A method and device for regulating cracking products of waste organic polymer materials

Abstract

The present invention belongs to the technical field of solid waste recycling, and relates to a method and device for regulating the cracking products of waste organic polymer materials. The waste organic polymer materials and the harmful element removal composite auxiliary agent are uniformly mixed in a mass ratio of 90:10, and placed at 400-450°C for cracking reaction; the primary cracking product after the reaction is contacted with a catalyst and placed at 550-800°C to obtain a cracking product. The present invention reduces the sulfur and chlorine content in the cracking oil by more than 85% by separating the waste organic polymer materials from the catalyst during the cracking process, and separately controlling the harmful element removal process and catalytic cracking process conditions; by the reverse flow of the waste organic polymer materials and the catalyst during the cracking process, and regulating the catalyst temperature, the cracking products are produced with more low-carbon olefins and aromatics, which significantly increases the economic added value of the cracking products and promotes the technological transformation of the cracking industry of waste rubber, waste plastics and other materials.

Description

Technical Field

[0001] The invention belongs to the technical field of solid waste recycling, in particular to the field of resource utilization of waste organic polymer materials, and specifically relates to a method and device for regulating cracking products of waste organic polymer materials. Background Art

[0002] Cracking is an effective way to recycle waste organic polymer materials. At present, the industrial cracking methods of waste organic polymer materials such as waste rubber and waste plastics basically use rotary kiln cracking, which is to put the waste organic polymer materials into a cracking reactor and give them a certain temperature to decompose them. However, since the decomposition of waste organic polymer materials is disordered, the quality of the cracking products is poor (mainly reflected in the cracking oil products). In order to improve the quality of cracking oil products, the industry gradually puts waste organic polymer materials and catalysts into the cracking reactor together, gives them a certain temperature, and allows them to decompose. This method is called catalytic cracking, which will improve the quality of cracking oil products under the action of the catalyst. However, this catalytic cracking method also has several problems:

[0003] (1) There is a big difference between the decomposition temperature of waste organic polymer materials and the optimal activity reaction temperature of the catalyst. In the industrial cracking process, waste organic polymer materials and catalysts are placed together. If the decomposition temperature of waste organic polymer materials is the main factor, the catalyst activity will not reach the best. If the optimal activity temperature of the catalyst is the main factor, the waste organic polymer materials will be severely broken, a large amount of cracking gas will be produced, and the output of cracking oil will be significantly reduced.

[0004] (2) Waste organic polymer materials such as waste rubber and waste plastics contain a large amount of harmful elements. For example, waste rubber contains sulfur, and PVC in waste plastics contains a large amount of chlorine. During the cracking process, sulfur and chlorine will decompose with organic matter to form new chlorine- and sulfur-containing compounds. These compounds will reduce the quality of cracked oil, poison the catalyst, corrode the cracking equipment, and cause a series of problems.

[0005] In order to solve the problems of reduced quality of cracked oil and waste catalyst in the current catalytic cracking method, the present invention has developed an industrial continuous waste organic polymer material cracking product control method and device. Summary of the invention

[0006] The purpose of the present invention is to solve the above-mentioned problems existing in the prior art, and a method and device for regulating the cracking products of waste organic polymer materials are proposed. By adding a harmful element removal composite auxiliary agent during the cracking process, harmful elements such as sulfur and chlorine are solidified into the harmful element removal composite auxiliary agent, and the cracking gas phase products are preliminarily regulated; the cracking gas phase products are then reacted with a catalyst, and the catalyst is maintained at the temperature with the highest activity, so as to further regulate the quality of the cracking gas phase products; at the same time, during the entire cracking process, the waste organic polymer material and the catalyst move in opposite directions, so as to maximize the contact time between the catalyst and the cracking gas phase products, thereby increasing the output of cracking oil products, and solving the problem of the influence of harmful elements on the quality of cracking products.

[0007] The technical solution of the present invention is:

[0008] The present invention separates the two key processes of waste organic polymer material cracking and product regulation, and sets the "waste organic polymer material cracking temperature and product regulation temperature" according to the decomposition temperature of the waste organic polymer material and the optimal temperature of the catalyst activity respectively. In order to further improve the quality of the cracking product, the waste organic polymer material cracking and harmful element removal processes are integrated according to the composition of the waste organic polymer material.

[0009] Based on this, the present invention provides a method for regulating the pyrolysis products of waste organic polymer materials, comprising the following steps:

[0010] (1) mixing the waste organic polymer material and the harmful element removal composite auxiliary agent in a mass ratio of 90:10, and placing the mixture under a waste organic polymer material cracking temperature of 400 to 450° C. to decompose the waste organic polymer material to produce a cracking primary product; since the waste organic polymer material and the harmful element removal composite auxiliary agent are mixed together, the cracking primary product is first contacted with the harmful element removal composite auxiliary agent, so that the sulfur and chlorine compounds in the primary cracking product can fully react and neutralize with the harmful element removal composite auxiliary agent, thereby reducing the sulfur and chlorine content in the cracked oil by more than 85%;

[0011] The 400-450°C pyrolysis temperature of the waste organic polymer material is controlled by a pyrolysis reactor heating device; the temperature is any temperature value within the range of 400-450°C, for example, it can be 400°C, 410°C, 420°C, 430°C, 440°C or 450°C, but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0012] (2) separating the waste organic polymer material mixed with the harmful element removal composite auxiliary agent from the catalyst, and arranging them in an upper and lower layer, with the catalyst being the upper layer and the mixture of the waste organic polymer material and the harmful element removal composite auxiliary agent being the lower layer, and making the movement directions of the materials in the upper layer and the lower layer opposite to each other, and maintaining the reverse flow, so that the primary cracking product after the reaction with the harmful element removal composite auxiliary agent is fully contacted with the catalyst, and placed under the product control temperature condition of 550 to 800° C., and the target product (low-carbon olefins and aromatic hydrocarbons) generation process is controlled under the action of the catalyst, so as to obtain a cracking final value product with a high content of aromatic hydrocarbons as the main component, so that the content of valuable chemical raw materials in the cracking product is significantly increased;

[0013] The above-mentioned product control temperature of 550-800°C is based on the internal temperature of the cracking reactor, and there is an electric heating auxiliary temperature control system (mainly a temperature control system composed of electric heating coils) at the bottom of the bottom plate, which further controls the temperature of the upper material (catalyst) to reach the catalyst's optimal activity temperature, ensuring that the catalyst is carried out at the optimal catalytic cracking temperature. The temperature is any temperature value within the range of 550-800°C, for example, it can be 550°C, 600°C, 650°C, 700°C, 750°C or 800°C, but is not limited to the listed values, and other unlisted values ​​within the range are equally applicable.

[0014] The catalyst is any one of or a mixture of waste oil refining catalyst, fly ash and red mud, and the harmful element removal composite auxiliary agent is an alkaline component with red mud as the main component.

[0015] In order to achieve the above two steps (1) and (2), the harmful element removal composite auxiliary agent and the catalyst of the waste organic polymer materials such as waste rubber and waste plastics are separated during the cracking process. It mainly refers to that the waste organic polymer materials such as waste rubber and waste plastics and the harmful element removal composite auxiliary agent are at the bottom of the cracking reactor, and the catalyst is placed above the waste organic polymer materials such as waste rubber and waste plastics, so as to form an ex situ catalytic cracking of the waste organic polymer materials such as waste rubber and waste plastics.

[0016] In order to further increase the contact time and degree between the primary cracking product and the catalyst in (2), the movement direction of the moving catalyst and the (waste organic polymer materials such as waste rubber and waste plastics, and harmful element removal composite additives) at the bottom of the cracking reactor is controlled so that the two move in opposite directions during the cracking process.

[0017] Furthermore, a mixture of the catalyst, the waste organic polymer material and the harmful element removal composite auxiliary agent is placed in a cracking reactor, arranged in an upper and lower layout, and the movement direction is controlled so that the catalyst in the upper layer and the waste organic polymer material and the harmful element removal composite auxiliary agent in the lower layer move in opposite directions during the cracking process, thereby performing ex situ catalytic cracking;

[0018] The above-mentioned heterogeneous catalytic cracking mainly refers to the waste organic polymer materials and the harmful element removal composite auxiliary agent at the bottom of the cracking reactor, and the catalyst is placed above the waste organic polymer materials, forming heterogeneous catalytic cracking of the waste organic polymer materials. The movement directions of the catalyst and the waste organic polymer materials during the cracking process are opposite, which can improve the catalytic cracking effect of the catalyst.

[0019] The waste organic polymer material includes waste rubber and waste plastic. When the waste organic polymer material is waste rubber, the mass ratio of the waste catalyst of oil refining, fly ash and red mud is 60:30:10; when the waste organic polymer material is waste plastic, the mass ratio of the waste catalyst of oil refining, fly ash and red mud is 45:40:15.

[0020] The catalyst used in the present invention is a low-cost composite catalyst prepared mainly from waste catalysts from petroleum processing, and its main component is a mixture of waste catalysts from oil refining, fly ash and red mud.

[0021] Furthermore, the harmful elements in the waste organic polymer material are cracked and reacted with the harmful element removal composite auxiliary agent to solidify the harmful elements into the harmful element removal composite auxiliary agent, wherein the harmful elements include sulfur, chlorine, and silicon;

[0022] The harmful element removal composite auxiliary agent also includes an alkaline substance and a binder. The alkaline substance includes calcium oxide, calcium carbonate, dolomite, magnesium oxide, sodium carbonate and mordenite. The harmful element removal composite auxiliary agent is prepared by mixing and granulating the following components in parts by weight: 20 to 25 parts of red mud, 15 to 20 parts of calcium oxide, 10 parts of calcium carbonate, 5 to 10 parts of dolomite, 5 to 10 parts of magnesium oxide, 10 to 15 parts of sodium carbonate, 10 to 15 parts of mordenite and 5 parts of binder.

[0023] The above-mentioned harmful element removal composite additive is used to neutralize harmful elements such as sulfur, chlorine, silicon, etc. in the cracking product. The harmful element removal composite additive is mainly red mud, with a certain proportion of calcium oxide, calcium carbonate, dolomite, magnesium oxide, sodium carbonate, mordenite and other alkaline substances added, and a certain amount of binder, and is prepared by mixing and granulating according to a certain weight ratio.

[0024] Among them, the optimal formula is: 20 parts of red mud, 15 parts of calcium oxide, 10 parts of calcium carbonate, 10 parts of dolomite, 10 parts of magnesium oxide, 15 parts of sodium carbonate, 10 parts of mordenite, and 5 parts of binder; or: 25 parts of red mud, 20 parts of calcium oxide, 10 parts of calcium carbonate, 5 parts of dolomite, 5 parts of magnesium oxide, 10 parts of sodium carbonate, 15 parts of mordenite, and 5 parts of binder.

[0025] The present invention also provides a device for implementing the above method, which includes a cracking reactor main body system, the cracking reactor main body system includes a catalyst quantitative addition device, a cracking furnace kettle body and a catalyst self-circulation device obliquely arranged inside the kettle body, the catalyst self-circulation device includes a screw, a bottom plate and a screw transmission system, and an electric heating coil is arranged at the bottom of the bottom plate; the interior of the screw is a hollow structure, and its inner and outer surfaces are both provided with spiral structures and the spiral rotation directions are opposite, wherein the internal spiral angle is 5 to 10% greater than the external surface spiral angle.

[0026] Furthermore, the tail of the screw is a spiral blade structure, and the rest of the screw is a spiral ridge structure. The thickness of the spiral blade is 1 / 5 to 1 / 3 of the thickness of the spiral ridge, and the rotation arc of the spiral blade is 3 to 4 times the rotation arc of the spiral ridge. The gap between the spiral ridge and the bottom plate is 1 to 3 mm, and the inclination angle of the bottom plate is 3 to 7 degrees. The bottom plate is fixedly installed inside the cracking furnace kettle in the axial direction in a left-higher-right lower arrangement.

[0027] Furthermore, the catalyst is circulated under the action of the catalyst self-circulation device, and the specific steps are: the catalyst input through the catalyst quantitative addition device moves from bottom to top under the pushing action of the screw until it reaches the top of the bottom plate, the catalyst is gradually accumulated, and the catalyst is sent into the hollow interior of the screw under the turning action of the spiral blade at the tail of the screw. Under the action of its own weight and the spiral edges inside the screw, the catalyst moves from top to bottom at a certain movement speed to the bottom end of the bottom plate, and flows out from the outlet of the hollow screw head, and this cycle is repeated to realize the self-circulation of the catalyst in the cracking process;

[0028] The catalyst self-circulation device has only one power source motor device, which drives the screw to rotate through the motor. The rotation of the screw drives the catalyst to move from bottom to top. The catalyst is flipped into the hollow screw through the flipping action of the spiral blades at the tail of the screw. The catalyst moves from top to bottom under the action of its own weight and the internal spiral edges.

[0029] Furthermore, the cracking reactor main system also includes a cracking furnace sealing device, a transmission gear, a chain transmission system and a catalyst unloading device. The chain transmission system drives the transmission gear and then transmits power to the cracking furnace kettle to make it rotate at a uniform speed. The cracking furnace sealing device is installed at both ends of the cracking furnace kettle and is used to keep the rotating cracking furnace kettle sealed. The catalyst unloading device is connected to the cracking furnace kettle and is used to unload the catalyst.

[0030] Furthermore, the middle of the bottom plate is sunken downward to form a groove structure, and a plurality of circular holes are provided at the upper position of the inner wall of the groove. When the catalyst particle size is less than 10 nm, the circular hole size is 3 to 6 mm, and when the catalyst particle size is greater than 100 nm, the circular hole size is 5 to 9 mm.

[0031] The two sides of the bottom plate are flat plate structures, and rectangular grooves are arranged on the flat plates. The length of the rectangular grooves is 1 / 5 to 1 / 4 of the width of the bottom plate, and the width is 2 to 5 mm.

[0032] Furthermore, the cracking furnace sealing device includes a cracking furnace side wall and a U-shaped sealing dynamic ring, the sealing dynamic ring is interference fit with the screw, and the sealing working plane of the sealing dynamic ring exceeds the working surface of the screw by 1 to 2 mm; the cracking furnace side wall and the sealing dynamic ring are provided with a static sealing upper ring and a static sealing lower ring at the matching position, the static sealing upper ring and the static sealing lower ring are both circular rings, the static sealing upper ring is 10 mm longer than the static sealing lower ring, and a sealing ring is provided between the sealing dynamic ring and the static sealing upper ring and the static sealing lower ring; the cracking furnace sealing device also includes a lubricating oil port.

[0033] Furthermore, the device also includes a feeding system, a combustion heating system and a cracking residue conveying system, the outlet of the feeding system is connected to the inlet of the cracking reactor main system, the outlet of the cracking reactor main system is connected to the cracking residue conveying system, the cracking reactor main system is connected to the cracking gas condensation recovery system and the non-condensable combustible gas recycling system above the cracking reactor main system, and the non-condensable combustible gas recycling system is connected to the combustion heating system and the tail gas treatment system in sequence.

[0034] Beneficial effects of the present invention:

[0035] (1) The present invention separates the catalyst from the waste organic polymer material and adds a harmful element removal composite auxiliary agent during the cracking process, so that the waste organic polymer material generates active components under the action of heat and first reacts with the harmful element removal composite auxiliary agent, preliminarily solidifies harmful elements such as sulfur and chlorine into the harmful element removal composite auxiliary agent, and preliminarily regulates the cracking gas phase product. The cracking gas phase product then reacts with the catalyst on the top of the cracking reactor. The bottom plate holding the catalyst is provided with an auxiliary heating device, which can keep it at the temperature with the highest catalyst activity. Under the action of the auxiliary heating device, the quality of the cracking gas phase product is further regulated and improved. At the same time, during the entire cracking process, the waste organic polymer materials such as waste rubber and waste plastics move in the opposite direction to the catalyst, which can maximize the contact time between the catalyst and the cracking gas phase product, thereby improving the quality of the cracking product.

[0036] (2) The present invention separates waste organic polymer materials such as waste rubber and waste plastic from the catalyst during the cracking process, and independently controls the harmful element removal process and catalytic cracking process conditions, so that the sulfur and chlorine compounds in the cracking products can fully react with the harmful element removal composite auxiliary agent to neutralize, thereby reducing the sulfur and chlorine content in the cracked oil by more than 85%; through the reverse flow of waste organic polymer materials such as waste rubber and waste plastic and the catalyst during the cracking process, and regulating the temperature of the active area of ​​the catalyst, the cracking intermediates of waste organic polymer materials such as waste rubber and waste plastic are fully in contact with the catalyst, thereby achieving more low-carbon olefins and aromatics in the cracking products, significantly improving the economic added value of the cracking products, and promoting technological changes in the cracking industry of waste organic polymer materials such as waste rubber and waste plastic. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 The schematic diagram of the method for controlling the pyrolysis products of waste organic polymer materials of the present invention;

[0038] Figure 2 It is a structural diagram of a control device for the cracking products of waste organic polymer materials;

[0039] Figure 3 It is the structural diagram of the main system of the cracking reactor;

[0040] Figure 4 It is a structural diagram of the catalyst self-circulation device;

[0041] Figure 5 A screw having a spiral hollow structure;

[0042] Figure 6 is the catalyst self-circulation direction diagram;

[0043] Figure 7 is a schematic diagram of the structure of the screw;

[0044] Figure 8 This is an enlarged view of area E (screw tail);

[0045] Fig. 9 A bottom plate with an electric heating coil at the bottom;

[0046] Fig.10 It is a structural diagram of the sealing device of the cracking furnace;

[0047] In the above figures, Ⅰ, main system of cracking reactor; Ⅱ, feeding system; Ⅲ, combustion heating system; Ⅳ, cracking residue conveying system; 1, catalyst quantitative addition device; 2, cracking furnace sealing device; 3, cracking furnace kettle; 4, transmission gear; 5, chain transmission system; 6, catalyst unloading device; 7, screw transmission system; 8, screw; 9, bottom plate; 10, catalyst self-circulation device; 11, sealing dynamic ring; 12, sealing ring; 13, cracking furnace side wall; 14, lubricating oil port; 15, static seal upper ring; 16, static seal lower ring; 17, electric heating coil. DETAILED DESCRIPTION

[0048] The following will be combined with the embodiments and drawings to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0049] Example 1

[0050] like Figure 1 As shown, the present invention provides a method for regulating the cracking products of waste organic polymer materials. The method adds a harmful element removal composite auxiliary agent to waste organic polymer materials such as waste rubber and waste plastics during the cracking process, and reacts at any temperature condition in the range of 400-450°C, so that the sulfur and chlorine compounds in the cracking intermediates can fully react and neutralize with the harmful element removal composite auxiliary agent, thereby reducing the sulfur and chlorine content in the cracked oil product; at the same time, the waste organic polymer materials and the catalyst are separated and the movement directions of the two during the cracking process are controlled to be opposite, and the temperature of the active area of ​​the catalyst is regulated to maintain the temperature of the catalyst at the best activity, for example, any temperature in the range of 550-800°C; through the reverse flow of waste organic polymer materials such as waste rubber and waste plastics and the catalyst during the cracking process, the cracking intermediates of waste organic polymer materials such as waste rubber and waste plastics are fully in contact with the catalyst, thereby achieving more low-carbon olefins and aromatics in the cracking products.

[0051] The catalyst used in the present invention is mainly a low-cost composite catalyst prepared mainly from waste catalysts from petroleum processing, and its main component is a mixture of waste catalysts from oil refining + fly ash + red mud (the ratio of waste rubber cracking is 60:30:10, and the ratio of waste plastic cracking is 45:40:15).

[0052] The above-mentioned harmful element removal composite auxiliary agent is a harmful element removal composite auxiliary agent, which is used to neutralize harmful elements such as sulfur, chlorine, silicon and other harmful elements in the cracking intermediates, thereby consolidating the harmful elements into the harmful element removal composite auxiliary agent. The harmful element removal composite auxiliary agent mainly refers to red mud as the main component, and a certain proportion of alkaline substances such as calcium oxide, calcium carbonate, dolomite, magnesium oxide, sodium carbonate, mordenite, etc. are added, and then a certain amount of binder is combined and prepared by mixing and granulating according to a certain weight ratio. Among them, the optimal formula is: 20 parts of red mud, 15 parts of calcium oxide, 10 parts of calcium carbonate, 10 parts of dolomite, 10 parts of magnesium oxide, 15 parts of sodium carbonate, 10 parts of mordenite, and 5 parts of binder; or: 25 parts of red mud, 20 parts of calcium oxide, 10 parts of calcium carbonate, 5 parts of dolomite, 5 parts of magnesium oxide, 10 parts of sodium carbonate, 15 parts of mordenite, and 5 parts of binder.

[0053] Example 2

[0054] like Figure 2 As shown, the present invention also provides a waste organic polymer material cracking product control device, which includes a cracking reactor main system I, a feeding system II, a combustion and heating system III and a cracking residue conveying system IV; wherein the upper A port in the main system of the cracking reactor I is connected to a cracking gas condensation recovery system and a non-condensable combustible gas recycling system, the non-condensable combustible gas recycling system is connected to the combustion and heating system III, and the combustion and heating system III is connected to an exhaust gas treatment system. The connection mode of each system in the device is as follows: the main system of the cracking reactor I is connected to the outlet of the feeding system II through a flange, the upper A port in the main system of the cracking reactor I is connected to the cracking gas condensation recovery system and a non-condensable combustible gas recycling system, the non-condensable combustible gas recycling system is connected to the combustion and heating system III, and the combustion and heating system III is connected to an exhaust gas treatment system; the main system of the cracking reactor I is connected to the cracking residue conveying system IV through the flange at the outlet.

[0055] The purpose of the device of the present invention is to realize the economic added value of the cracking products of waste organic polymer materials such as waste rubber and waste plastics. This device is designed based on low-cost catalysts, wherein the main system of the Ⅰ cracking reactor is the core of the device. The Ⅱ feeding system, the Ⅲ combustion and heating system and the Ⅳ cracking residue conveying system belong to the structures disclosed in the prior art, for example, the Ⅱ feeding system is disclosed in Chinese patent CN108518965A, the Ⅲ combustion and heating system, the cracking gas condensation recovery system, the non-condensable combustible gas recycling system and the tail gas treatment system are disclosed in patent CN111303927A, and the Ⅳ cracking residue conveying system is disclosed in patent CN108373929A.

[0056] Ⅰ The specific structure of the main system of the cracking reactor is as follows Figure 3As shown, it includes a catalyst quantitative adding device 1, a cracking furnace sealing device 2, a cracking furnace kettle 3, a transmission gear 4, a chain transmission system 5, a catalyst unloading device 6, a screw transmission system 7, and a catalyst self-circulation device 10.

[0057] The catalyst self-circulation device 10 is installed above the interior of the cracking furnace kettle 3 and has a certain inclination angle, which is generally suitable in the range of 3 to 7 degrees. The catalyst self-circulation device 10 includes a screw 8 and a bottom plate 9. Figure 4 As shown, the screw 8 is connected to the screw drive system 7 through a coupling, and the screw drive system 7 is lower than the tail of the screw 8. The middle part of the screw 8 is designed to have a spiral hollow structure, and its spiral rotation direction is opposite to the spiral rotation direction of the outer surface of the screw 8, and the spiral angle is 5-10% greater than the spiral angle of the outer surface of the screw 8, so as to keep the catalyst conveying rate inside and the external moving rate similar. It is the internal channel for catalyst conveying. Figure 5 As shown, port C is the hollow conveying feed port, and port D is the hollow conveying discharge port.

[0058] In a specific embodiment, except for the tail of the screw 8, the screw 8 has spiral ridges from the head to the tail, and the thickness of the spiral ridges is the same. However, the tail is a spiral blade structure, which is welded to the tail of the screw 8 separately. The thickness of the spiral blades here is 1 / 5 to 1 / 3 of the thickness of the spiral ridges. Thinner spiral blades can achieve larger curvature bending, which is useful for delivering the catalyst into the hollow screw 8.

[0059] The catalyst is delivered into the hollow screw 8 mainly by the special structure of the spiral blade at the tail of the screw 8. At the tail of the screw 8, the tail of the screw 8 becomes thinner, the spiral blade becomes longer as a whole, and the rotation arc of the spiral blade is 3 to 4 times the rotation arc of the conventional spiral edge at the front end.

[0060] In a specific embodiment, the outer spiral edge of the screw 8 is used in conjunction with the bottom plate 9, and the bottom plate 9 is welded above the cracking furnace kettle 3. The gap between the outer spiral edge of the screw 8 and the bottom plate 9 is always maintained between 1 and 3 mm (except the tail of the screw 8), and the best is 1 mm.

[0061] In a specific embodiment, during the heterogeneous catalytic cracking of waste organic polymer materials, the catalyst is pushed by the screw 8 on the bottom plate 9 with holes to achieve axial movement. The size and position of the holes in the bottom plate 9 with holes are mainly determined by the movement characteristics of the catalyst under the push of the screw 8. The bottom plate 9 has a certain inclination, generally 3 to 7 degrees, 5 degrees is the best, and is arranged in the axial direction with the left higher and the right lower, so that the catalyst is always in the rising process during the movement process, and the movement process of the catalyst is completely driven by the screw 8.

[0062] The present invention provides a device capable of regulating the self-circulation of the catalyst, wherein the catalyst is circulated in the cracking furnace kettle 3 by the self-circulation method, such as Figure 6 The figure shows the direction of catalyst self-circulation. The self-circulation method of the catalyst means that under the action of the screw transmission system 7, the screw 8 is always moving at a certain speed, and the catalyst moves from bottom to top under the driving action of the screw 8 until it reaches the top of the bottom plate 9, and the catalyst gradually accumulates. Under the turning action of the spiral blades at the tail of the screw 8, the catalyst is sent from the gap between the screw 8 and the bottom plate 9 into the hollow screw 8. The catalyst entering the screw 8 moves from top to bottom at a certain speed to the bottom of the screw 8 under the action of its own weight and the spiral edges inside the screw 8, and flows out from the outlet of the head of the hollow screw 8, and the cycle is repeated to realize the self-circulation of the catalyst in the cracking process.

[0063] The entire circulation method has only one power source motor device, which drives the screw 8 to rotate. The rotation of the screw 8 drives the catalyst to move from bottom to top. The catalyst is flipped into the hollow screw 8 by the flipping action of the spiral blades at the tail of the screw 8. The catalyst moves from top to bottom under the action of the catalyst's own weight and the internal spiral edges.

[0064] The catalyst quantitative addition device 1 is used to add catalyst. During the cracking process, the catalyst will be partially deactivated due to friction transportation and accumulation of harmful substances in the cracking intermediates. It needs to be replenished regularly. The catalyst is added to the catalyst self-circulation device 10 through the catalyst quantitative addition device 1 connected to the bottom of the screw 8.

[0065] In a specific embodiment, if Figure 7 As shown, the spiral blades in the E region (the tail of the screw 8) are upward-curved and cooperate with the relative position of the bottom plate 9 to realize the automatic flipping of the catalyst into the C port. Figure 8 As shown, it is an enlarged view of the structure of the E area.

[0066] It should be noted that a certain number of circular holes with a certain aperture size are set in the upper middle of the bottom plate 9, and a certain number of rectangular grooves are randomly opened in the horizontal position of the upper part of the bottom plate 9. The size of the rectangular grooves is: the length is preferably 1 / 5 to 1 / 4 of the width of the bottom plate 9, and the width is preferably 2 to 5 mm. The setting position of the circular hole needs to be determined by the type of catalyst and the running speed of the screw 8. The position setting principle is: at a certain running speed of the screw 8, the highest height of the catalyst running on the bottom plate 9 under the push of the screw 8 cannot reach the lowest position of the circular hole. When the particle size D of the catalyst is less than 10 nanometers, the circular hole size The running speed of the screw 8 is 3-6 mm, and the running speed is the smallest value; when the particle size of the catalyst is large, greater than 100 nanometers, the hole size The running speed of the screw 8 is 5 to 9 mm, and the running speed thereof is set to a minimum value.

[0067] like Fig. 9 As shown, an electric heating coil 17 is installed in the non-perforated area below the bottom plate 9, which can assist in heating the bottom plate 9 in real time according to the temperature change in the cracking reactor, so that the catalyst is always at the optimal cracking temperature. The separate control of the harmful element removal process and the catalytic cracking process conditions involved in the present invention is mainly based on the cracking temperature control to regulate the maximum reaction activity of the harmful element removal composite auxiliary agent and the catalyst, wherein the temperature of the harmful element removal process is controlled by the cracking reactor heating device, and the catalytic cracking process is based on the internal temperature of the cracking reactor. There is an electric heating auxiliary temperature control system (mainly a temperature control system composed of an electric heating coil 17) at the bottom of the bottom plate 9 to ensure that the catalyst is carried out at the optimal catalytic cracking temperature.

[0068] Furthermore, the main system of the cracking reactor also includes a transmission gear 4, a chain transmission system 5 and a catalyst unloading device 6. The chain transmission system 5 drives the transmission gear 4, and then transmits power to the cracking furnace kettle 3 to make it rotate at a uniform speed. The cracking furnace sealing device 2 is installed at both ends of the cracking furnace kettle 3 and is used to keep the rotating cracking furnace kettle 3 sealed. The catalyst unloading device 6 is connected to the cracking furnace kettle 3 and is used to unload the catalyst.

[0069] like Fig.10 As shown, the cracking furnace sealing device 2 includes a sealing dynamic ring 11, a sealing ring 12, a cracking furnace side wall 13, a lubricating oil port 14, a static sealing upper ring 15 and a static sealing lower ring 16. The sealing dynamic ring 11 is a U-shaped structure, interference fit to the corresponding part of the screw 8, and the sealing working plane of the sealing dynamic ring 11 exceeds the working surface of the screw 8 by 1 to 2 mm; two circular rings are welded at the matching part of the cracking furnace side wall 13 and the sealing dynamic ring 11 to form a precision sealing ring (static sealing upper ring 15 and static sealing lower ring 16 respectively), wherein the static sealing upper ring 15 is 10 mm longer than the static sealing lower ring 16; the sealing ring 12 is located in the sealing working area between the sealing dynamic ring 11 and the static sealing upper ring 15 and the static sealing lower ring 16; the lubricating oil port 14 is passed through the lubricating oil to lubricate the sealing working area.

[0070] Example 3

[0071] The present embodiment provides a method for industrial continuous regulation of waste organic polymer material cracking products using the control device of the present invention, wherein a mixture of waste organic polymer material and a composite auxiliary agent for removing harmful elements is transported to the device separately from a catalyst and arranged in an upper and lower manner, wherein the upper layer is a catalyst, which is pushed by a screw 8 to achieve axial movement on a bottom plate 9 with pores and a certain inclination; the lower layer is a mixture of waste organic polymer material and a harmful element removal auxiliary agent, which is pushed by a spiral structure at the bottom of the cracking reactor to move axially, and the movement of the upper and lower materials is maintained in reverse flow.

[0072] The specific process flow of the control method is as follows:

[0073] Waste organic polymer materials such as waste rubber and waste plastics and the harmful element removal composite auxiliary agent enter the cracking furnace kettle body 3 of the main system of the cracking reactor I at the same time under the action of the II feeding system. The cracking reactor drives the chain transmission system 5 and the transmission gear 4 through the motor reducer, and then transmits the power to the cracking furnace kettle body 3 to make it rotate at a uniform speed, and the rotating cracking furnace kettle body 3 is kept sealed under the action of the cracking furnace sealing device 2; under the action of the III combustion and heating system, the temperature of the main system of the cracking reactor I is maintained between 400 and 450°C, so that the molecular chain of the waste organic polymer material is broken to produce active components, and the components are initially reacted with the harmful element removal composite auxiliary agent, so that the harmful components such as sulfur and chlorine in the product are solidified into the cracking solid phase product; the active components after the initial reaction are then contacted with the catalyst to undergo a catalytic reaction, thereby further regulating the quality of the cracking product.

[0074] The catalyst is inputted into the catalyst self-circulation device 10 by the catalyst quantitative adding device 1 at a fixed time and quantity. Under the action of the screw transmission system 7, the screw 8 is always moving at a certain speed, and the catalyst is urged to move from the bottom to the top at a certain speed until it reaches the top of the bottom plate 9. The catalyst gradually accumulates. Under the action of the unique spiral ridge structure in the screw 8E area, the catalyst is turned from the gap between the screw 8 and the bottom plate 9 to the inside of the screw 8. The catalyst entering the inside of the screw 8 is uniformly transported to the bottom of the screw 8 at a certain speed under the action of the internal spiral ridge and its own weight, and flows out from the outlet of the head of the hollow screw 8. This cycle is repeated to realize the self-circulation of the catalyst during the cracking process. In addition, in the process of catalyst self-circulation, in order to achieve effective regulation of the cracking product, based on the temperature of the cracking reactor, the temperature of the catalyst self-circulation system is assisted by adjusting the electric heating system of the bottom plate 9, so that the catalyst is always at the optimal temperature during the cracking process, thereby improving the quality of the cracking product.

[0075] After the catalyst has been used for a period of time, its activity decreases and it needs to be replenished regularly. In this case, it is added to the catalyst self-circulation device 10 through the catalyst quantitative addition device 1 at the bottom of the screw 8. When the catalyst in the catalyst self-circulation device 10 reaches 40% of the total volume of the catalyst self-circulation device 10, all the catalyst needs to be unloaded through the catalyst unloading device 6, and then new catalyst is added again through the catalyst quantitative addition device 1.

[0076] After the cracking gas product reacts with the harmful element removal composite additive and catalyst, it passes through the A port and is connected to the cracking gas condensation recovery system for sedimentation and cooling to form cracking oil products. The uncondensed cracking gas continues to enter the non-condensable combustible gas recycling system, and the non-condensable combustible gas recycling system is connected to the III combustion heating system to provide energy for the cracking reaction; the cracking residue generated by the cracking of the waste organic polymer material passes through the I cracking reactor main system through the outlet flange and enters the IV cracking residue transportation system; the flue gas generated after combustion passes through the exhaust gas treatment system and meets the emission standards.

[0077] Test Example 1

[0078] The control device of the present invention was used to conduct a systematic waste tire pyrolysis experimental study, and compared with the traditional pyrolysis method (rotary kiln pyrolysis reactor, pyrolysis temperature controlled at 500°C), the specific results are as follows:

[0079] Experimental materials: Waste car tires, crushed into blocks of about 15 cm.

[0080] Experimental data:

[0081] (1) Material balance experimental data

[0082] Table 1 Material balance of pyrolysis of mixed waste plastics

[0083]

[0084] The cracking product control method provided by the present invention can significantly increase the output of cracking oil products and reduce the output of cracking gas, thereby greatly improving the economic benefits and production safety of cracking enterprises.

[0085] (2) Analysis of cracking oil performance

[0086] Table 2 Oil performance analysis

[0087]

[0088]

[0089] From the above experimental data, it can be seen that the closed cup flash point and kinematic viscosity of the cracked oil obtained by the cracking product regulation method of the present invention are higher than those of the traditional cracking method, the oil density is lower than that of the traditional method, and the oil distillation recovery temperatures are lower than those obtained by the traditional method, indicating that the light components in the oil are significantly increased and the oil quality is significantly improved.

[0090] (3) Content of valuable substances in cracking oil products

[0091] Table 3 Analysis of the content of valuable substances in oil products

[0092]

[0093] (4) Analysis of cracking residues

[0094] Table 4 Cracking residue data analysis

[0095]

[0096] It can be seen from the above experimental data that the high calorific value of the residue after cracking using the method of the present invention is significantly reduced, indicating that the cracking is more complete and the content of harmful elements in the cracking residue is significantly reduced.

[0097] In summary, the device and method of the present invention can significantly improve the pyrolysis effect of mixed waste plastics, significantly improve the yield and quality of pyrolysis oil products, and make the entire pyrolysis process more complete.

[0098] Test Example 2

[0099] The device of the present invention was used to conduct a systematic waste plastic pyrolysis experimental study, and compared with the traditional pyrolysis method (rotary kiln pyrolysis reactor, pyrolysis temperature controlled at 500°C), the specific results are as follows:

[0100] Experimental raw materials: waste plastics from paper mills

[0101] Experimental data:

[0102] (1) Material balance experimental data

[0103] Table 5 Material balance of pyrolysis of mixed waste plastics

[0104]

[0105] The method of the invention can significantly increase the output of cracking oil products, transform mixed waste plastics into liquid products, reduce the output of cracking gas, and thus greatly improve the economic benefits and production safety of cracking enterprises.

[0106] (2) Analysis of cracking oil performance

[0107] Table 6 Oil performance analysis

[0108]

[0109]

[0110] From the above experimental data, it can be seen that the closed flash point and kinematic viscosity of the cracked oil obtained by the method of the present invention are higher than those of the traditional cracking method, the oil density is lower than that of the traditional method, and the oil distillation recovery temperatures are lower than those obtained by the traditional method, indicating that the light components in the oil are significantly increased and the oil quality is significantly improved.

[0111] (3) Content of valuable substances in cracking oil

[0112] Table 7 Analysis of the content of valuable substances in oil products

[0113]

[0114] (4) Analysis of cracking residues

[0115] Table 8 Cracking residue data analysis

[0116]

[0117] It can be seen from the above experimental data that the high calorific value of the residue after cracking by the present invention is significantly reduced, indicating that the cracking is more complete and the content of harmful elements in the cracking residue is significantly reduced.

[0118] In summary, the device and method of the present invention can significantly improve the pyrolysis effect of mixed waste plastics, significantly improve the yield and quality of pyrolysis oil products, and make the entire pyrolysis process more complete.

[0119] The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art can still modify the technical solutions described in the above embodiments, or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, modification, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for regulating the pyrolysis products of waste organic polymer materials, characterized in that: The following steps are involved: (1) mixing the waste organic polymer material and the harmful element removal composite auxiliary agent in a mass ratio of 90:10, and placing the mixture under a waste organic polymer material cracking temperature of 400 to 450° C. to decompose the waste organic polymer material to produce a cracking primary product; (2) separating the waste organic polymer material mixed with the harmful element removal composite auxiliary agent from the catalyst, placing them in an upper and lower layout, with the upper layer being the catalyst and the lower layer being the mixture of the waste organic polymer material and the harmful element removal composite auxiliary agent, and making the movement directions of the materials in the upper and lower layers opposite to each other, maintaining the reverse flow, and fully contacting the primary cracking product after the reaction with the harmful element removal composite auxiliary agent with the catalyst, and placing the product under a product control temperature condition of 550 to 800° C., to obtain a cracking final value product mainly composed of aromatic hydrocarbons; The catalyst is any one of oil refining waste catalyst, fly ash, red mud or a mixture of several thereof, and the harmful element removal composite auxiliary agent is an alkaline component with red mud as the main component.

2. The method according to claim 1, characterized in that A mixture of a catalyst, waste organic polymer materials and a harmful element removal composite auxiliary agent is placed in a cracking reactor, arranged in an upper and lower layout, and the movement direction is controlled so that the catalyst in the upper layer and the waste organic polymer materials and the harmful element removal composite auxiliary agent in the lower layer move in opposite directions during the cracking process, so as to perform ex situ catalytic cracking; The waste organic polymer material includes waste rubber and waste plastic. When the waste organic polymer material is waste rubber, the mass ratio of the waste catalyst of oil refining, fly ash and red mud is 60:30:10; when the waste organic polymer material is waste plastic, the mass ratio of the waste catalyst of oil refining, fly ash and red mud is 45:40:

15.

3. The method according to claim 1, characterized in that The harmful elements in the waste organic polymer material are cracked and reacted with the harmful element removal composite auxiliary agent to solidify the harmful elements into the harmful element removal composite auxiliary agent, wherein the harmful elements include sulfur, chlorine and silicon; The harmful element removal composite auxiliary agent also includes an alkaline substance and a binder, wherein the alkaline substance includes calcium oxide, calcium carbonate, dolomite, magnesium oxide, sodium carbonate and mordenite; The harmful element removal composite auxiliary agent is prepared by mixing and granulating the following components in parts by weight: 20-25 parts of red mud, 15-20 parts of calcium oxide, 10 parts of calcium carbonate, 5-10 parts of dolomite, 5-10 parts of magnesium oxide, 10-15 parts of sodium carbonate, 10-15 parts of mordenite, and 5 parts of a binder.

4. A device for implementing the method according to any one of claims 1 to 3, characterized in that: The device comprises a cracking reactor main body system, which comprises a catalyst quantitative adding device, a cracking furnace kettle body and a catalyst self-circulation device obliquely arranged inside the kettle body, and the catalyst self-circulation device comprises a screw, a bottom plate and a screw transmission system, and an electric heating coil is arranged at the bottom of the bottom plate; the interior of the screw is a hollow structure, and the inner and outer surfaces thereof are both provided with spiral structures with opposite spiral rotation directions, wherein the inner spiral angle is 5-10% greater than the outer surface spiral angle.

5. The device according to claim 4, characterized in that The tail of the screw is a spiral blade structure, and the rest of the screw is a spiral ridge structure. The thickness of the spiral blade is 1 / 5 to 1 / 3 of the thickness of the spiral ridge, and the rotation arc of the spiral blade is 3 to 4 times the rotation arc of the spiral ridge. The gap between the spiral ridge and the bottom plate is 1 to 3 mm, and the inclination angle of the bottom plate is 3 to 7 degrees. The bottom plate is fixedly installed inside the cracking furnace kettle in the axial direction according to the arrangement of left high and right low.

6. The device according to claim 5, characterized in that The catalyst is circulated under the action of the catalyst self-circulation device, and the specific steps are: the catalyst input through the catalyst quantitative addition device moves from bottom to top under the pushing action of the screw until it reaches the top of the bottom plate, the catalyst is gradually accumulated, and the catalyst is sent into the hollow interior of the screw under the turning action of the spiral blade at the tail of the screw. The catalyst moves from top to bottom at a certain movement speed to the bottom end of the bottom plate under the action of its own weight and the spiral edges inside the screw, and flows out from the outlet of the hollow screw head, and the cycle is repeated to realize the self-circulation of the catalyst in the cracking process; The catalyst self-circulation device has only one power source motor device, which drives the screw to rotate through the motor. The rotation of the screw drives the catalyst to move from bottom to top. The catalyst is flipped into the hollow screw through the flipping action of the spiral blades at the tail of the screw. The catalyst moves from top to bottom under the action of its own weight and the internal spiral edges.

7. The device according to claim 4, characterized in that The cracking reactor main body system also includes a cracking furnace sealing device, a transmission gear, a chain transmission system and a catalyst unloading device. The chain transmission system drives the transmission gear and then transmits power to the cracking furnace kettle to make it rotate at a uniform speed. The cracking furnace sealing device is installed at both ends of the cracking furnace kettle and is used to keep the rotating cracking furnace kettle sealed. The catalyst unloading device is connected to the cracking furnace kettle and is used to unload the catalyst.

8. The device according to claim 4, characterized in that The middle part of the bottom plate is sunken downward to form a groove structure, and a plurality of circular holes are provided at the upper position of the inner wall of the groove. When the catalyst particle size is less than 10nm, the circular hole size is 3-6mm, and when the catalyst particle size is greater than 100nm, the circular hole size is 5-9mm; Both sides of the bottom plate are flat plate structures, and rectangular grooves are arranged on the flat plates. The length of the rectangular grooves is 1 / 5 to 1 / 4 of the width of the bottom plate, and the width is 2 to 5 mm.

9. The device according to claim 7, characterized in that The cracking furnace sealing device comprises a cracking furnace side wall and a sealing dynamic ring of a U-shaped structure, the sealing dynamic ring is interference fit with the screw, and the sealing working plane of the sealing dynamic ring exceeds the working surface of the screw by 1 to 2 mm; the matching position between the cracking furnace side wall and the sealing dynamic ring is provided with a static sealing upper ring and a static sealing lower ring, both of which are circular rings, the static sealing upper ring is 10 mm longer than the static sealing lower ring, and a sealing ring is provided between the sealing dynamic ring and the static sealing upper ring and the static sealing lower ring; the cracking furnace sealing device also comprises a lubricating oil port.

10. The device according to claim 4, characterized in that The device also includes a feeding system, a combustion heat supply system and a cracking residue conveying system. The outlet of the feeding system is connected to the inlet of the cracking reactor main system, the outlet of the cracking reactor main system is connected to the cracking residue conveying system, the top of the cracking reactor main system is connected to a cracking gas condensation recovery system and a non-condensable combustible gas recycling system, and the non-condensable combustible gas recycling system is connected to the combustion heat supply system and the tail gas treatment system in sequence.

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