Simulation reaction device for on-line monitoring of generation and conversion of organic amine in incineration flue gas

Abstract

The invention provides a simulated reaction device for on-line monitoring of generation and conversion of organic amine in incineration flue gas, and relates to the technical field of on-line monitoring of incineration flue gas, the simulated reaction device comprises a reaction tube, the reaction tube is vertically arranged at the center of a tubular furnace, and the upper and lower ends of the reaction tube protrude out of the upper and lower ends of the reaction furnace; a first sealing joint is arranged at the upper end of the reaction tube, a second sealing joint is arranged at the lower end of the reaction tube, the first sealing joint is connected with a gas path system, the second sealing joint is respectively connected with a tail gas tube and a reaction instrument gas outlet tube, and the reaction instrument gas outlet tube is connected with a capillary tube of an analysis instrument. The middle part of the reaction tube is connected with one end of a thermocouple, and the other end of the thermocouple is connected with a temperature control module; according to the invention, the problems of deposition, adsorption and dead volume of a gas path system are avoided, and most gas-solid reactions and gas-gas reactions can be simulated, so that online monitoring of the reaction process is realized.

Description

Technical Field

[0001] The present invention relates to the technical field of on-line monitoring of incineration flue gas, and in particular, to a simulation reaction device for on-line monitoring of the generation and conversion of organic amines in incineration flue gas. Background Art

[0002] As the most important nitrogen-containing compound in the atmosphere, organic amines make important contributions to the formation of secondary aerosols and the generation of new particles. However, due to their low abundance and rapid chemical conversion reactions, there have been few studies on organic amines by domestic and foreign scholars. The on-line monitoring technology of organic amines is an effective means to study the dynamic emission characteristics of organic amines.

[0003] However, the presence of gas small molecules, organic chlorine, inorganic chlorine, and metal particles in incineration flue gas, as well as the introduction of ammonia water, urea, and catalysts, have increased the complexity of the generation and conversion of organic amines, making it difficult to identify the key influencing factors of organic amine emissions and analyze the generation and conversion mechanism. Therefore, a laboratory simulation reaction device with controllable temperature and atmosphere is a necessary means to simulate the elementary reactions of organic amines, identify the key influencing factors, and analyze the generation and conversion mechanism.

[0004] The difficulty of the existing simulation reaction device lies in the process of introducing the flue gas after the reaction into the analytical and detection instruments. To analyze and detect the flue gas after the simulation reaction, usually two methods are adopted: 1. Collecting the flue gas sample by an adsorption tube and analyzing and detecting it after thermal desorption. This method is an off-line detection method, with cumbersome steps, long cycle, and unable to achieve real-time monitoring; 2. Directly introducing the gas path into the instrument for analysis and detection. However, the target substances are easily adsorbed and deposited on the pipe wall, and there is a problem of dead volume. Generally, heating and heat preservation of the pipeline are used to eliminate such problems. To sum up, there is a need to invent a simulation reaction device that can not only achieve on-line monitoring but also does not use an introduction gas path to avoid pipeline adsorption and dead volume problems. Summary of the Invention

[0005] In view of the above technical problems of easy adsorption and dead volume of the transmission pipeline of the existing simulation reaction device, a simulation reaction device for on-line monitoring of the generation and conversion of organic amines in incineration flue gas is provided. The present invention directly connects the reaction device with the detection instrument, avoiding the problems of deposition, adsorption, and dead volume of the gas path system.

[0006] The technical means adopted by the present invention are as follows:

[0007] An on-line monitoring simulation reaction device for the generation and transformation of organic amines in incineration flue gas, comprising a reaction tube, which is vertically arranged at the center of a tube furnace, with the upper and lower ends of the reaction tube protruding from the upper and lower ends of the reaction furnace. A first sealing joint is arranged at the upper end of the reaction tube, and a second sealing joint is arranged at the lower end of the reaction tube. The first sealing joint is connected to a gas path system, and the second sealing joint is respectively connected to a tail gas pipe and an outlet pipe of a reaction instrument. The outlet pipe of the reaction instrument is connected to a capillary of an analytical instrument. The middle part of the reaction tube is connected to one end of a thermocouple, and the other end of the thermocouple is connected to a temperature control module;

[0008] When the simulation reaction device simulates a gas-solid reaction, a solid catalyst or a solid reactant is arranged inside the reaction tube, and quartz wool is placed under the solid catalyst or the solid reactant.

[0009] Further, the reaction tube is a quartz reaction tube.

[0010] Further, the first sealing joint and the second sealing joint are stainless steel three-way quick connectors.

[0011] Further, the reaction temperature range of the simulation reaction device is from room temperature to 1100 °C.

[0012] Further, the gas path system includes several parallel inlet gas pipelines, a precursor pipeline and mass flow meters. A reaction gas is introduced into each inlet gas pipeline, and a precursor is introduced into the precursor pipeline. Mass flow meters are arranged on the inlet gas pipelines, and a mass flow meter is arranged on the precursor pipeline. The precursor pipeline is connected to the first sealing joint, and the inlet gas pipelines are connected to the first sealing joint.

[0013] Further, the reaction gas includes any one or several of ammonia, nitrogen oxides, carbon monoxide, carbon dioxide, amines, halogenated hydrocarbons, aromatic hydrocarbons, olefins, alcohols, aldehydes, ketones, chlorobenzene, chlorophenol, nitrogen, oxygen, air, and water.

[0014] Further, the nitrogen oxides are any one of nitric oxide and nitrogen dioxide or a mixture of the two; the active substances are any one of carbon monoxide and carbon dioxide or a mixture of the two; the diluent gas is any one of nitrogen and air or a mixture of the two.

[0015] Further, when ammonia and nitrogen oxides are present in the reaction gas, the molar ratio range of ammonia and nitrogen oxides is 0.5 - 3.0.

[0016] Further, the material of the reaction tube is a high-temperature resistant silica gel tube.

[0017] Further, the tube furnace is a vertical tube furnace, the inner diameter of the tube furnace ranges from 10 to 30 mm, the length of the tube furnace ranges from 200 to 400 mm, and the temperature control range of the tube furnace is from room temperature to 1100 °C.

[0018] Compared with the prior art, the present invention has the following advantages:

[0019] 1. In this application, the reaction device is directly connected to the detection instrument, avoiding the problems of deposition, adsorption and dead volume in the gas path system.

[0020] 2. In the gas path system of this application, each gas path is independently controlled by a mass flow meter, and the types and quantities of gases can be arbitrarily increased or decreased according to the reaction requirements, which can meet the needs of most gas-gas reactions and gas-solid reactions.

[0021] 3. The temperature adjustment range of the heating system in this application is from room temperature to 1100 °C, which can meet the reaction requirements at different temperatures. Description of the Drawings

[0022] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0023] Figure 1 It is a schematic diagram of the device for the gas-gas reaction of the present invention.

[0024] Figure 2 It is a schematic diagram of the device for the gas-solid reaction of the present invention.

[0025] In the figure: 1. Reaction tube; 2. Tube furnace; 3. First sealing joint; 4. Second sealing joint; 5. Tail gas pipe; 6. Reaction instrument outlet pipe; 7. Thermocouple; 8. Temperature control module; 9. Solid catalyst or solid reactant; 10. Quartz wool; 11. Inlet gas pipeline; 12. Mass flow meter; 13. Precursor pipeline. Detailed Embodiments

[0026] It should be noted that, without conflict, the embodiments in the present invention and the features in the embodiments can be combined with each other. The following will refer to the drawings and combine the embodiments to detail the present invention.

[0027] To make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Apparently, the described embodiments are only a part rather than all of the embodiments of the present invention. The description of at least one exemplary embodiment is actually only illustrative and in no way restricts the present invention and its application or use. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0028] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments of the present invention. As used herein, unless otherwise clearly specified in the context, the singular form is also intended to include the plural form. In addition, it should be understood that when the terms "comprise" and / or "include" are used in this specification, they indicate the presence of features, steps, operations, devices, components and / or their combinations.

[0029] Unless otherwise specifically stated, the relative arrangements, numerical expressions and values of the components and steps set forth in these embodiments do not limit the scope of the present invention. At the same time, it should be clear that, for the sake of description, the dimensions of the various parts shown in the drawings are not drawn in actual proportional relationship. Technologies, methods and devices known to those of ordinary skill in the relevant art may not be discussed in detail, but where appropriate, the said technologies, methods and devices should be regarded as part of the authorized specification. In all the examples shown and discussed here, any specific values should be construed as merely exemplary and not as a limitation. Therefore, other examples of the exemplary embodiments may have different values. It should be noted that like reference numerals and letters denote like items in the following drawings, and thus, once an item is defined in one drawing, it does not need to be further discussed in subsequent drawings.

[0030] In the description of the present invention, it should be understood that the orientation terms such as "front, rear, upper, lower, left, right", "lateral, vertical, perpendicular, horizontal" and "top, bottom", etc. generally indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings. They are only for the convenience of describing the present invention and simplifying the description. Without contrary description, these orientation terms do not indicate and imply that the device or element referred to must have a specific orientation or be constructed and operated in a specific orientation. Therefore, they should not be construed as limiting the protection scope of the present invention. The orientation terms "inside, outside" refer to the inside and outside relative to the contour of each component itself.

[0031] In addition, it should be noted that the use of terms such as "first" and "second" to limit components is only for the convenience of distinguishing the corresponding components. Without additional statements, the above terms have no special meanings, so they should not be construed as limitations on the protection scope of the present invention.

[0032] As Figure 1 and 2 shown, the present invention provides a simulation reaction device for on-line monitoring of the generation and conversion of organic amines in incineration flue gas, including a reaction tube 1. The reaction tube 1 is vertically arranged at the center of a tube furnace 2. The upper and lower ends of the reaction tube 1 protrude from the upper and lower ends of the reaction furnace. A first sealing joint 3 is arranged at the upper end of the reaction tube 1, and a second sealing joint 4 is arranged at the lower end of the reaction tube 1. The first sealing joint 3 is connected to a gas path system, and the second sealing joint 4 is respectively connected to a tail gas pipe 5 and a reaction instrument outlet pipe 6. Excess gas is exhausted through the tail gas pipe 5. The reaction instrument outlet pipe 6 is connected to a capillary of an analytical instrument, and the reaction gas is sampled and analyzed by the analytical instrument. The middle part of the reaction tube 1 is connected to one end of a thermocouple 7, and the other end of the thermocouple 7 is connected to a temperature control module 8; temperature control and temperature reading-back are performed by the thermocouple 7 and the temperature control module 8. The temperature control system includes a thermocouple 7 for sensing temperature and a sensing module for real-time temperature reading-back. The temperature reading-back system returns a temperature data every second to form a temperature change curve.

[0033] When the simulation reaction device simulates a gas-solid reaction, a solid catalyst or a solid reactant 9 is arranged inside the reaction tube 1, and quartz wool 10 is provided below the solid catalyst or the solid reactant 9.

[0034] The gas path system includes a plurality of parallel inlet gas pipelines 11, a precursor pipeline 13, and mass flow meters 12. A reaction gas is introduced into each inlet gas pipeline 11, and a precursor is introduced into the precursor pipeline 13. Mass flow meters 12 are arranged on the inlet gas pipelines 11, and mass flow meters 12 are arranged on the precursor pipeline 13. The precursor pipeline 13 is connected to the first sealing joint 3, and the inlet gas pipelines 11 are connected to the first sealing joint 3. Each of the inlet gas pipelines 11 and the precursor pipeline 13 is precisely controlled by its respective mass flow meter to create the gas atmosphere required for the reaction.

[0035] The reaction tube 1 is a quartz reaction tube 1.

[0036] The first sealing joint 3 and the second sealing joint 4 are stainless steel three-way quick connectors. One end of the first sealing joint 3 is connected to the reaction tube 1 with an inner diameter of 8 - 28 mm, and the other two ends are connected to the gas path system with an inner diameter of either 3 mm or 4 mm.

[0037] The reaction temperature range of the described simulation reaction device is from room temperature to 1100 °C. The tubular furnace 2 is a vertical tubular furnace, the inner diameter range of the tubular furnace 2 is 10 - 30 mm, the length range of the tubular furnace 2 is 200 - 400 mm, and the temperature control range of the tubular furnace 2 is from room temperature to 1100 °C.

[0038] The reaction gas includes but is not limited to any one or several of ammonia, nitrogen oxides, active substances, reaction gases, diluent gases, oxygen, water, halogenated hydrocarbons, olefins, aromatic hydrocarbons, alcohols, and aldehydes and ketones.

[0039] The nitrogen oxides are any one of nitric oxide and nitrogen dioxide or a mixture of the two; the active substances are any one of carbon monoxide and carbon dioxide or a mixture of the two; the diluent gas is any one of nitrogen and air or a mixture of the two.

[0040] When ammonia and nitrogen oxides are present in the reaction gas, the molar ratio range of ammonia to nitrogen oxides is 0.5 - 3.0.

[0041] The material of the reaction tube 1 is a high-temperature resistant silica tube, with an outer diameter of 8 - 28 mm, a wall thickness of 1.5 - 3.0 mm, and a length of 300 - 500 mm. The two ends of the reaction tube 1 are open.

[0042] Example 1

[0043] The specific working method of the gas-gas reaction of the present invention is as follows:

[0044] A. Install and fix the reaction tube 1 and the thermocouple 7 in the tubular furnace 2 with the sealing joints 3 and 4, directly connect the outlet pipe 6 of the reaction instrument to the sampling capillary of the analysis and detection instrument, and ensure that the tail gas pipe 5, the inlet gas pipeline 11, and the precursor pipeline 13 are well connected;

[0045] B. Open the mass flowmeter 12 and set the gas flow rates of each pipeline. The total gas flow rate is 100 - 1000 mL / min;

[0046] C. After the gas flow is stable, turn on the temperature control module and set different reaction temperatures, from room temperature to 1100 °C;

[0047] D. At the same time, start collecting data in the online monitoring mode and observe the dynamic changes of the reaction products during the heating process and at the specified temperature.

[0048] Example 2

[0049] The specific working method of the gas-solid reaction of the present invention is as follows:

[0050] A. Fix the calcined quartz wool 10 in the middle of the reaction tube 1 and load 0.2 - 2.0 g of the solid catalyst or solid reactant 9;

[0051] B. Install and fix the reaction tube 1 and the thermocouple 7 in the tubular furnace 2 with the sealing joints 3 and 4, directly connect the gas outlet pipe 6 of the reaction instrument to the sampling capillary of the analytical detection instrument, and ensure that the tail gas pipe 5, the inlet gas pipeline 11 and the precursor pipeline 13 are well connected;

[0052] C. Open the mass flowmeter 12 and set the gas flow rates of each pipeline. The total gas flow rate is 100 - 1000 mL / min;

[0053] D. After the gas flow is stable, turn on the temperature control module and set different reaction temperatures, from room temperature to 1100 °C;

[0054] E. At the same time, start collecting data in the online monitoring mode, observe the heating process and the dynamic changes of the reaction products at the specified temperature. The gaseous reactants are shown in Table 1.

[0055] Table 1

[0056]

[0057]

[0058] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A simulation reaction device for on-line monitoring of the generation and transformation of organic amines in incineration flue gas, characterized in that: It includes a reaction tube (1), the reaction tube (1) is vertically arranged at the center of a tube furnace (2), the upper and lower ends of the reaction tube (1) protrude from the upper and lower ends of the reaction furnace, a first sealing joint (3) is arranged at the upper end of the reaction tube (1), a second sealing joint (4) is arranged at the lower end of the reaction tube (1), the first sealing joint (3) is connected to a gas path system, the second sealing joint (4) is respectively connected to a tail gas pipe (5) and a reaction instrument outlet pipe (6), the reaction instrument outlet pipe (6) is connected to a capillary of an analytical instrument, the middle part of the reaction tube (1) is connected to one end of a thermocouple (7), and the other end of the thermocouple (7) is connected to a temperature control module (8); When the simulation reaction device simulates a gas-solid reaction, a solid catalyst or a solid reactant (9) is arranged inside the reaction tube (1), and a quartz wool (10) is supported under the solid catalyst or the solid reactant (9).

2. The simulation reaction device for on-line monitoring of the generation and transformation of organic amines in incineration flue gas according to claim 1, characterized in that, the reaction tube (1) is a quartz reaction tube (1).

3. The simulation reaction device for on-line monitoring of the generation and transformation of organic amines in incineration flue gas according to claim 1, characterized in that, the first sealing joint (3) and the second sealing joint (4) are stainless steel three-way quick connectors.

4. The simulation reaction device for on-line monitoring of the generation and transformation of organic amines in incineration flue gas according to claim 1, characterized in that, the reaction temperature range of the simulation reaction device is from room temperature to 1100 °C.

5. The simulation reaction device for on-line monitoring of the generation and transformation of organic amines in incineration flue gas according to claim 1, characterized in that, the gas path system includes a plurality of parallel inlet gas pipelines (11), a precursor pipeline (13) and a mass flowmeter (12). Each inlet gas pipeline (11) is filled with a reaction gas, the precursor pipeline (13) is filled with a precursor, a mass flowmeter (12) is arranged on the inlet gas pipeline (11), a mass flowmeter (12) is arranged on the precursor pipeline (13), the precursor pipeline (13) is connected to the first sealing joint (3), and the inlet gas pipeline (11) is connected to the first sealing joint (3).

6. The simulation reaction device for on-line monitoring of the generation and transformation of organic amines in incineration flue gas according to claim 5, characterized in that, the reaction gas includes any one or several of ammonia, nitrogen oxides, carbon monoxide, carbon dioxide, amines, halogenated hydrocarbons, aromatic hydrocarbons, olefins, alcohols, aldehydes, ketones, chlorobenzene, chlorophenol, nitrogen, oxygen, air, and water.

7. The simulation reaction device for on-line monitoring of the generation and transformation of organic amines in incineration flue gas according to claim 6, characterized in that, The nitrogen oxides are any one of nitric oxide and nitrogen dioxide or a mixture of the two; the active substances are any one of carbon monoxide and carbon dioxide or a mixture of the two; the diluting gas is any one of nitrogen and air or a mixture of the two.

8. The simulation reaction device for on-line monitoring of the generation and conversion of organic amines in incineration flue gas according to claim 6, characterized in that when ammonia and nitrogen oxides are present in the reaction gas, the molar ratio of ammonia to nitrogen oxides ranges from 0.5 to 3.

0.

9. The simulation reaction device for on-line monitoring of the generation and conversion of organic amines in incineration flue gas according to claim 1, characterized in that the reaction tube (1) is made of high-temperature resistant silica gel tube.

10. The simulation reaction device for on-line monitoring of the generation and conversion of organic amines in incineration flue gas according to claim 1, characterized in that the tubular furnace (2) is a vertical tubular furnace, the inner diameter of the tubular furnace (2) ranges from 10 to 30 mm, the length of the tubular furnace (2) ranges from 200 to 400 mm, and the temperature control range of the tubular furnace (2) is from room temperature to 1100 °C.

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