A high temperature pyrolysis reactor and method

Abstract

The present application relates to a kind of high-temperature pyrolysis reaction device and method, the device includes sample introduction unit, reaction unit, product separation and collection unit.The device can realize the pyrolysis reaction of pyrolysis temperature up to 2000 DEG C, reaction time is millisecond level, and can be used for the high-temperature pyrolysis test research of hydrocarbon raw material.

Description

Technical Field

[0001] This invention relates to the petrochemical field, and more specifically to a high-temperature pyrolysis reaction apparatus and method. Background Technology

[0002] Domestically, due to declining crude oil reserves and increased environmental awareness, the availability of inferior oil and increased processing profits have led to a decrease in the market share of low-quality gasoline and diesel. Simultaneously, increased demand for high-quality gasoline and a slowing economy have resulted in a structural surplus of diesel, further reducing its market share. Meanwhile, there remains a shortage of chemical raw materials such as low-carbon olefins and aromatics. Therefore, a transformation in refining is needed for development. This necessitates the development of high-temperature cracking technology for producing chemical raw materials from inferior heavy oil, thereby achieving the transformation from refining to chemical processing.

[0003] Acetylene is an important basic organic chemical raw material. The main industrial methods for producing acetylene include the calcium carbide method, the partial oxidation of methane, and the methane arc cracking method. Among these, the calcium carbide method is a mature technology and accounts for the vast majority of industrial production, but it has relatively high pollution and energy consumption. Plasma pyrolysis of coal to produce acetylene is a new and promising direct coal chemical conversion pathway. Related research began in the 1960s at the University of Sheffield in the UK: in a high-temperature, high-enthalpy, and highly reactive arc thermal plasma jet, the volatiles and even fixed carbon of coal can be directly converted into acetylene. Subsequently, a large amount of research focused on countries such as the UK, the US, Germany, India, and the Soviet Union. Since the 1990s, Chinese scholars and engineers have conducted extensive basic and engineering research in this field. With technological advancements, some researchers have also applied plasma to the production of acetylene from coal tar, asphalt, and oil slurry, but no industrial reports have been found.

[0004] Carbon black feedstocks are classified into three categories: coal tar, ethylene tar, and catalytic cracking residue. Carbon black feedstocks require high aromatic content, high BMCI value, low sulfur content, and low asphaltenes. Coal tar and its distillate oils (including anthracene oil and preservative oil) are ideal carbon black feedstocks, but the supply of coal tar has peaked and is gradually declining. Ethylene tar, produced by cracking naphtha to produce ethylene, has a high aromatic content and low sulfur content, making it ideal for carbon black production. However, ethylene produced by cracking hydrocarbon oils or crude diesel oil has a low aromatic content and high asphaltenes, which is unfavorable for carbon black production. Therefore, in the United States, catalytic cracking residue is widely used for carbon black production. Carbon black technology mainly utilizes the oil furnace method for production. The average plant size is around 70,000 tons / year, with the largest reaching 240,000 tons / year. The production equipment and processes are basically the same for each company. In recent years, foreign carbon black companies have been moving towards energy-saving and environmentally friendly production equipment and processes. Currently, some new technologies and processes are still under development. For example, exhaust gas is passed through a water scrubbing tower, maintaining the temperature at 40℃ to remove excess water vapor, carbon black dust, etc., thus achieving ideal environmental protection results. Secondly, installing waste gas desulfurization devices can prevent low-sulfur oxides from polluting the environment. Additionally, in terms of product packaging, powdered carbon black can be compressed into blocks and then packaged in vacuum bags. During use, the entire bag of carbon black is placed in grinding equipment, which directly reduces dust pollution during transportation and use, and also avoids the problem of carbon black absorbing moisture.

[0005] Currently, well-known conductive carbon blacks internationally include Lion Corporation's Ketjenblack series of superconducting carbon blacks (Ketjenblack EC-300J and EC-600JD), Cabot's VXC series of conductive carbon blacks, and Evonik Degussa's PRINTEX XE2-B, PRINTEX L6, and HIBLAXK 40B2. World-renowned carbon black manufacturers, such as Cabot, Columbia, and Akzo, have long invested significant resources in developing and producing conductive carbon blacks, conducting specialized research on their application performance, and developing conductive carbon black varieties suitable for various fields. These companies' conductive carbon black products are characterized by large specific surface area, high oil absorption value, good conductivity, and high purity. Europe, America, and Japan have all invested heavily in the development of new energy vehicles, with lithium-ion battery-powered electric vehicles being a primary focus. The core technology is the development of lithium-ion batteries, and the core technologies of lithium-ion batteries are improving specific capacity, cycle life, and safety. Conductive carbon black is an indispensable conductive agent in batteries, and its performance directly affects the implementation of core battery technologies and the battery's cost-effectiveness. Therefore, major international carbon black companies have targeted this market, investing heavily in the development of conductive carbon black specifically for power lithium-ion batteries or improving existing products to enhance conductivity and meet the requirements of power batteries. The United States is the world's largest producer of carbon black, with Cabot Corporation ranking among the top sellers of conductive carbon black globally. Meanwhile, Lion Corporation of Japan's Ketjen Black series of superconducting carbon blacks are considered top-quality conductive carbon blacks, particularly suitable for high-end conductive plastics and conductive rubbers. Other well-known international conductive carbon black manufacturers include Evonik Degussa, Denki Chemical Co., Ltd. (Japan), and Termec GmbH (Switzerland).

[0006] Traditional oil refining experimental research equipment is limited by heating methods, reactor types, and reactor materials, resulting in reaction temperatures generally below 700℃ and residence times that are relatively long. However, the formation conditions of some high-end chemical products or materials, such as acetylene and carbon black, have more stringent requirements for reaction temperature and residence time, which current oil refining experimental equipment cannot meet. Summary of the Invention

[0007] The purpose of this invention is to provide an ultra-high temperature millisecond pyrolysis reaction device, which can be used for experimental research on high-temperature pyrolysis of hydrocarbon feedstocks.

[0008] A first aspect of the present invention provides a high-temperature pyrolysis reaction apparatus, the apparatus comprising:

[0009] The sample introduction unit includes a raw material feed pump, a raw material preheating furnace, and a raw material purge gas preheating furnace;

[0010] The reaction unit includes:

[0011] The first preheating furnace for carrier gas is used to heat the carrier gas;

[0012] The second carrier gas preheating furnace is provided with a second carrier gas preheating inner tube and a second carrier gas preheating outer tube, which is used to further heat the carrier gas that has been heated by the first carrier gas preheating furnace. The second carrier gas preheating furnace is heated by a first high-frequency induction heating device, which includes a first electromagnetic induction coil sleeved on the outer periphery of the second carrier gas preheating outer tube.

[0013] The reactor is provided with an inner reaction tube, an inner reaction sleeve, and an outer reaction sleeve. The reactor is also provided with a raw material inlet, which is connected to the raw material preheating furnace and the raw material purge gas preheating furnace of the sample injection unit through pipelines. The reactor is heated by a second high-frequency induction heating device, which includes a second electromagnetic induction coil sleeved on the outer periphery of the outer reaction tube.

[0014] Product separation and collection unit, comprising:

[0015] A product cooler is provided with a cooling medium inlet, a cooling medium outlet, and a product gas outlet, and the product cooler is connected to the outlet of the reactor via a pipeline;

[0016] A gas product collector is connected to the product gas outlet of the product cooler.

[0017] According to the apparatus of the first aspect, the materials of the second preheating inner tube of the carrier gas and / or the reaction inner tube are selected from one or more of the following: graphite, tungsten, molybdenum, tantalum, niobium, vanadium, chromium, titanium, zirconium, rare earth borides, rare earth carbides, rare earth nitrides, rare earth silicides, rare earth phosphides, and rare earth sulfides.

[0018] The rare earth element is selected from one or more of lanthanum, cerium, praseodymium, and neodymium.

[0019] According to the apparatus of the first aspect, the materials of the inner reaction sleeve, the outer reaction sleeve, and / or the second preheating outer carrier gas sleeve are selected from quartz and / or boron nitride.

[0020] According to the apparatus of the first aspect, a filter element is provided at the outlet connection of the reactor for filtering the product carbon black;

[0021] Preferably, the filter element is a quartz wool filter and / or a porous component;

[0022] More preferably, the quartz wool filter screen has a mesh size of 50-300 mesh; and / or the material of the porous component is selected from one or more of the following: tungsten, graphite, tungsten, molybdenum, tantalum, niobium, vanadium, chromium, titanium, zirconium, rare earth borides, rare earth carbides, rare earth nitrides, rare earth silicides, rare earth phosphides, and rare earth sulfides; wherein the rare earth is selected from one or more of lanthanum, cerium, praseodymium, and neodymium.

[0023] According to the apparatus of the first aspect, a gas-solid separator is provided at the bottom of the reaction jacket of the reactor;

[0024] Preferably, the gas-solid separator uses cyclone separation and / or sedimentation separation as the separation method;

[0025] More preferably, the gas-solid separator is also connected to a filter, which is preferably a sintered metal filter element or a container filled with washing liquid.

[0026] According to the apparatus of the first aspect, the apparatus further includes a thermometer for testing the temperature of the reactor;

[0027] Preferably, the thermometer is a non-contact infrared thermometer.

[0028] According to the apparatus of the first aspect, the upper part of the product cooler is provided with a nozzle for spraying a cooling medium; and / or

[0029] The product cooler is inverted conical in shape.

[0030] A second aspect of the present invention provides an ultra-high temperature millisecond pyrolysis method, the method using the apparatus described in the first aspect for pyrolysis, comprising the following steps:

[0031] (1) Introduce carrier gas into the device to replace the air in the device;

[0032] (2) Heat the feed oil, feed purging gas and carrier gas to the first preheating temperature respectively. Introduce the carrier gas into the carrier gas second preheating furnace for further heating to the second preheating temperature and then enter the reactor. Under the action of the feed purging gas, the feed oil is purged into the reactor through the feed inlet on the reactor to undergo a cracking reaction.

[0033] (3) The carbon black product is collected in the reactor, and the pyrolysis gas product is introduced into the product cooler. After being cooled by the cooling medium spray, the gas product enters the gas product collector for collection.

[0034] According to the method of the second aspect, the first preheating temperature of the raw material oil is 100-300℃;

[0035] The first preheating temperature of the raw material purging gas is 150-350℃;

[0036] The first preheating temperature of the carrier gas is 200-500℃; and / or

[0037] The second preheating temperature of the carrier gas is 1000-2000℃.

[0038] According to the method of the second aspect, the purge gas and / or carrier gas is selected from one or more of the following: nitrogen, helium, argon, methane, C2-C4 light hydrocarbons; and / or

[0039] The raw material oil is selected from one or more of the following: gasoline, diesel, heavy oil, oil slurry, dry gas, waste plastic oil, and tire oil.

[0040] According to the method of the second aspect, the pyrolysis reaction conditions in the reactor are as follows:

[0041] Temperature range: 500-3000℃;

[0042] The reaction time is 3 milliseconds to 2 seconds;

[0043] The feed ratio of carrier gas to cracked feedstock is 1-15 liters / gram per unit time; and / or

[0044] The carrier gas flow rate is 0.05-30 liters / minute, preferably 0.1-10 liters / minute.

[0045] According to the method of the second aspect, the cooling medium is selected from one or more of the following: water, argon, nitrogen, preferably water.

[0046] The advantages of this invention are:

[0047] (1) Heating the high-temperature pyrolysis reactor with electromagnetic induction coil can achieve rapid heating of the high-temperature pyrolysis reactor, and the reaction temperature control is simple and the operation is stable.

[0048] (2) It can provide ultra-high temperature and millisecond-level residence time to realize direct cracking of hydrocarbon feedstocks, with high yields of acetylene, hydrogen and carbon black.

[0049] (3) The reaction linear velocity is controlled by the flow rate of the carrier gas introduced through the carrier gas inlet, thereby adjusting the rate at which the pyrolysis feedstock passes through the reaction inner tube to control the reaction residence time.

[0050] (4) The type of inner sleeve can avoid direct contact between the inner tube and the product, and can realize electromagnetic induction heating control, thereby protecting the inner tube. In particular, it can effectively prevent oxidation of the reaction tube and avoid contamination of the product carbon black.

[0051] (5) A filter component is installed at the bottom of the inner tube of the reaction to effectively filter out the carbon black produced by the reaction and prevent carbon black from clogging the subsequent pipeline. Attached Figure Description

[0052] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used together with the following detailed description to explain the invention, but do not constitute a limitation thereof. In the drawings:

[0053] Figure 1 The diagram illustrates the structure and process of one specific embodiment of the system of the present invention.

[0054] Figure 2 A schematic diagram of the reactor of the present invention is shown.

[0055] Explanation of reference numerals in the attached figures:

[0056] 1. Preheating carrier gas pipeline; 2. Raw material purge gas pipeline; 3. Raw material oil pipeline; 4. Product gas pipeline I; 5. Product gas pipeline II; 6. Cooling medium inlet pipeline; 7. Cooling medium outlet pipeline; 8. Electromagnetic induction coil I; 9. Electromagnetic induction coil II; 101. Raw material preheating furnace; 102. Raw material purge gas preheating furnace; 103. Raw material inlet; 201. Thermometer; 202. Reactor; 203. Second carrier gas preheating furnace; 204. High-frequency induction heating device I; 205. High-frequency induction heating device II; 206. First carrier gas preheating furnace; 221. Inner reaction tube; 222. Inner reaction sleeve; 223. Outer reaction sleeve; 224. Inner sleeve seal; 225. Filter component; 226. Porous component; 301. Product cooler; 302. Gas product collector. Detailed Implementation

[0057] The present application will now be described in further detail with reference to the accompanying drawings and embodiments. Through these descriptions, the features and advantages of the present application will become clearer and more apparent.

[0058] The term “exemplary” as used herein means “serving as an example, embodiment, or illustration.” Any embodiment illustrated herein as “exemplary” is not necessarily to be construed as superior to or better than other embodiments. Although various aspects of embodiments are shown in the accompanying drawings, the drawings are not necessarily drawn to scale unless specifically indicated otherwise.

[0059] Furthermore, the technical features involved in the different embodiments of this application described below can be combined with each other as long as they do not conflict with each other.

[0060] This invention provides a high-temperature pyrolysis reaction apparatus, the apparatus comprising:

[0061] The sample introduction unit includes a raw material feed pump, a raw material preheating furnace, and a raw material purge gas preheating furnace;

[0062] The reaction unit includes:

[0063] The first preheating furnace for carrier gas is used to heat the carrier gas;

[0064] The second carrier gas preheating furnace is provided with a second carrier gas preheating inner tube and a second carrier gas preheating outer tube, which is used to further heat the carrier gas that has been heated by the first carrier gas preheating furnace. The second carrier gas preheating furnace is heated by a first high-frequency induction heating device, which includes a first electromagnetic induction coil sleeved on the outer periphery of the second carrier gas preheating outer tube.

[0065] The reactor is provided with an inner reaction tube, an inner reaction sleeve, and an outer reaction sleeve. The reactor is also provided with a raw material inlet, which is connected to the raw material preheating furnace and the raw material purge gas preheating furnace of the sample injection unit through pipelines. The reactor is heated by a second high-frequency induction heating device, which includes a second electromagnetic induction coil sleeved on the outer periphery of the outer reaction tube.

[0066] Product separation and collection unit, comprising:

[0067] A product cooler is provided with a cooling medium inlet, a cooling medium outlet, and a product gas outlet, and the product cooler is connected to the outlet of the reactor via a pipeline;

[0068] A gas product collector is connected to the product gas outlet of the product cooler.

[0069] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, but the present invention is not limited thereto.

[0070] like Figure 1 As shown, the present invention provides an ultra-high temperature millisecond pyrolysis reaction device, the device including a sample injection unit (including a raw material preheating furnace 101, a raw material purge gas preheating furnace 102 and a raw material injection port 103), a reaction unit (including a thermometer 201, a reactor 202, a carrier gas second preheating furnace 203, a high-frequency induction heating device I 204 and a high-frequency induction heating device II 205), and a product separation and collection system (product cooler 301 and gas product collector 302).

[0071] The ultra-high temperature millisecond pyrolysis device sample introduction system includes a raw material preheating furnace 101, a raw material purge gas preheating furnace 102, and a raw material inlet 103. The raw material is introduced into the raw material preheating furnace via a raw material oil pump, then into the raw material inlet via a raw material oil pipeline, and finally into the reactor 202 via preheated purge gas. At the same time, a large flow of carrier gas is preheated in the first carrier gas preheating furnace 206 and then introduced into the second carrier gas preheating furnace 203 before entering the reactor 202. The reactants undergo pyrolysis from top to bottom. The resulting product gas is filtered by a filter component located at the bottom of the reactor 202 to remove carbon black. The pyrolysis gas then enters the product cooler 301 via pipeline 4, is rapidly cooled by a quenching medium, and then enters the gas collection tank via pipeline 5.

[0072] The electromagnetic induction coil I8 is connected to the high-frequency induction heating device I204 and is used for heating the carrier gas.

[0073] The electromagnetic induction coil II9 is ​​connected to the high-frequency induction heating device II205 and is used for reactor heating.

[0074] In one embodiment, the material of the second preheating inner tube of the carrier gas and / or the reaction inner tube is selected from one or more of the following: graphite, tungsten, molybdenum, tantalum, niobium, vanadium, chromium, titanium, zirconium, rare earth borides, rare earth carbides, rare earth nitrides, rare earth silicides, rare earth phosphides, and rare earth sulfides.

[0075] The rare earth element is selected from one or more of lanthanum, cerium, praseodymium, and neodymium.

[0076] In one embodiment, the materials of the inner reaction sleeve, the outer reaction sleeve, and / or the second preheating outer carrier gas sleeve are selected from quartz and / or boron nitride.

[0077] According to the present invention, such as Figure 1 As shown, the reaction apparatus includes a first carrier gas preheating furnace 206 and a second carrier gas preheating furnace 203. The carrier gas preheating furnace has a carrier gas inlet and a preheated carrier gas outlet. The preheated material outlet of the first carrier gas preheating furnace is connected to the inlet of the second carrier gas preheating furnace 203 via pipeline 1. The second carrier gas preheating furnace also has a carrier gas inlet and a preheated material outlet, and its preheated material outlet is connected to the reactor 202. The reaction apparatus further includes a raw material preheating furnace 101, which has a raw material inlet and a preheated raw material outlet. The outlet of the raw material preheating furnace is connected to the raw material inlet 103 of the reactor 202 via pipeline 3. The reaction apparatus also includes a raw material purge gas preheating furnace 102, which has a gas inlet and a preheated material outlet. The outlet of the raw material purge gas preheating furnace is connected to the raw material inlet 103 of the reactor 202 via pipeline 2. Preheating the pyrolysis raw material and carrier gas can enable the pyrolysis raw material and carrier gas to quickly reach the reaction temperature in the high-temperature pyrolysis reactor and improve the pyrolysis yield.

[0078] This invention employs electromagnetic induction heating of a high-temperature pyrolysis reactor, enabling rapid and stable temperature rise. Compared to plasma reactors, the equipment is simpler, easier to implement, and more convenient to operate, with a significantly reduced size, facilitating the construction of laboratory setups. Furthermore, the yields of acetylene and hydrogen can reach the levels of plasma reactor pyrolysis.

[0079] An electromagnetic induction coil is fitted around the outer circumference of the outer sleeve to heat the inner reaction tube through the alternating magnetic field generated by the electromagnetic induction coil. High-frequency electromagnetic induction heating equipment is well known to those skilled in the art. On the one hand, it can supply power to the electromagnetic induction coil, and on the other hand, it can be equipped with an electromagnetic heating controller to control the frequency of the alternating current input to the electromagnetic induction coil. Electromagnetic heating controllers are well known to those skilled in the art, and will not be described in detail in this invention.

[0080] In one embodiment, a filter element is provided at the outlet connection of the reactor for filtering the product carbon black;

[0081] Preferably, the filter element is a quartz wool filter and / or a porous component;

[0082] More preferably, the quartz wool filter screen has a mesh size of 50-300 mesh; and / or the material of the porous component is selected from one or more of the following: tungsten, graphite, tungsten, molybdenum, tantalum, niobium, vanadium, chromium, titanium, zirconium, rare earth borides, rare earth carbides, rare earth nitrides, rare earth silicides, rare earth phosphides, and rare earth sulfides; wherein the rare earth is selected from one or more of lanthanum, cerium, praseodymium, and neodymium.

[0083] like Figure 2 As shown, reactor 202 includes an inner reaction tube 221, an inner reaction sleeve 222, and an outer reaction sleeve 223. One end of the inner reaction sleeve 222 is closed, and the open end is inserted into the inner reaction tube 221 and then sealed with an inner sleeve seal 224. The outlet end of the outer reaction sleeve 223 is also provided with a filter component 225 and a porous component 226.

[0084] The inner reaction tube is used for electromagnetic induction heating. The inner reaction sleeve and the inner sleeve seal can prevent direct contact between the inner reaction tube and the product, and can also realize electromagnetic induction heating control, thereby protecting the inner reaction tube. In particular, it can effectively prevent the oxidation of the inner reaction tube and avoid contamination of the product carbon black. The outer reaction sleeve is the site of the pyrolysis reaction. The filter component and the porous component are used to filter out the carbon black produced by the reaction and prevent carbon black from clogging the subsequent pipeline. The porous component provides support for the filter component.

[0085] In one embodiment, a gas-solid separator is provided at the bottom of the reactor's outer reaction jacket.

[0086] Preferably, the gas-solid separator uses cyclone separation and / or sedimentation separation as the separation method;

[0087] More preferably, the gas-solid separator is also connected to a filter, which is preferably a sintered metal filter element or a container filled with washing liquid.

[0088] In one embodiment, the upper middle part of the product cooler is provided with a spray nozzle for spraying cooling medium; and / or

[0089] The product cooler is inverted conical in shape.

[0090] According to the present invention, in order to further purify and collect gaseous products, the system further includes a gaseous product collector 302 and an optional gas-solid separator and / or filter. The gas-solid separator is disposed at the bottom of the outer casing of the reactor 202. The gas-solid separator is used to perform coarse separation of the reaction products, which can be cyclone separation, sedimentation separation, etc. The filter further separates the gaseous products obtained by the gas-solid separator. It can be a sintered metal filter element or a container containing washing liquid. The filtration accuracy of the sintered metal filter element can be below 5 micrometers. The gaseous product collector 302 can be a gas tank, gas bag, or other container.

[0091] In one embodiment, the device further includes a thermometer for testing the temperature of the reactor;

[0092] Preferably, the thermometer is a non-contact infrared thermometer.

[0093] To control and monitor the reaction temperature, such as Figure 1 As shown, the reaction system may further include a thermometer 201, which is preferably a non-contact infrared high-temperature thermometer. The thermometer can measure the temperature near the outlet of the inner reaction tube, and then adjust the heating power of the heat source based on this temperature. Preferably, a PID controller is used in a closed-loop control mode to adjust the heating power of the heat source in real time according to the temperature measured by the thermometer.

[0094] The present invention also provides an ultra-high temperature millisecond pyrolysis method, wherein the method uses the above-mentioned apparatus to perform pyrolysis, and includes the following steps:

[0095] (1) Introduce carrier gas into the device to replace the air in the device;

[0096] (2) Heat the feed oil, feed purging gas and carrier gas to the first preheating temperature respectively. Introduce the carrier gas into the carrier gas second preheating furnace for further heating to the second preheating temperature and then enter the reactor. Under the action of the feed purging gas, the feed oil is purged into the reactor through the feed inlet on the reactor to undergo a cracking reaction.

[0097] (3) The carbon black product is collected in the reactor, and the pyrolysis gas product is introduced into the product cooler. After being cooled by the cooling medium spray, the gas product enters the gas product collector for collection.

[0098] In one embodiment, the first preheating temperature of the raw oil is 100-300°C;

[0099] The first preheating temperature of the raw material purging gas is 150-350℃;

[0100] The first preheating temperature of the carrier gas is 200-500℃; and / or

[0101] The second preheating temperature of the carrier gas is 1000-2000℃.

[0102] In one embodiment, the purge gas and / or carrier gas is selected from one or more of the following: nitrogen, helium, argon, methane, C2-C4 light hydrocarbons; and / or

[0103] The raw material oil is selected from one or more of the following: gasoline, diesel, heavy oil, oil slurry, dry gas, waste plastic oil, and tire oil.

[0104] In one embodiment, the pyrolysis reaction conditions in the reactor are as follows:

[0105] Temperature range: 500-3000℃;

[0106] The reaction time is 3 milliseconds to 2 seconds;

[0107] The feed ratio of carrier gas to cracked feedstock is 1-15 liters / gram per unit time; and / or

[0108] The carrier gas flow rate is 0.05-30 liters / minute, preferably 0.1-10 liters / minute.

[0109] In one embodiment, the cooling medium is selected from one or more of the following: water, liquid nitrogen, nitrogen gas, preferably water.

[0110] Specifically, the high-temperature pyrolysis apparatus provided by this invention performs the following steps for the high-temperature pyrolysis reaction:

[0111] (1) After the inner tube 221 of the reaction is installed into the inner sleeve 222 of the reactor, it is sealed with the inner sleeve seal 224. The inner sleeve 222 of the reactor is installed into the outer sleeve 223 of the reaction. Quartz wool is installed at the bottom of the outer sleeve as a filter component 225 and a porous component 226 is used as a support for the filter component. The outlet of the outer sleeve is sealed to the product quench tank. Check the air tightness of the device. Turn on the carrier gas flow to replace the air in the reaction system.

[0112] (2) Turn on the heating switch. The feed oil is preheated through the feed oil preheating furnace, the carrier gas is preheated through the first carrier gas preheating furnace, and the purge gas is preheated through the purge gas preheating furnace. When the temperature reaches the set value, the carrier gas second preheating furnace 203 is heated to the preset high-temperature carrier gas preheating temperature through the electromagnetic induction coil 8. Then, the pyrolysis feedstock preheated by the feedstock preheating furnace 101 is introduced into the reactor 202 from the pyrolysis feedstock inlet. Under the action of the high-temperature preheating carrier gas outlet and the high temperature of the reactor, the pyrolysis feedstock is gasified and undergoes a pyrolysis reaction. At this time, the reaction residence time of the pyrolysis feedstock in the inner tube of the reaction can be controlled by controlling the flow rate of the carrier gas such as nitrogen entering from the carrier gas pipeline 1, thereby optimizing the distribution of pyrolysis reaction products. The flow rate of the carrier gas can be adjusted within a large range as needed, for example, 50-10000 ml / min. The pyrolysis reaction products obtained from the pyrolysis in the reactor 202 are introduced into the product cooler 301 through the pipeline 4 after passing through the carbon black separation at the bottom of the reactor 202. The product cooler 301 is preferably a product quench tank. After being cooled by the spray of the quenching medium, it enters the gas product collector 302.

[0113] The present invention will be further illustrated by the following examples, but the present invention is not limited thereto.

[0114] In the examples and comparative examples:

[0115] The reaction temperature refers to the temperature in the middle of the reaction tube covered by the electromagnetic induction coil;

[0116] Reaction time = Length of inner reaction tube / Flow rate of reactants in inner reaction tube;

[0117] Product yield = Product weight / Cracking feed weight × 100%;

[0118] The gaseous reaction products were determined by gas chromatography.

[0119] Example 1 - Example 2

[0120] Examples 1 and 2 are respectively in Figure 1 The apparatus shown uses catalytic diesel oil with properties as described in Table 1 as the cracking feedstock according to the process of the aforementioned specific embodiment. The feedstock preheating temperature is 250°C, the purge gas preheating temperature is 250°C, the carrier gas is nitrogen, the temperature of the first carrier gas preheating furnace is 500°C, and the temperature of the second carrier gas preheating furnace is 1200°C. Figure 2A schematic diagram of the reactor structure of the present invention is shown, wherein the total height of the reactor is H, and the height of the raw material inlet is h. In this embodiment, tungsten tubes are used as inner reaction tubes, with a quantity of 5 tubes, an inner diameter of 2 mm, an outer diameter of 3 mm, and a height of 90 mm. The inner reaction sleeve is a quartz tube with one closed end, an inner diameter of 4 mm, an outer diameter of 5 mm, and a height of 110 mm. The open end of the inner reaction sleeve is inserted into the inner reaction tube and then sealed with quartz wool. The outer reaction sleeve is a quartz tube with an inner diameter of 14 mm, an outer diameter of 22 mm, and a height H of 270 mm. The height h of the raw material inlet is 250 mm. The top of the inner reaction sleeve is located at the raw material inlet. An electromagnetic induction coil, with an inner diameter of 25 mm, is fitted around the outer circumference of the reaction inner sleeve 5 mm below the inlet. The upper and lower ends of the coil are approximately 5 mm below the upper and lower ends of the inner sleeve, respectively. A porous component, a tungsten plate, is 10 mm from the bottom of the tungsten tube, with an opening ratio of 32.45% and a pore size of 0.053 mm. A quartz wool filter is also 10 mm from the bottom of the tungsten tube, with a mesh size of 60 mesh. The porous component supports the filter component. Water is used as the quenching medium, and a gas collection bag is used. Specific reaction conditions and results are shown in Table 2.

[0121] As can be seen from the results in Table 2, the device can achieve high-temperature, millisecond-level pyrolysis reactions, and the device has good material balance and parallelism.

[0122] Table 1

[0123] <![CDATA[Density (20°C) / (g / cm 3 )]]> 0.8965 Refractive index (20℃) 1.5579 Sulfur content (%) 0.231 Nitrogen content (µg / g) 548 Carbon percentage by weight % 89.23 Hydrogen percentage (by weight) 10.32 Hydrocarbon composition / ℃ Alkanes, % by weight 16.9 Cycloalkanes, % by weight 6.0 Monocyclic aromatic hydrocarbons, % by weight 56.0 Bicyclic aromatic hydrocarbons, % by weight 21.1 Tricyclic aromatic hydrocarbons, % by weight 0.0 Total aromatics, % by weight 77.1 Gel, weight % 0.0

[0124] Table 2

[0125] Cracking feedstock Catalytic diesel Catalytic diesel Reaction temperature, °C 1450 1450 Carrier gas flow rate, liters per minute 4 4 Oil inlet rate, grams per minute 0.5 0.5 Oil injection time, minutes 2 2 Response time, milliseconds 19.06 20.78 gaseous product yield, % by weight 18.12 18.49 Acetylene yield, % by weight 12.34 12.56 Hydrogen yield, wt% 6.89 6.76 Carbon black yield, % by weight 78.52 78.25 Total, by weight % 96.64 96.74 Loss, weight % 3.36 3.26

[0126] In the description of this application, it should be noted that, unless otherwise expressly specified and limited, the terms "installation," "connection," and "linking" should be interpreted broadly. Those skilled in the art can understand the specific meaning of these terms in this application based on the specific circumstances.

[0127] The present application has been described above with reference to preferred embodiments; however, these embodiments are merely exemplary and illustrative. Various substitutions and modifications can be made to the present application based on these embodiments, all of which fall within the protection scope of the present application.

Claims

1. A high-temperature pyrolysis reaction apparatus, characterized in that, The device includes: The sample introduction unit includes a raw material feed pump, a raw material preheating furnace, and a raw material purge gas preheating furnace; The reaction unit includes: The first preheating furnace for carrier gas is used to heat the carrier gas; The second carrier gas preheating furnace is provided with a second carrier gas preheating inner tube and a second carrier gas preheating outer tube, which is used to further heat the carrier gas that has been heated by the first carrier gas preheating furnace. The second carrier gas preheating furnace is heated by a first high-frequency induction heating device, which includes a first electromagnetic induction coil sleeved on the outer periphery of the second carrier gas preheating outer tube. The reactor is provided with an inner reaction tube, an inner reaction sleeve, and an outer reaction sleeve. The reactor is also provided with a raw material inlet, which is connected to the raw material preheating furnace and the raw material purge gas preheating furnace of the sample injection unit through pipelines. The reactor is heated by a second high-frequency induction heating device, which includes a second electromagnetic induction coil sleeved on the outer periphery of the outer reaction sleeve. The inner reaction tube is used for electromagnetic induction heating. Product separation and collection unit, comprising: A product cooler is provided with a cooling medium inlet, a cooling medium outlet, and a product gas outlet, and the product cooler is connected to the outlet of the reactor via a pipeline; A gaseous product collector is connected to the product gas outlet of the product cooler; The reactor is equipped with a filter element at its outlet connection to filter out the carbon black product. The high-temperature pyrolysis reaction apparatus also includes a thermometer for testing the temperature of the reactor, and the thermometer is a non-contact infrared thermometer.

2. The apparatus according to claim 1, characterized in that, The materials of the second preheating inner tube of the carrier gas and / or the reaction inner tube are selected from one or more of the following: graphite, tungsten, molybdenum, tantalum, niobium, vanadium, chromium, titanium, zirconium, rare earth borides, rare earth carbides, rare earth nitrides, rare earth silicides, rare earth phosphides, and rare earth sulfides. The rare earth element is selected from one or more of lanthanum, cerium, praseodymium, and neodymium.

3. The apparatus according to claim 1, characterized in that, The materials of the inner reaction sleeve, the outer reaction sleeve, and / or the second preheating outer carrier gas sleeve are selected from quartz and / or boron nitride.

4. The apparatus according to claim 1, characterized in that, The filter element is a quartz wool filter screen.

5. The apparatus according to claim 1, characterized in that, The filter element is a porous component.

6. The apparatus according to claim 4, characterized in that, The quartz wool filter screen has a mesh size of 50-300.

7. The apparatus according to claim 5, characterized in that, The porous component is made of one or more of the following materials: graphite, tungsten, molybdenum, tantalum, niobium, vanadium, chromium, titanium, zirconium, rare earth borides, rare earth carbides, rare earth nitrides, rare earth silicides, rare earth phosphides, and rare earth sulfides; wherein the rare earth is selected from one or more of lanthanum, cerium, praseodymium, and neodymium.

8. The apparatus according to claim 1, characterized in that, A gas-solid separator is installed at the bottom of the reactor's outer reaction jacket.

9. The apparatus according to claim 8, characterized in that, The gas-solid separator uses cyclone separation and / or sedimentation separation as its separation methods.

10. The apparatus according to claim 9, characterized in that, The gas-solid separator is also connected to a filter.

11. The apparatus according to claim 10, characterized in that, The filter is a sintered metal filter element or a container filled with washing liquid.

12. The apparatus according to claim 1, characterized in that, The upper part of the product cooler is provided with a spray nozzle for spraying cooling medium; and / or The product cooler is inverted conical in shape.

13. A method for ultra-high temperature millisecond pyrolysis, characterized in that, The method uses the apparatus of any one of claims 1 to 12 to perform pyrolysis, comprising the following steps: (1) Introduce carrier gas into the device to replace the air in the device; (2) Heat the feed oil, feed purging gas and carrier gas to the first preheating temperature respectively. Introduce the carrier gas into the second preheating furnace and heat it to the second preheating temperature before entering the reactor. Under the action of the feed purging gas, the feed oil is purged into the reactor through the feed inlet on the reactor to undergo a cracking reaction. (3) The carbon black product is collected in the reactor, and the pyrolysis gas product is introduced into the product cooler. After being cooled by the cooling medium spray, the gas product enters the gas product collector for collection.

14. The method according to claim 13, characterized in that, The first preheating temperature of the raw material oil is 100-300℃; The first preheating temperature of the raw material purging gas is 150-350℃; The first preheating temperature of the carrier gas is 200-500℃; and / or The second preheating temperature of the carrier gas is 1000-2000℃.

15. The method according to claim 13, characterized in that, The purging gas and / or carrier gas are selected from one or more of the following: nitrogen, helium, argon, methane, C2-C4 light hydrocarbons; and / or The raw material oil is selected from one or more of the following: gasoline, diesel, oil slurry, waste plastic oil, and tire oil.

16. The method according to claim 13, characterized in that, The pyrolysis reaction conditions in the reactor are as follows: Temperature range: 500-3000℃; The reaction time is 3 milliseconds to 2 seconds; The feed ratio of carrier gas to cracked feedstock is 1-15 liters / gram per unit time; and / or The carrier gas flow rate is 0.05-30 liters / minute.

17. The method according to claim 16, characterized in that, The carrier gas flow rate is 0.1-10 liters / minute.

18. The method according to claim 13, characterized in that, The cooling medium is selected from one or more of the following: water, argon, and nitrogen.

19. The method according to claim 18, characterized in that, The cooling medium is water.

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