplement pressure when the system pressure is insufficient (due to a small amount of reaction gaseous products during the reaction process, resulting in insufficient system pressure); on the other hand, it is used to quickly vent gas from the system to reduce pressure when the system needs to be depressurized. Specifically, during the reaction, the system pressure is monitored by the pressure measuring device 16. When the system needs to supplement pressure, gas (preferably nitrogen) is introduced into the raw material gas cylinder 3. At this time, the common end of the switching valve 17 is connected to the pressure reducing device 4, and the gas enters the system through the pressure reducing device 4 and the back pressure device 18 to supplement the system pressure. When pressure needs to be depressurized, the reaction gaseous products generated in the system flow through the collection tank 14, and the common end of the switching valve 17 is connected to the gas discharge device 19. The reaction gaseous products are discharged through the gas outlet 20 and the gas discharge device 19.

[0079] A second aspect of the present invention provides a method for online sampling of high-pressure solid-containing media, wherein the method is performed in the online sampling system for high-pressure solid-containing media described in the first aspect.

[0080] In a preferred embodiment, the method includes:

[0081] S1, Reaction Stage: Gas and liquid reactants are introduced into the reaction unit and mixed to obtain a solid-containing mixed product. At this time, the first three-way valve, the second three-way valve and the third three-way valve are all de-energized. The solid-containing mixed product flows through the first three-way valve and the third three-way valve into the collection tank.

[0082] S2, Sampling stage: The first three-way valve and the third three-way valve are energized, and the second three-way valve is de-energized. The solid-containing mixed product flows through the first three-way valve, the sampling tank, and the second three-way valve, and enters the collection tank from the common terminal COM of the third three-way valve. During this stage, the sampling tank is filled with the product to be collected and analyzed.

[0083] S3. Sampling stage: The first three-way valve and the third three-way valve are de-energized, and the second three-way valve is energized. The solid mixture flows through the first three-way valve and the third three-way valve into the collection tank. At the same time, the product to be collected and analyzed stored in the sampling tank in step S2 flows through the second three-way valve into the sampling device under its own weight and / or gas pressure.

[0084] The above-described preferred embodiments have the advantages of good sampling reproducibility, high degree of automation, and high applicability to solid products.

[0085] In this invention, the selection range of conditions for the reaction unit is relatively wide. Preferably, the pressure of the reaction unit is 0.1-5 MPa and the temperature is 50-500°C; more preferably, the pressure of the reaction unit is 0.1-2 MPa and the temperature is 50-200°C. The advantage of this preferred embodiment is its strong applicability, and the preferred reaction conditions are particularly suitable for microchannel reactors.

[0086] In this invention, there is no particular limitation on the type of gas. Preferably, the gas is selected from inert gases and / or reactant gases.

[0087] The specific embodiments of the present invention will be described in detail below with reference to the examples, but are not limited to the following examples.

[0088] Example 1

[0089] Reference Figure 1 In this embodiment, the gas in the raw material cylinder 3 is nitrogen, and the raw material tank 1 contains a slurry of catalyst, solvent, and liquid raw materials. Before system operation, the heat exchanger 7 is turned on to raise the temperature of the reaction device 8 to 180°C and the cooling temperature to 50°C. The stirring device 2 and the feed pump 5 are turned on to mix the catalyst and liquid raw materials evenly before entering the reaction unit. The gas feed valve 6 is closed, and the switching valve 17 is switched to the state where the gas and pressure control unit are connected, so that the gas fills the entire system. The back pressure device 18 is adjusted so that the pressure measuring device 16 displays a pressure of 0.5 MPa.

[0090] After nitrogen, catalyst and liquid raw materials enter the reaction unit, they react at a reaction temperature of 180℃ and a reaction pressure of 0.5MPa. After cooling, a solid-containing mixed product of gas, liquid and catalyst particles is obtained.

[0091] Reference Figure 2During the reaction stage, the first three-way valve 9, the second three-way valve 12, and the third three-way valve 10 are all de-energized. The reaction products pass through the common terminal COM and normally open terminal NO of the first three-way valve 9 and the normally open terminal NO and common terminal COM of the third three-way valve 10, and enter the collection tank 14. The sampling tank 11 contains no solid mixed products, and the volume of the sampling tank 11 is 5 mL.

[0092] Reference Figure 3 When the system starts the automatic sampling function and switches to the sampling stage, the first three-way valve 9 and the third three-way valve 10 are immediately energized, while the second three-way valve 12 remains de-energized. The solid-containing mixed product after the reaction flows through the common end COM and normally closed end NC of the first three-way valve 9 through the sampling tank 11, and then through the common end COM and normally open end NO of the second three-way valve 12, and the normally closed end NC and common end COM of the third three-way valve 10 into the collection tank 14. In this stage, the tank 11 is filled with the solid-containing mixed product to be analyzed, and the volume of the collection tank 14 is 3000mL.

[0093] Reference Figure 4 When the sampling phase ends, the system switches to the sampling phase. The first three-way valve 9 and the third three-way valve 10 are immediately de-energized, and the second three-way valve 12 is then energized. The solid-containing mixed product flowing out of the reaction unit enters the collection tank 14 through the common terminal COM and normally open terminal NC of the first three-way valve 9 and the normally open terminal NC and common terminal COM of the third three-way valve 10. At the same time, the solid-containing mixed product to be analyzed stored in the sampling tank 11 during the sampling phase enters the sampling device 13 through the common terminal COM and normally closed terminal NC of the second three-way valve 12.

[0094] See attached document Figure 2 After the sampling device 13 has collected the product, the second three-way valve 12 is de-energized, and the next sampling process begins.

[0095] In order to successfully remove the solid-containing mixed product to be analyzed from the sampling tank 11, the first three-way valve 9 is set perpendicular to the sampling tank 11 and / or the second three-way valve 12, the sampling tank 11 and the sampling device 13 are set perpendicular to each other, and the distance between the second three-way valve 12 and the sampling device 13 is 0.005m.

[0096] The reaction pressure of this system is regulated and controlled by the back pressure device 18. Specifically, nitrogen is introduced through the raw material gas cylinder 3 to quickly establish the system pressure before the system is started, while avoiding the situation where the reaction pressure drops due to insufficient gas production during operation.

[0097] After the reaction is complete, switching valve 17 is switched to the state where the pressure control unit and gas emission device 19 are connected, and all waste gas is discharged. The discharge valve 15 is opened to collect the reaction products for offline product analysis. The raw material tank 1 is replaced with cleaning medium water to flush the entire system. After flushing, the feed pump 5 is turned off, and the gas feed valve 6 is opened to purge the entire system.

[0098] Using the above system and method, after the reaction started, a sample was taken every 10 minutes, and the volume of the sample was measured each time. The results of the sampling volumes were repeated 5 times, and are shown in Table 1.

[0099] Example 2

[0100] The system and method of Example 1 differ in that H2 is used as the gaseous feedstock, 3L of aromatic nitro compound is placed in feedstock tank 1, and 10g of halogenated nitro hydrogenation catalyst is packed in reaction apparatus 8.

[0101] Reference Figure 1 The gaseous feedstock is H2. Switch valve 17 is closed, gas feed valve 6 is opened, and back pressure device 18 is adjusted so that pressure measuring device 16 displays a value of 1.8 MPa. Heat exchange device 7 is turned on to raise the temperature of reaction device 8 to 200°C and the cooling temperature to 50°C. Liquid feedstock is placed in feed tank 1, catalyst is loaded into reaction device 8, and feed pump 6 is started.

[0102] The reaction yields a gas-liquid mixture or a mixture containing a small amount of catalyst particles, as per [reference needed]. Figure 2 , Figure 3 , Figure 4 Sampling and collection are carried out through online sampling units and product collection units.

[0103] Using the above system and method, after the reaction started, a sample was taken every 10 minutes, and the volume of the sample was measured each time. The results of the sampling volumes were repeated 5 times, and are shown in Table 1.

[0104] Comparative Example 1

[0105] Following the reaction conditions of Example 2, refer to... Figure 5 The system shown only has a first three-way valve 9. During the sampling stage, the solid-containing mixed product directly enters the sampling device 13 for sampling via the first three-way valve and the throttle valve 21. Using the above system and method, after the reaction begins, samples are taken every 10 minutes, and the volume of each sample is measured. The sampling volume results are shown in Table 1 after repeating the sampling five times.

[0106] Table 1

[0107]

[0108]

[0109] Note: In Table 1, 1, 2, 3, 4, and 5 represent the number of samplings.

[0110] The results above show that the valve group switching sampling method in the system of the present invention has significantly better sampling reproducibility (the values ​​of the 5 sampling results are consistent) and operational flexibility.

[0111] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A high-pressure online sampling system for solid-containing media, characterized in that, The system includes: a liquid feeding unit, a gas feeding unit, a reaction unit, an online sampling unit, a product collection unit, and a pressure control unit; The outlets of the liquid feeding unit and the gas feeding unit are respectively connected to the inlet of the reaction unit; The outlet of the reaction unit is connected to the inlet of the online sampling unit and the inlet of the product collection unit, respectively. The pressure control unit is used to control the pressure of the system. The outlet of the product collection unit is connected to the inlet of the reaction unit; The online sampling unit includes a sampling device and at least two three-way pneumatic valves connected in series. The three-way pneumatic valve includes a first three-way valve and a second three-way valve. The common terminal COM of the first three-way valve is connected to the outlet of the reaction unit, the normally closed terminal NC of the first three-way valve is connected to the common terminal COM of the second three-way valve, and the normally closed terminal NC of the second three-way valve is connected to the inlet of the sampling device. The system also includes a third three-way valve disposed between the first three-way valve and the product collection unit. The normally open terminal NO of the third three-way valve is connected to the normally open terminal NO of the first three-way valve, the normally closed terminal NC of the third three-way valve is connected to the normally open terminal NO of the second three-way valve, and the common terminal COM of the third three-way valve is connected to the inlet of the product collection unit. Both the first three-way valve and the second three-way valve are ball valve structures without throttling points.

2. The system according to claim 1, wherein, The liquid feeding unit is used to supply liquid reaction raw materials to the reaction unit, and the liquid feeding unit includes a raw material tank and a feed pump connected in the direction of liquid reaction raw material flow.

3. The system according to claim 2, wherein, The raw material tank is equipped with a stirring device.

4. The system according to claim 1 or 2, wherein, The gas feeding unit is used to supply gas to the reaction unit.

5. The system according to claim 4, wherein, The gas feeding unit includes a raw material gas cylinder, a pressure reducing device, and a gas feeding valve that are connected in the gas direction.

6. The system according to claim 1 or 2, wherein, The reaction unit is used to react liquid reactants and gases to obtain a solid-containing mixed product.

7. The system according to claim 1 or 2, wherein, The reaction unit includes a heat exchange device and a reaction device.

8. The system according to claim 1 or 2, wherein, The online sampling unit is used for online sampling and analysis of solid-containing mixed products.

9. The system according to claim 8, wherein, The online sampling unit also includes a sampling tank, which is disposed between the first three-way valve and the second three-way valve.

10. The system according to claim 9, wherein, The inlet of the sampling tank is connected to the normally closed end NC of the first three-way valve, and the outlet of the sampling tank is connected to the common end COM of the second three-way valve.

11. The system according to claim 9, wherein, The volume of the sampling container is 1-10 mL.

12. The system according to claim 9, wherein, The first three-way valve is vertically connected to the sampling tank and / or the second three-way valve.

13. The system according to claim 9, wherein, The sampling container is vertically connected to the sampling device.

14. The system according to claim 1 or 2, wherein, The distance between the second three-way valve and the sampling device is 0-0.005m.

15. The system according to claim 1 or 2, wherein, The product collection unit is used to collect mixed products containing solids.

16. The system according to claim 15, wherein, The product collection unit includes a collection tank and a discharge valve installed at the outlet of the collection tank.

17. The system according to claim 16, wherein, The volume of the collection tank is 1000-10000mL.

18. The system according to claim 17, wherein, The discharge valve is a ball valve structure without a throttling point.

19. The system according to claim 1 or 2, wherein, The pressure control unit is located on the connecting pipeline between the gas outlet of the product collection unit and the inlet of the reaction unit.

20. The system according to claim 1 or 2, wherein, The pressure control unit includes a back pressure device and a gas discharge device connected in series. The outlet of the back pressure device is connected to the gas outlet of the product collection unit, and the inlet of the back pressure device is connected to the inlet of the reaction unit.

21. The system according to claim 20, wherein, The pressure control unit also includes a pressure measuring device disposed between the back pressure device and the gas outlet of the product collection unit, for measuring the reaction pressure of the system.

22. A method for online sampling of high-pressure solid-containing media, wherein, The method is performed in the high-pressure solid-containing medium online sampling system described in any one of claims 1-21.

23. The method according to claim 22, wherein, The method includes: S1, Reaction Stage: Gas and liquid reactants are introduced into the reaction unit and mixed to obtain a solid-containing mixed product. At this time, the first three-way valve, the second three-way valve and the third three-way valve are all de-energized. The solid-containing mixed product flows through the first three-way valve and the third three-way valve into the collection tank. S2. Sampling stage: The first three-way valve and the third three-way valve are energized, and the second three-way valve is de-energized. The solid-containing mixed product flows through the first three-way valve, the sampling tank, and the second three-way valve, and enters the collection tank from the common terminal COM of the third three-way valve. During this stage, the sampling tank is filled with the product to be collected and analyzed. S3. Sampling stage: The first three-way valve and the third three-way valve are de-energized, and the second three-way valve is energized. The solid mixture flows through the first three-way valve and the third three-way valve into the collection tank. At the same time, the product to be collected and analyzed stored in the sampling tank in step S2 flows through the second three-way valve into the sampling device under its own weight and / or gas pressure.

24. The method according to claim 22 or 23, wherein, The pressure of the reaction unit is 0.1-5 MPa, and the temperature is 50-500℃.

25. The method according to claim 24, wherein, The pressure of the reaction unit is 0.1-2 MPa, and the temperature is 50-200℃.

26. The method according to claim 23, wherein, The gas is selected from inert gases and / or raw material gases that participate in the reaction.

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