Device for preparing halogen hydride in smoke toxic gas of flame-retardant polymer material and testing method

Abstract

The invention relates to the field of gas preparation and detection, and particularly provides a device for preparing halogen hydride in smoke toxic gas of a flame-retardant polymer material and a testing method, the device comprises a high-temperature pyrolysis system, a high-temperature solid particle filtering system and a gas collecting system, and a flame-retardant polymer is pyrolyzed in the high-temperature pyrolysis system; the high-temperature pyrolysis system comprises an upper furnace body, a lower furnace body, a heating cavity, an arc-shaped groove and a furnace tube assembly, and the heating cavity, the arc-shaped groove and the furnace tube assembly are arranged between the upper furnace body and the lower furnace body; the furnace tube assembly comprises a detachable quartz connecting tube, a quartz boat in the quartz connecting tube, a stainless steel hook connected with one end of the quartz boat and a built-in magnet at the other end of the stainless steel hook, a handheld magnet is arranged outside the quartz tube and opposite to the built-in magnet, and the quartz boat can move towards the heating cavity or be far away from the heating cavity by operating the handheld magnet. The device can controllably and conveniently analyze the components of the flame-retardant polymer pyrolysis gas, makes up the blank in the field of analysis of the flame-retardant polymer pyrolysis gas, and is convenient to sample and high in safety.

Description

Technical Field

[0001] This invention relates to an apparatus and method for generating and detecting toxic gases from the pyrolysis of materials, specifically to an apparatus and method for generating and testing hydrogen halide in the toxic gases from flame-retardant polymer materials. Background Technology

[0002] Flame-retardant polymer materials are a key focus of military new material development. Adopting advanced flame-retardant polymer materials can significantly reduce the weight of weapons and equipment, improve tactical and technical specifications, and has significant practical value in the military. High-performance epoxy resins, high-efficiency multifunctional polyurethane materials, carbon fibers, and other polymer materials have been successfully used in armored vehicles. For example, using resin-based polymer materials on armored vehicles of the same volume can reduce weight by 60%–70% compared to steel components and 30% compared to aluminum alloys, while also reducing manufacturing costs by 20%–30%. The toxic gases produced by the high-temperature pyrolysis of flame-retardant polymer materials include large amounts of CO2, CO, various nitrogen oxides, and irritating toxins such as hydrogen halides (HF, HCl, HBr). These toxins can corrode factory equipment and precision instruments, causing losses in production and daily life, and also harming human health. For example, highly corrosive hydrogen fluoride can cause leaks in storage tanks and valves, and in the air, it can damage the skin and bones, even leading to death.

[0003] However, there is relatively little research on the impact of hydrogen halides produced by thermal decomposition on equipment environment and human health. There is also a lack of analytical methods to simulate the toxic gases of hydrogen halides produced by high-temperature pyrolysis of flame-retardant polymer materials. Therefore, it is of great significance to propose a method for simulating the analysis of the toxic gas components of hydrogen halides produced by high-temperature pyrolysis of flame-retardant polymer materials. Summary of the Invention

[0004] To address the challenge of studying the hydrogen halide (HF, HCl, HBr) content in the toxic gases from the high-temperature pyrolysis of flame-retardant polymer materials in existing technologies, this invention proposes a device for generating hydrogen halide from the toxic gases of flame-retardant polymer materials, as well as a qualitative and quantitative method for detecting these toxic gas components. This method overcomes the shortcomings in existing methods for studying the toxic gases from the high-temperature pyrolysis of flame-retardant polymers, offering convenient sample introduction and high safety.

[0005] The specific technical solution of this invention is as follows:

[0006] This invention first provides a device for the preparation and testing of hydrogen halide in the toxic smoke of flame-retardant polymer materials. The device includes a high-temperature pyrolysis system, a high-temperature solid particle filtration system, and a gas collection system. The toxic smoke generated by the pyrolysis of the flame-retardant polymer material to be tested in the high-temperature pyrolysis system is collected in the gas collection system through the high-temperature solid particle filtration system. The gas is then pumped into an analytical instrument by a high-temperature pump for qualitative and quantitative analysis of the components in the toxic smoke.

[0007] The flame-retardant polymer is selected from one of the following: epoxy resin flame-retardant polymer materials, phenolic resin flame-retardant polymer materials, polyurethane flame-retardant polymer materials, polymethyl methacrylate flame-retardant polymer materials, and polystyrene flame-retardant polymer materials.

[0008] The hydrogen halide mentioned is HF, HCl, or HBr.

[0009] Furthermore, the high-temperature pyrolysis system is a device for producing hydrogen halide from the toxic smoke of flame-retardant polymer materials. It includes a base, an operation panel on one side of the base, a furnace body on the top of the base, a furnace tube assembly, a heating chamber, heating wires, and an arc-shaped groove. The furnace body consists of a lower furnace body and an upper furnace body that is hinged to the top of the lower furnace body. The furnace tube assembly is placed between the lower and upper furnace bodies. A heating chamber is located in the middle of the furnace body, and several heating wires are evenly installed in the heating chamber.

[0010] The furnace tube assembly includes a quartz furnace tube, a quartz frosted gas outlet, a detachable quartz connecting tube, a quartz boat, a stainless steel hook, a built-in magnet, and a handheld magnet. The quartz furnace tube is placed in the middle of the lower and upper furnace bodies. One end of the quartz furnace tube is equipped with a quartz frosted gas outlet, and the other end is equipped with a detachable quartz connecting tube. A quartz boat is placed inside the quartz furnace tube, and one end of the quartz boat is connected to a stainless steel hook. One end of the stainless steel hook is equipped with a built-in magnet. A handheld magnet is installed on the outside of the detachable quartz connecting tube at the position corresponding to the built-in magnet.

[0011] Preferably, the heating wire is a Ni-Cr alloy heating wire.

[0012] Preferably, the stainless steel hook is made of SUS310 stainless steel.

[0013] Preferably, a locking buckle for fixing the upper furnace body is installed on one side of the lower furnace body, and two split handles are symmetrically installed on one side of the upper furnace body; arc-shaped grooves are opened at both ends of the lower and upper furnace bodies corresponding to the positions of the quartz furnace tubes.

[0014] Preferably, a handle is provided on one side of the handheld magnet, and the handle is provided with anti-slip texture.

[0015] Preferably, the furnace chambers of the lower and upper furnace bodies are made of alumina.

[0016] On the other hand, the present invention also provides a method for testing hydrogen halide in the smoke toxicity gas of flame-retardant polymer materials using the above-mentioned device, as follows:

[0017] 1) Dry the flame-retardant polymer to be tested, cut it into pieces, and then seal and store it.

[0018] 2) Place a certain amount of flame-retardant polymer in a quartz boat, place the quartz boat in the quartz furnace tube of the high-temperature pyrolysis system, and adjust the high-temperature pyrolysis system to the corresponding experimental conditions to pyrolyze the flame-retardant polymer.

[0019] 3) The gas generated by the pyrolysis of flame-retardant polymer is filtered through a high-temperature solid particle filtration system and then collected in a gas collection system.

[0020] 4) Perform qualitative and quantitative analysis on the collected gases.

[0021] Preferably, in step 1), an oven is used to dry the flame-retardant polymer at a temperature of 80–120°C.

[0022] Preferably, the qualitative and quantitative analysis methods in step 3) include Fourier transform infrared spectroscopy, ultraviolet-visible spectrophotometry, gas chromatography, and mass spectrometry.

[0023] Preferably, the high-temperature solid particle filtration system consists of multiple metal membrane assemblies, using sintered metal membranes as filter elements, which can filter and intercept micron-sized and submicron-sized particles in toxic smoke gases, and the filter is insulated with an external insulation layer.

[0024] Preferably, the gas collection system uses a collection bag with a volume of not less than 5L for collection. The collection bag is made of a high-temperature resistant material, and the outside of the gas collection bag is insulated with a heat insulation layer.

[0025] Preferably, the collection bag is made of Teflon.

[0026] The technical effects achieved by this invention are as follows:

[0027] 1) This invention fills the gap in laboratory analysis and research on the toxic smoke gases generated by the high-temperature pyrolysis of flame-retardant polymer materials. It designs a device and method for simulating the generation, collection, qualitative and quantitative analysis of toxic smoke gases generated by flame-retardant polymer materials at high temperatures.

[0028] 2) The built-in magnet and handheld magnet can move the quartz boat left and right, which can push the material inside the quartz boat from the cold end into the high-temperature furnace for experimentation, improving the convenience of operation and ensuring both the conduct of the experiment and the safety of the operator.

[0029] 3) After the toxic gas is produced, the micron- or submicron-sized particles contained in the toxic gas are filtered and intercepted by a high-temperature solid particle filtration system, and the toxic gas is collected in a collection bag. Qualitative and quantitative analysis is performed using various analytical instruments (UV-Vis spectrophotometer, Fourier transform infrared spectrometer, mass spectrometer, gas chromatograph, etc.), providing a feasible method for the qualitative and quantitative analysis of hydrogen halide, a toxic gas from the high-temperature pyrolysis of flame-retardant polymer materials. Attached Figure Description

[0030] Figure 1 A flowchart for the preparation and testing of hydrogen halides in the toxic gases of flame-retardant polymer materials;

[0031] Figure 2 This is a schematic diagram of the preparation device;

[0032] Figure 3 This is a schematic diagram of the internal structure of the furnace body in the production device;

[0033] Figure 4 This is a schematic diagram of the furnace tube assembly inside the production device;

[0034] Figure 5 This is a magnified view of a portion of the magnet inside the preparation device;

[0035] The following are labeled in the diagram: 1. Base; 2. Control panel; 3. Lower furnace body; 4. Upper furnace body; 5. Lock; 6. Split handle; 7. Furnace tube assembly; 701. Quartz furnace tube; 702. Quartz frosted gas outlet; 703. Detachable quartz connecting tube; 704. Quartz boat; 705. Stainless steel hook; 706. Built-in magnet; 707. Handheld magnet; 8. Heating chamber; 9. Heating wire; 10. Arc groove. Detailed Implementation

[0036] The technical solution of the present invention will be further described below with reference to specific embodiments. These embodiments are only used to illustrate the technical solution of the present invention in more detail and should not be construed as limiting the scope of protection of the present invention.

[0037] The epoxy resin flame-retardant polymer material was purchased from Jinan Beifang Taihe New Materials Co., Ltd.; the polyurethane flame-retardant polymer material was purchased from Jinan Beifang Taihe New Materials Co., Ltd.; the polymethyl methacrylate was purchased from Shandong Non-metallic Materials Research Institute; and the rest, unless otherwise specified, are commercially available products.

[0038] Example 1

[0039] An apparatus for producing hydrogen halides (HF, HCl, HBr) from toxic gases from flame-retardant polymer materials, such as... Figure 2 and Figure 3 As shown, the furnace includes a base 1 at the bottom, an operation panel 2 on one side of the base 1, and a furnace body at the top of the base 1. The furnace body consists of a lower furnace body 3 and an upper furnace body 4 that is hinged to the top of the lower furnace body 3. It also includes a furnace tube assembly 7, a heating chamber 8, heating wires 9, and an arc groove 10. The furnace tube assembly 7 is placed between the lower furnace body 3 and the upper furnace body 4. The heating chamber 8 is located in the middle of the furnace body. Several heating wires 9 are evenly installed in the heating chamber 8.

[0040] The furnace tube assembly 7 includes a quartz furnace tube 701, a quartz frosted gas outlet 702, a detachable quartz connecting tube 703, a quartz boat 704, a stainless steel hook 705, a built-in magnet 706, and a handheld magnet 707. The quartz furnace tube 701 is placed in the middle of the lower furnace body 3 and the upper furnace body 4. One end of the quartz furnace tube 701 is provided with a quartz frosted gas outlet 702, and the other end of the quartz furnace tube 701 is provided with a detachable quartz connecting tube 703. The quartz boat 704 is placed inside the quartz furnace tube 701. One end of the quartz boat 704 is connected to a stainless steel hook 705, and one end of the stainless steel hook 705 is equipped with a built-in magnet 706. A handheld magnet 707 is provided on the outside of the detachable quartz connecting tube 703 at the position corresponding to the built-in magnet 706.

[0041] Heating wire 9 is made of Ni-Cr alloy, which makes the general operating temperature of heating wire 9 between 1000 and 1100℃, and the maximum operating temperature between 1100 and 1200℃.

[0042] A latch 5 for fixing the upper furnace body 4 is installed on one side of the lower furnace body 3. Two split handles 6 are symmetrically installed on one side of the upper furnace body 4. The latch 5 is used to fasten the lower furnace body 3 and the upper furnace body 4 when in use. The split handles 6 are used to open and close the upper furnace body 4.

[0043] Arc-shaped grooves 10 are provided at both ends of the lower furnace body 3 and the upper furnace body 4 at the positions corresponding to the quartz furnace tube 701, so as to facilitate the connection and use of the lower furnace body 3 and the upper furnace body 4 with the quartz furnace tube 701.

[0044] The handheld magnet 707 has a handle on one side, and the handle has anti-slip texture, which makes it easy to hold the magnet 707 and has good anti-slip performance.

[0045] The furnace chambers of the lower furnace body 3 and the upper furnace body 4 are made of alumina, which facilitates the use of the lower furnace body 3 and the upper furnace body 4.

[0046] In use, place the quartz furnace tube 701 between the lower furnace body 3 and the upper furnace body 4. Place the material to be heated inside the quartz boat 704, then place the quartz boat 704 inside the quartz furnace tube 701. Connect one end of the stainless steel hook 705 to the quartz boat 704. Place the stainless steel hook 705 and its other end's handheld magnet 707 (with built-in magnet 706) inside the detachable quartz connecting tube 703. Position the handheld magnet 707 outside the quartz connecting tube 703, corresponding to the built-in magnet 706. Then, fix the detachable quartz connecting tube 703 to one end of the quartz furnace tube 701. After installation, proceed with... When the material is heated, push the handheld magnet 707 to the right. Due to the attraction between the handheld magnet 707 and the built-in magnet 706, the handheld magnet 707 pushes the built-in magnet 706 to the right. The built-in magnet 706 moves and pushes the stainless steel hook 705. The stainless steel hook 705 pushes the quartz boat 704 and the material inside it from the cold end of the quartz furnace tube 701 to the heating section inside it, so that the material inside the quartz boat 704 can be heated. The gas generated by the high-temperature pyrolysis of the material is discharged from the quartz frosted gas outlet 702. After being filtered by the high-temperature solid particle filtration system, it is collected in a collection bag for testing equipment.

[0047] The high-temperature solid particle filtration system consists of multiple metal membrane modules, using sintered metal membranes as filter elements. It can filter and intercept micron- and submicron-sized particles in toxic gases. The filter is insulated with an external insulation layer.

[0048] Preferably, the gas collection system uses a collection bag with a volume of not less than 5L for collection. The collection bag is made of a high-temperature resistant material, and the outside of the gas collection bag is insulated with a heat insulation layer.

[0049] Preferably, the collection bag is made of Teflon.

[0050] Example 2

[0051] A method for preparing and testing smoke toxic gases from epoxy resin flame-retardant polymer materials, the specific steps of which are as follows:

[0052] Using the flame-retardant polymer material smoke toxic gas generation device described in Example 1, the epoxy resin flame-retardant polymer material sample was thoroughly dried in a 110°C constant temperature oven and then placed in a sample bottle for later use. 10g of the sample was weighed and placed inside a quartz boat 704. Under an air flow of 30mL / min, the temperature was increased from room temperature (25°C) to 1100°C at a rate of 10°C / min. A handheld magnet 707 was used to push the quartz boat 704 and its contents from the cold end of the quartz furnace tube 701 to the heating section inside, thus heating the material inside the quartz boat 704. The gas generated by the high-temperature pyrolysis of the material was discharged through the quartz frosted gas outlet 702. After filtration through a high-temperature solid particle filtration system, the smoke toxic gas was collected in a collection bag to simulate the smoke toxic gas released by the flame-retardant polymer material when heated to high temperatures.

[0053] The collected gas was filtered again at high temperature through a back-end filter, and then drawn into a Fourier transform infrared spectrometer using a high-temperature vacuum pump for analysis. A multi-component mixed gas of nitrogen containing hydrogen chloride, hydrogen fluoride, and hydrogen bromide was used to perform linear fitting on the Fourier transform infrared spectrometer, and the composition and content were determined by comparison with calibration curves. The high-temperature vacuum pump speed was 10 L / min, and the test temperature was 150℃.

[0054] Example 3

[0055] A method for preparing and testing the smoke toxicity gases from polyurethane flame-retardant polymer materials, comprising the following specific steps:

[0056] Using the flame-retardant polymer material smoke toxic gas generation device provided in Example 1, the polyurethane flame-retardant polymer material sample was thoroughly dried in a 110°C constant temperature oven and then placed in a sample bottle for later use. 10g of the sample was weighed and placed inside a quartz boat 704. Under an air flow of 30mL / min, the temperature was increased from room temperature (25°C) to 1100°C at a rate of 10°C / min. A handheld magnet 707 was used to push the quartz boat 704 and its contents from the cold end of the quartz furnace tube 701 to the heating section inside, thus heating the material inside the quartz boat 704. The gas generated by the high-temperature pyrolysis of the material was discharged through the quartz frosted gas outlet 702. After filtration through a high-temperature solid particle filtration system, the smoke toxic gas was collected in a collection bag to simulate the smoke toxic gas released by the flame-retardant polymer material when heated to high temperatures.

[0057] The collected gas was filtered again at high temperature through a back-end filter, and then drawn into a Fourier transform infrared spectrometer using a high-temperature vacuum pump for analysis. A multi-component mixed gas of hydrogen chloride, hydrogen fluoride, and hydrogen bromide was used to perform linear fitting on the Fourier transform infrared spectrometer, and the composition and content were determined by comparing the calibration curves. The high-temperature vacuum pump speed was 10 L / min, and the test temperature was 150℃.

[0058] Example 4

[0059] A method for preparing and testing toxic gases from the pyrolysis of polymethyl methacrylate, the specific steps of which are as follows:

[0060] Using the flame-retardant polymer material smoke toxic gas generation device provided in Example 1, the polymethyl methacrylate polymer material sample was thoroughly dried in a 110°C constant temperature oven and then placed in a sample bottle for later use. 10g of the sample was weighed and placed inside a quartz boat 704. Under an air flow of 30mL / min, the temperature was increased from room temperature (25°C) to 1100°C at a rate of 10°C / min. A handheld magnet 707 was used to push the quartz boat 704 and its contents from the cold end of the quartz furnace tube 701 to the heating section inside, thus heating the material inside the quartz boat 704. The gas generated by the high-temperature pyrolysis of the material was discharged through the quartz frosted gas outlet 702. After filtration through a high-temperature solid particle filtration system, the smoke toxic gas was collected in a collection bag to simulate the smoke toxic gas released by the flame-retardant polymer material when heated to high temperatures.

[0061] The collected gas was filtered again at high temperature through a back-end filter, and then pumped into a Fourier transform infrared spectrometer for analysis using a high-temperature pump. A multi-component mixed gas of hydrogen chloride, hydrogen fluoride, and hydrogen bromide was used to perform linear fitting on the Fourier transform infrared spectrometer, and the composition and content were determined by comparing the calibration curves.

[0062] The measurement ranges for hydrogen chloride, hydrogen fluoride, and hydrogen bromide are HCl: (0.1~5000)μmol / mol, HF: (0.1~1000)μmol / mol, and HBr: (0.1~1000)μmol / mol, respectively. The high-temperature vacuum pump speed is 10L / min and the test temperature is 150℃.

[0063] The above embodiments are intended to help those skilled in the art better understand the present invention. The implementation of the present invention is not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention should be considered equivalent substitutions and are included within the protection scope of the present invention.

Claims

1. A device for generating hydrogen halide from toxic smoke gases of flame-retardant polymer materials, comprising a base (1), characterized in that: The base (1) is provided with a furnace body at the top, and also includes a furnace tube assembly (7), a heating chamber (8), heating wires (9) and an arc groove (10); the furnace body is composed of a lower furnace body (3) and an upper furnace body (4) installed at the top of the lower furnace body (3) by a hinge, the furnace tube assembly (7) is placed between the lower furnace body (3) and the upper furnace body (4), the heating chamber (8) is provided in the middle of the furnace body, and several heating wires (9) are evenly installed in the heating chamber (8); The furnace tube assembly (7) includes a quartz furnace tube (701), a quartz frosted gas outlet (702), a detachable quartz connecting tube (703), a quartz boat (704), a stainless steel hook (705), a built-in magnet (706), and a handheld magnet (707). The quartz furnace tube (701) is placed in the middle of the lower furnace body (3) and the upper furnace body (4). One end of the quartz furnace tube (701) is provided with a quartz frosted gas outlet (702), and the other end of the quartz furnace tube (701) is provided with a detachable quartz connecting tube (703). The quartz boat (704) is placed inside the quartz furnace tube (701). One end of the quartz boat (704) is connected to a stainless steel hook (705), and one end of the stainless steel hook (705) is equipped with a built-in magnet (706). A handheld magnet (707) is provided on the outside of the detachable quartz connecting tube (703) at the position corresponding to the built-in magnet (706).

2. The apparatus for producing hydrogen halide from toxic smoke gases from flame-retardant polymer materials according to claim 1, characterized in that: The base (1) has an operation panel (2) on one side, and the heating wire (9) is made of Ni-Cr alloy heating wire.

3. The apparatus for producing hydrogen halide from the toxic smoke of flame-retardant polymer materials according to claim 1, characterized in that: A latch (5) for fixing the upper furnace body (4) is installed on one side of the lower furnace body (3), and two opposing handles (6) are symmetrically installed on one side of the upper furnace body (4).

4. The apparatus for producing hydrogen halide from toxic smoke gases of flame-retardant polymer materials according to claim 1, characterized in that: Arc-shaped grooves (10) are provided at both ends of the lower furnace body (3) and the upper furnace body (4) corresponding to the positions of the quartz furnace tube (701); a hand handle is provided on one side of the hand magnet (707), and anti-slip texture is provided on the hand handle.

5. The apparatus for producing hydrogen halide from the toxic smoke of flame-retardant polymer materials according to claim 1, characterized in that: The furnace chambers of the lower furnace body (3) and the upper furnace body (4) are made of alumina.

6. A method for testing hydrogen halides in the smoke toxicity gases of flame-retardant polymer materials using the apparatus described in claim 1, characterized in that, Specifically as follows: 1) Dry the flame-retardant polymer to be tested, cut it into pieces, and then seal and store it. 2) Place a certain amount of flame-retardant polymer in a quartz boat, place the quartz boat in the quartz furnace tube of the high-temperature pyrolysis system, and adjust the high-temperature pyrolysis system to the corresponding experimental conditions to pyrolyze the flame-retardant polymer. 3) The gas generated by the pyrolysis of flame-retardant polymer is filtered through a high-temperature solid particle filtration system and then collected in a gas collection system. 4) Perform qualitative and quantitative analysis on the collected gases.

7. The method for testing hydrogen halide in the smoke toxicity gas of flame-retardant polymer materials according to claim 6, characterized in that, In step 1), the flame-retardant polymer is dried in an oven at a temperature of 80–120°C.

8. The method for testing hydrogen halide in the smoke toxicity gas of flame-retardant polymer materials according to claim 6, characterized in that, In step 1), the flame retardant polymer to be tested is selected from one of the following: epoxy resin flame retardant polymer materials, phenolic resin flame retardant polymer materials, polyurethane flame retardant polymer materials, polymethyl methacrylate flame retardant polymer materials, and polystyrene flame retardant polymer materials.

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