Structure-reconstructed pyrolytic carbon black and preparation method therefor, and device

Abstract

A structure-reconstructed pyrolytic carbon black and a preparation method therefor, and a device, relating to the technical field of solid waste recycling. The preparation method comprises: in a protective gas atmosphere, setting a temperature to 830-980°C, and bringing an external carbon source and a pyrolytic carbon black into full contact with a reaction-initiating active carrier for 5-12 s to obtain a modified pyrolytic carbon black; treating the modified pyrolytic carbon black at a temperature of 450-550°C for 1-3 min by means of a plasma at a discharge power of 200-400 W; and then placing the treated modified pyrolytic carbon black in a 4-9 mol / L acidic solution for soaking for 5-15 min, wherein the carbon source is any one of a gaseous hydrocarbon, a high carbon content polymer, or a thermosetting resin, and the reaction-initiating active carrier is a copper foil carrier. By using the method and device, an external carbon source is consolidated to the surface of a pyrolytic carbon black under high temperature conditions, so that new pore structures and chemical functional groups are formed, thereby reconstructing the structure of the pyrolytic carbon black and the microchemical environment on the surface, thus enhancing the bonding performance of the pyrolytic carbon black and a rubber composite material.

Description

Structurally reconstructed pyrolysis carbon black and preparation method and device thereof TECHNICAL FIELD

[0001] The present application belongs to the technical field of solid waste recycling, and particularly relates to a structurally reconstructed pyrolysis carbon black and a preparation method and device thereof, especially to pyrolysis carbon black obtained by pyrolysis of waste tires, which is remodeled in structure and surface micro-chemical environment to increase the bonding performance of the pyrolysis carbon black and rubber composites. BACKGROUND

[0002] With the continuous increase of the number of automobiles in China, the annual production of waste tires is increasing year by year, which has caused serious waste of energy resources and environmental pollution. Pyrolysis can convert waste tires into oil rich in aromatic hydrocarbons, gas with high calorific value, and reusable carbon black and steel wire, which can realize the maximum recovery of energy and resource recycling of waste tires, and is the most effective way of waste tire resource treatment. Compared with other final treatment methods of waste tires, pyrolysis has the advantages of large treatment capacity, high economic benefit and small pollution. At present, the United States and some European countries have banned burning, landfilling and stacking, and only allowed pyrolysis, considering that pyrolysis is the most effective and thorough treatment method.

[0003] Pyrolysis carbon black is the second largest product of waste tire pyrolysis, accounting for about 30-35%, which is very complex in composition and mainly contains fillers (carbon black, white carbon black) added during tire manufacturing, vulcanization aids (zinc oxide), and reaction derivatives (zinc sulfide and other substances generated by the reaction of zinc oxide and sulfur) generated during pyrolysis. It has many impurities and low activity, and compared with industrialized carbon black, it has the disadvantages of large particle size, low structure, and low surface activity, which makes it unable to be reused in the preparation process of new tires. Therefore, the pyrolysis carbon black needs to be modified before reuse.

[0004] There are many methods for activating and modifying pyrolysis carbon black, and a large number of patents have been reported. However, the methods involved are basically based on the obtained pyrolysis carbon black for impurity removal and activation treatment. Although the strength of the treated pyrolysis carbon black is improved to some extent, its 300% modulus of elongation is still very low, which cannot meet the use requirements of tires. The 300% modulus of elongation is mainly related to the structure of the pyrolysis carbon black. The higher the structure of the pyrolysis carbon black, the greater the value of the 300% modulus of elongation. According to the correlation between material properties and material structure, it can be clearly understood that the current methods and processes for treating pyrolysis carbon black have not fundamentally solved the problem of low structure of pyrolysis carbon black.

[0005] SUMMARY

[0006] The present application aims at solving the above problems in the prior art, and provides a structure-reconstructed pyrolysis carbon black and a preparation method and device thereof.

[0007] The technical scheme of the present application is:

[0008] The present application provides a preparation method of structure-reconstructed pyrolysis carbon black, which is to solidify an additional carbon source to the surface of pyrolysis carbon black under certain temperature conditions, form new pore structures and chemical functional groups, reshape the structure and surface micro-chemical environment of pyrolysis carbon black, and includes the following steps:

[0009] S1: under a protective atmosphere, set the temperature to 830-980℃, and fully contact the additional carbon source, pyrolysis carbon black and an initiating reaction active carrier for 5-12s, grow new pore structures on the surface of pyrolysis carbon black, change the primary particle morphology of pyrolysis carbon black, and form new chemical functional groups on the surface of pyrolysis carbon black to obtain modified pyrolysis carbon black;

[0010] The number of surface chemical functional groups of the modified pyrolysis carbon black in step S1 is mainly related to the residence time of the carbon source on the surface of pyrolysis carbon black. Only when the carbon source is fully contacted with the pyrolysis carbon black can the functional groups be formed on the surface of the pyrolysis carbon black (the optimal residence time is 2-5 seconds). In the present application, the carbon source includes gaseous and solid carbon sources. However, when the carbon source is in the form of gas, it only needs to be heated to a certain temperature to decompose and react with the pyrolysis carbon black. When the carbon source is in the form of solid, it needs to be decomposed into gaseous carbon source and then react with the pyrolysis carbon black. Therefore, the reaction time is set to 5-12s.

[0011] The reaction temperature is any temperature value in the range of 830-980℃, for example, it can be 830℃, 850℃, 870℃, 880℃, 890℃, 895℃, 900℃, 910℃, 920℃, 925℃, 940℃, 950℃, 970℃, or 980℃, but is not limited to the listed values, and other unlisted values in this range are also applicable.

[0012] The contact time is any value in the range of 5-12s, for example, it can be 5s, 6s, 7s, 8s, 9s, 10s, 11s or 12s, but is not limited to the listed values, and other unlisted values in this range are also applicable.

[0013] S2: the modified pyrolysis carbon black is treated by 200-400W plasma discharge power at 450-550℃ for 1-3min; step S2 improves the ordered distribution characteristics of carbon structure by local oxidation and etching, increases the activity, and enriches the surface active functional groups.

[0014] S3: the treated modified pyrolysis carbon black is placed in an acid solution with a concentration of 4-9mol / L for 5-15min;

[0015] The acid solution concentration is any value in the range of 4-9mol / L, for example, it can be 4mol / L, 5mol / L, 6mol / L, 7mol / L, 8mol / L or 9mol / L, etc., but is not limited to the listed values, and other unlisted values in this range are also applicable.

[0016] The soaking time is any time in the range of 5-15min, for example, it can be 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min or 15min, etc., but is not limited to the listed values, and other unlisted values in this range are also applicable.

[0017] S4: drying;

[0018] S5: the supercritical carbon dioxide is fully mixed with the structure-reconstructed pyrolysis carbon black, sprayed out through a special nozzle, and the strong high-frequency pulsating shear force field formed by the rapid expansion of the critical carbon dioxide refines the pyrolysis carbon black particle size, and finally the structure-reconstructed pyrolysis carbon black is obtained;

[0019] The carbon source is any one of gaseous hydrocarbons, high-carbon-content polymers or thermosetting resins;

[0020] The initiation reaction active carrier is a copper foil carrier; it needs to be particularly pointed out that under the condition of different initiation reaction active carriers, the method of the present application can produce modified pyrolysis carbon black with completely different properties. The formation of new chemical functional groups on the surface of the pyrolysis carbon black in the present application is formed under the condition of the copper foil-based initiation reaction active carrier, and if other systems of initiation reaction active carriers are replaced, different chemical functional groups will be formed.

[0021] The present application adopts the above preparation method, which can fix the additional carbon source to the surface of the pyrolysis carbon black, grow new pore structures on the surface of the pyrolysis carbon black, change the primary particle morphology of the pyrolysis carbon black, and form new chemical functional groups on the surface of the pyrolysis carbon black.

[0022] Further, the protective atmosphere is selected from inert gas atmosphere, including nitrogen and argon;

[0023] The gaseous hydrocarbon is selected from gaseous hydrocarbons with a carbon content of more than 90%, including methane.

[0024] The high-carbon-content polymer includes any one of polyethylene, polypropylene, polystyrene, or a mixture of several thereof.

[0025] Further, when the carbon source is a gaseous hydrocarbon, the gaseous hydrocarbon is continuously introduced at an inlet amount of 20 ml / min, and is fully contacted with the pyrolytic carbon black and the reaction-initiating active carrier under an argon protective atmosphere at a temperature rising rate of 10-15 K / min and a final temperature of 900-950℃ for 5-10 seconds.

[0026] The temperature rising rate is any rate within the range of 10-15 K / min, for example, 10 K / min, 11 K / min, 12 K / min, 13 K / min, 14 K / min, or 15 K / min, etc., but is not limited to the listed values, and other values not listed within the range are also applicable. Among them, the optimal temperature rising rate is 13 K / min.

[0027] The reaction temperature is preferably 930℃.

[0028] The contact time is any value within the range of 5-10 seconds, for example, 5 seconds, 6 seconds, 7 seconds, 8 seconds, 9 seconds, or 10 seconds, etc., but is not limited to the listed values, and other values not listed within the range are also applicable. Among them, the optimal contact time is 8 seconds.

[0029] When the carbon source is a high-carbon-content polymer, the mass ratio of the high-carbon-content polymer to the pyrolytic carbon black is 1.5-2:100, and the pyrolytic carbon black is fully contacted with the high-carbon-content polymer decomposition product and the reaction-initiating active carrier under an argon protective atmosphere at a temperature rising rate of 5-10 K / min and a final temperature of 830-880℃ for 8-12 seconds.

[0030] The mass ratio 1.5-2:100 can be 1.5:100, 1.6:100, 1.7:100, 1.8:100, 1.9:100, or 1:50, etc., but is not limited to the listed values, and other values not listed within the range are also applicable.

[0031] The temperature rising rate is any rate within the range of 5-10 K / min, for example, 5 K / min, 6 K / min, 7 K / min, 8 K / min, 9 K / min, or 10 K / min, etc., but is not limited to the listed values, and other values not listed within the range are also applicable. Among them, the optimal temperature rising rate is 8 K / min.

[0032] The reaction temperature is preferably 850℃.

[0033] The contact time can be any value in the range of 8-12 seconds, such as 8 seconds, 9 seconds, 10 seconds, 11 seconds or 12 seconds, but is not limited to the listed values, and other values not listed in the range are also applicable. The optimal contact time is 10 seconds.

[0034] When the carbon source is a thermosetting resin, the mass ratio of the thermosetting resin to the pyrolytic carbon black is 2.5-3.5:100, and the pyrolytic carbon black is fully contacted with the decomposition product of the thermosetting resin and the reaction active carrier under the protection of a nitrogen atmosphere at a temperature rising rate of 2-5 K / min and a final temperature of 950-980℃ for 5-8 seconds.

[0035] The mass ratio of 2.5-3.5:100 can be 2.5:100, 2.6:100, 2.7:100, 2.8:100, 2.9:100, 3.0:100, 3.1:100, 3.2:100, 3.3:100, 3.4:100 or 3.5:100, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0036] The temperature rising rate can be any rate in the range of 2-5 K / min, such as 2 K / min, 3 K / min, 4 K / min or 5 K / min, but is not limited to the listed values, and other values not listed in the range are also applicable. The optimal temperature rising rate is 3 K / min.

[0037] The reaction temperature is preferably 970℃.

[0038] The contact time can be any value in the range of 5-8 seconds, such as 5 seconds, 6 seconds, 7 seconds or 8 seconds, but is not limited to the listed values, and other values not listed in the range are also applicable. The optimal contact time is 7 seconds.

[0039] Further, in the step S1, the additional carbon source is fixed to the surface of the pyrolytic carbon black to form a chemical functional group; the formation of the new chemical functional group on the surface of the pyrolytic carbon black is closely related to the form and structure reconstruction process of the carbon source; under the above reaction conditions, when the gaseous hydrocarbon is used as the carbon source, the functional group is mainly hydroxyl; when the high-carbon-content polymer is used as the carbon source, the functional group is mainly hydroxyl and amide; and when the thermosetting resin is used as the carbon source, the functional group is mainly hydroxyl and aromatic.

[0040] Further, the step S2 is to locally oxidize the modified pyrolytic carbon black, i.e., the modified pyrolytic carbon black is used to strengthen the surface carbon source structure at a certain temperature by plasma; which includes:

[0041] The modified pyrolytic carbon black is treated by a 200 W plasma discharge power at a temperature of 450℃ for 3 min; or,

[0042] The modified pyrolysis carbon black is treated by a discharge power of 300W plasma for 2min at a temperature of 500℃; or,

[0043] The modified pyrolysis carbon black is treated by a discharge power of 400W plasma for 1min at a temperature of 550℃.

[0044] Further, the step S3 is etching the modified pyrolysis carbon black, and the acid solution is one or both of sulfuric acid and hydrofluoric acid.

[0045] In the sulfuric acid condition, the concentration is 5-9mol / L, and the soaking time is 10-15min; preferably, the optimal concentration is 7mol / L, and the optimal soaking time is 12min.

[0046] In the hydrofluoric acid condition, the concentration is 4-7mol / L, and the soaking time is 5-10min; preferably, the optimal concentration is 5mol / L, and the optimal soaking time is 7min.

[0047] After the new chemical functional groups are formed on the surface of the pyrolysis carbon black, the partial oxidation and etching can improve the ordered distribution characteristics of the carbon structure, increase the activity, and enrich the surface active functional groups.

[0048] The application also provides the structural reconstruction pyrolysis carbon black prepared by the preparation method.

[0049] The preparation method of the structural reconstruction pyrolysis carbon black provided by the application can control the size, growth thickness of the surface pore structure of the pyrolysis carbon black, and the type and quantity of the surface chemical functional groups by adjusting and optimizing the adding proportion of the pyrolysis carbon black and the additional carbon source, the reaction atmosphere, the reaction temperature, the reaction time, and the partial oxidation and etching conditions.

[0050] The above-mentioned external multi-field strengthening refers to introducing a magnetic field, ultrasonic, plasma and other fields in the pyrolysis carbon black treatment process, activating the gas around the surface of the pyrolysis carbon black, changing the aggregation state evolution of the structural reconstruction pyrolysis carbon black, and thus achieving the effect of strengthening the structural reconstruction of the pyrolysis carbon black.

[0051] The above-mentioned multi-process parameter control is adjusting the structural reconstruction process parameters of the pyrolysis carbon black according to the performance requirements of the target product pyrolysis carbon black, such as the structure degree, the aggregation state structure, the chemical composition, the surface morphology, and the surface chemical group properties.

[0052] The performance requirements of the structure degree of the target product pyrolysis carbon black are mainly achieved by adjusting the process parameters of the adding proportion of the pyrolysis carbon black and the additional carbon source, the reaction atmosphere, and the reaction temperature.

[0053] The performance requirements of the target product pyrolytic carbon black aggregate structure are mainly realized by adjusting the reaction time, reaction atmosphere, reaction temperature, and local oxidation and etching conditions.

[0054] The performance requirements of the target product pyrolytic carbon black chemical composition are mainly realized by adjusting the pyrolytic carbon black and the added proportion of the external carbon source, the reaction atmosphere, and the reaction temperature.

[0055] The performance requirements of the target product pyrolytic carbon black surface morphology are mainly realized by adjusting the reaction time, reaction temperature, local oxidation and etching conditions.

[0056] The performance requirements of the target product pyrolytic carbon black surface chemical group properties are mainly realized by adjusting the local oxidation and etching conditions.

[0057] Further, the structure reconstructed pyrolytic carbon black is mixed with rubber to prepare a structure reconstructed pyrolytic carbon black rubber composite material.

[0058] In order to increase the binding performance of the pyrolytic carbon black and the rubber composite material, the structure reconstructed pyrolytic carbon black rubber composite material preparation mixing process is also needed; in the mixing process, the composite material needs to be added with small materials first, then added with rubber, then added with white carbon black, and then the structure reconstructed pyrolytic carbon black is added with operating oil into the mixing system, and the glue is discharged after the mixing temperature reaches 155 DEG C, and then cooled.

[0059] The application further provides a device for realizing the preparation method.

[0060] Further, the continuous feeding extruder is fixedly connected with the device body and forms a 45-degree angle with the shell.

[0061] The shell is further provided with a protective gas inlet and a protective gas outlet, and the protective gas inlet and the protective gas outlet are respectively connected with both ends of the protective gas channel.

[0062] The protective gas channel is installed in the middle of the conveying assembly at a position 20% higher than the middle;

[0063] The position where the shell cooperates with the driving wheel of the conveying assembly and the driven wheel of the conveying assembly is provided with a sealing assembly, the sealing assembly comprises a shell side wall, a driving wheel center shaft and a sealing movable ring in interference fit with the driving wheel center shaft, the sealing movable ring is a U-shaped structure, the sealing movable ring sealing working plane exceeds the working surface of the driving wheel center shaft by 1-2mm, the shell side wall is provided with a static seal upper ring and a static seal lower ring at the cooperation position of the shell side wall and the sealing movable ring, the static seal upper ring and the static seal lower ring are both circular rings, the static seal upper ring is 10mm longer than the static seal lower ring, a sealing ring is arranged between the sealing movable ring and the static seal upper ring and the static seal lower ring, and the sealing assembly further comprises a lubricating oil port.

[0064] The beneficial effects of the present application are as follows:

[0065] The present application can adjust and optimize the ratio of pyrolysis carbon black and additional carbon source, control the reaction atmosphere, optimize the reaction temperature, adjust the reaction time, and optimize the local oxidation and etching conditions, so as to control the size and growth thickness of the pore structure on the surface of the pyrolysis carbon black, and the type and quantity of the surface chemical functional groups, and develop a complete set of pyrolysis carbon black structure reconstruction device.

[0066] The present application realizes the transformation of the tire life cycle from a linear mode of "resource-product-waste" to a circular mode of "resource-product-regenerated resource", which is of great significance for promoting the construction of ecological civilization in China and building a resource-saving and environment-friendly society. BRIEF DESCRIPTION OF DRAWINGS

[0067] Fig. 1 is a schematic diagram of the device structure provided by the present application;

[0068] Fig. 2 is a cross-sectional view of the device structure provided by the present application;

[0069] Fig. 3 is a schematic diagram of the sealing assembly provided by the present application;

[0070] In the above figures, I, continuous feeding extruder; II, device body; III, continuous discharging extruder; IV, rack; 1, sealing assembly; 2, protective gas inlet; 3, protective gas outlet; 4, bearing assembly; 4-1, sealing dynamic ring; 4-2, sealing ring; 4-3, static sealing upper ring; 4-4, static sealing lower ring; 5, transmission assembly; 6, shell; 6-1, shell side wall; 6-2, lubricating oil port; 7, protective gas channel; 8, conveying assembly; 9, conveying assembly driving wheel; 9-1, driving wheel center shaft; 10, conveying assembly driven wheel. DETAILED DESCRIPTION

[0071] The technical solutions of the present application will be described clearly and completely below in combination with specific embodiments and drawings. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the present application.

[0072] Embodiment 1

[0073] In this embodiment, gaseous hydrocarbon is used as carbon source to reconstruct the structure of pyrolysis carbon black under the condition.

[0074] (1) Reconstructing process of pyrolysis carbon black structure:

[0075] S1: In the process of reconstructing the structure of pyrolysis carbon black, methane is used as carbon source. Methane is continuously fed into the reaction device at a rate of 20 ml / min. Under the protection of argon atmosphere, the temperature is raised at a rate of 13 K / min, and the final temperature is 950℃. Under the high temperature condition, the methane and pyrolysis carbon black are fully contacted on the copper foil carrier for 10 seconds.

[0076] S2: The modified pyrolysis carbon black produced in step S1 is treated by 200W plasma discharge power for 3min at a temperature of 450℃.

[0077] S3: The modified pyrolysis carbon black treated in step S2 is soaked in sulfuric acid with a concentration of 7mol / L for 12min.

[0078] S4: The modified pyrolysis carbon black prepared in step S3 is dried.

[0079] (2) Preparation process of rubber composite material of reconstructed pyrolysis carbon black:

[0080] S1: The modified pyrolysis carbon black prepared by reconstructing the structure of pyrolysis carbon black is weighed according to the requirements of the rubber composite material formula. The formula components and proportions are shown in Table 1 below:

[0081] Table 1: Formula component names and proportions

[0082] S2: The mixing process parameters are set as follows:

[0083] The mixing chamber temperature is 60℃, the rotating speed is 60r / min, the filling coefficient is 0.65, and the upper plunger pressure is 0.7MPa;

[0084] S3: The mixing process is as follows:

[0085] First, add the rubber, mix for 40S, then add zinc oxide ZnO, stearic acid SAD, accelerator 4020, antioxidant RD, microcrystalline wax, plasticizer A; after mixing for 40S, add coupling agent Si69, precipitated white carbon black; after mixing for 40S, slowly and in multiple times add pyrolysis carbon black and operating oil; after mixing for 40S, pull the plug, and finally mix to 155℃ to remove the gum.

[0086] S4: The rubber material obtained by mixing in S3 is pressed and vulcanized, and then the performance of the rubber material is tested.

[0087] (3) Test results

[0088] Table 1 Performance test data of structure reconstructed pyrolysis carbon black

[0089] Table 2 Performance analysis of rubber composite material

[0090] Example 2

[0091] In this embodiment, a high-carbon-content polymer is used as a carbon source to reconstruct the structure of pyrolysis carbon black under the above conditions.

[0092] (1) Structure reconstruction process of pyrolysis carbon black:

[0093] S1: In the structure reconstruction process of pyrolysis carbon black, polyethylene is used as a carbon source, and under an argon protective atmosphere, the temperature is raised at a rate of 8K / min, and the final temperature is 850℃. The pyrolysis carbon black and polyethylene decomposition products with a mass ratio of 1.8:100 are fully contacted on a copper foil carrier for 10 seconds.

[0094] S2: The modified pyrolysis carbon black produced in step S1 is treated by a 300W plasma discharge power at a temperature of 500℃ for 2min;

[0095] S3: The modified pyrolysis carbon black treated in step S2 is immersed in sulfuric acid with a concentration of 7mol / L for 12min.

[0096] S4: The modified pyrolysis carbon black prepared in step S3 is dried.

[0097] (2) Rubber composite material preparation process of structure reconstructed pyrolysis carbon black:

[0098] S1: The modified pyrolysis carbon black prepared by the structure reconstruction of pyrolysis carbon black was weighed according to the requirements of the rubber composite material formula; the formula components and proportions are shown in Table 1 in Example 1.

[0099] S2: The mixing process parameters were set as follows:

[0100] The mixing chamber temperature was 60°C, the rotation speed was 60 r / min, the filling coefficient was 0.65, and the upper plunger pressure was 0.7 MPa;

[0101] S3: The mixing process was as follows:

[0102] First, the rubber was added, and after mixing for 40S, zinc oxide ZnO, stearic acid SAD, accelerator 4020, antioxidant RD, microcrystalline wax, and plasticizer A were added; after mixing for 40S, coupling agent Si69 and precipitated white carbon black were added; after mixing for 40S, the pyrolysis carbon black and the operating oil were slowly and repeatedly added; after mixing for 40S, the plunger was removed, and finally the glue was discharged when the temperature reached 155°C.

[0103] S4: The glue obtained by mixing in S3 was pressed and vulcanized, and then the glue performance was tested.

[0104] (3) Test results

[0105] Table 3: Performance test data of structure reconstruction pyrolysis carbon black

[0106] Table 4: Performance analysis of rubber composite material

[0107] Example 3

[0108] In this example, thermosetting resin was used as a carbon source to reconstruct the structure of pyrolysis carbon black under the condition.

[0109] (1) Structure reconstruction process of pyrolysis carbon black:

[0110] S1: In the structure reconstruction process of pyrolysis carbon black, acrylic resin was used as a carbon source under the condition of nitrogen protection atmosphere, with a heating rate of 3K / min, and the final temperature was 980°C. The pyrolysis carbon black and the decomposition product of acrylic resin with a mass ratio of 3:100 were fully contacted on a copper foil carrier for 8 seconds.

[0111] S2: The modified pyrolysis carbon black produced in step S1 was treated by 400W plasma discharge power for 1min at a temperature of 550°C;

[0112] S3: The modified pyrolysis carbon black treated in step S2 was immersed in sulfuric acid with a concentration of 7mol / L for 12min.

[0113] S4: drying the modified pyrolysis carbon black prepared in step S3.

[0114] (2) Preparation process of the structure-reformed pyrolysis carbon black rubber composite material:

[0115] S1: The modified pyrolysis carbon black prepared by structure-reforming pyrolysis carbon black is weighed according to the rubber composite material formula; the formula components and the proportions are shown in Table 1 in Example 1.

[0116] S2: The mixing process parameters are set as follows:

[0117] The mixing chamber temperature is 60℃, the rotating speed is 60r / min, the filling coefficient is 0.65, and the upper plunger pressure is 0.7MPa.

[0118] S3: The mixing process is as follows:

[0119] First, the rubber is added, and after mixing for 40S, zinc oxide ZnO, stearic acid SAD, accelerator 4020, antioxidant RD, microcrystalline wax, and plasticizer A are added; after mixing for 40S, coupling agent Si69 and precipitated white carbon black are added; after mixing for 40S, the pyrolysis carbon black and the operating oil are slowly and repeatedly added; after mixing for 40S, the plunger is lifted, and finally the glue is discharged when the temperature is 155℃.

[0120] S4: The glue obtained by mixing in S3 is pressed and vulcanized, and then the glue performance is tested.

[0121] (3) Test results

[0122] Table 5: Performance test data of structure-reformed pyrolysis carbon black

[0123] Table 6: Performance analysis of rubber composite material

[0124] From the above experimental data, it can be seen that the performance of the structure-reformed pyrolysis carbon black rubber composite material prepared by the present application far exceeds that of the traditional pyrolysis carbon black rubber composite material, and the 300% modulus reaches 18.65MPa, meeting the performance requirements of car tire tread glue.

[0125] Example 4

[0126] This example provides a device for preparing structure-reformed pyrolysis carbon black, as shown in Figures 1 and 2, which comprises a continuous feeding extruder I, a device body II, and a continuous discharging extruder III connected in sequence, and further comprises a rack IV for supporting.

[0127] The device body II includes a shell 6, on which an electric heating coil for heating and maintaining temperature is installed. Inside the shell 6, a conveying assembly 8 and a protective gas channel 7 are arranged, the protective gas channel 7 is installed at a position slightly above the middle of the conveying assembly 8, and in a specific embodiment, the protective gas channel 7 is installed at a position 20% above the middle of the conveying assembly 8. Further, the shell 6 is also provided with a protective gas inlet 2 and a protective gas outlet 3, which are respectively connected to both ends of the protective gas channel 7.

[0128] It can be understood that the conveying assembly 8 is mainly related to the reaction active carrier material (in this specific embodiment, mainly copper foil material), therefore, the conveying assembly 8 is made of copper foil material, so that the pyrolysis carbon black realizes the growth of the surface functional groups of the pyrolysis carbon black under the action of the copper foil reaction active carrier at the modification temperature.

[0129] The continuous feeding extruder I is fixed on the device body II through a flange, and the continuous feeding extruder I is inserted into the device body II and extends to the top of the conveying assembly 8. The continuous discharging extruder III is fixedly connected with the device body II through a flange, and the continuous discharging extruder III is installed at the lowermost position of the device body II and forms a 45-degree angle with the shell 6, so as to realize the continuous entry and output of the pyrolysis carbon black.

[0130] The device body II is fixedly installed with a transmission assembly 5 and a bearing assembly 4; the conveying assembly 8 is respectively provided with a conveying assembly main drive wheel 9 and a conveying assembly driven wheel 10 at both ends, the transmission assembly 5 drives the bearing assembly 4 and the conveying assembly main drive wheel 9 to rotate, thereby driving the conveying assembly 8 and the conveying assembly driven wheel 10 to rotate at a constant speed.

[0131] As shown in FIG. 3, in order to ensure that the protective gas in the device body II does not leak, a sealing assembly 1 needs to be arranged at the cooperation part of the shell 6 and the conveying assembly main drive wheel 9 and the conveying assembly driven wheel 10. The sealing assembly 1 is composed of a transmission wheel center shaft 9-1, a sealing movable ring 4-1, a sealing ring 4-2, a shell side wall 6-1, a lubricating oil port 6-2, a static sealing upper ring 4-3, a static sealing lower ring 4-4, etc., wherein the sealing movable ring 4-1 is a U-shaped structure, which is interference-fitted to the corresponding position of the transmission wheel center shaft 9-1, and the sealing working plane of the sealing movable ring 4-1 exceeds the working surface of the transmission wheel center shaft 9-1 by 1-2 mm; two circular rings are welded at the cooperation part of the shell side wall 6-1 and the sealing movable ring 4-1, to form a precision sealing ring (the static sealing upper ring 4-3 and the static sealing lower ring 4-4), wherein the static sealing upper ring 4-3 is 10 mm longer than the static sealing lower ring 4-4; the sealing ring 4-2 is located in the sealing working area between the sealing movable ring 4-1 and the static sealing upper ring 4-3 and the static sealing lower ring 4-4. The lubricating oil port 6-2 is connected to the lubricating oil to lubricate the sealing working area.

[0132] The pyrolysis carbon black structure reconstruction device has the advantages of simple structure, convenient operation, high efficiency, low cost, and the like.

[0133] The pyrolysis carbon black and the additional carbon source are uniformly and continuously introduced into the conveying assembly 8 in the device body II through the continuous feeding extruder I, the shell 6 in the device body II is provided with an electric heating coil, so that the device body II always maintains the high temperature required by the pyrolysis carbon black modification process, and under the action of the transmission assembly 5, the bearing assembly 4 and the conveying assembly main transmission wheel 9 are driven to rotate, the conveying assembly main transmission wheel 9 drives the conveying assembly 8 and the conveying assembly driven transmission wheel 10 to rotate at a constant speed. Since the material of the conveying assembly 8 is the copper foil material required as an initiating reaction active carrier in the pyrolysis carbon black structure reconstruction process, under the action of the additional carbon source, new functional group structures grow on the surface of the pyrolysis carbon black under high temperature. The whole process needs to be carried out under a certain reaction atmosphere, the reaction atmosphere is mainly introduced into the protective gas passage 7 through the protective gas inlet 2, the protective gas passage 7 is installed at a position about 20% above the middle of the conveying assembly 8, so that the protective gas directly acts on the pyrolysis carbon black reaction active area, and part of the protective gas is discharged from the protective gas outlet 3. The treated pyrolysis carbon black is continuously output to the outside of the equipment through the continuous discharging extruder III.

[0134] The above description is only the preferred embodiment of the present application, and is not a limitation of the present application. Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art can modify the technical solutions recorded in the foregoing embodiments, or make equivalent replacements to some technical features. Any modification, equivalent replacement, modification, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A method for producing a structurally reconstructed pyrolytic carbon black, characterized by, The preparation method is to solidify the additional carbon source to the surface of the pyrolysis carbon black under certain temperature conditions, form new pore structure and chemical functional groups, reshape the structure of the pyrolysis carbon black and the surface micro-chemical environment, and comprises the following steps: S1: under a protective atmosphere, setting the temperature to 830-980 DEG C, fully contacting the additional carbon source, the pyrolysis carbon black and the reaction active carrier to obtain modified pyrolysis carbon black; S2: treating the modified pyrolysis carbon black under the temperature condition of 450-550 DEG C by the discharge power of 200-400 W plasma for 1-3 min; S3: placing the treated modified pyrolysis carbon black in an acidic solution with a concentration of 4-9 mol / L for 5-15 min; S4: drying; S5: fully mixing the supercritical carbon dioxide and the structure-reconstructed pyrolysis carbon black, spraying out by a special nozzle, and forming a strong high-frequency pulsating shear force field by the rapid expansion of the critical carbon dioxide to refine the particle size of the pyrolysis carbon black, and finally obtaining the structure-reconstructed pyrolysis carbon black; The carbon source is any one of gaseous hydrocarbon, high-carbon-content polymer or thermosetting resin; The reaction active carrier is a copper foil carrier.

2. The production method according to claim 1, characterized by, The protective atmosphere is selected from inert gas atmosphere, including nitrogen and argon; The gaseous hydrocarbon is selected from gaseous hydrocarbon with carbon content exceeding 90%, including methane; The high-carbon-content polymer includes any one or mixture of several of polyethylene, polypropylene and polystyrene.

3. The preparation method according to claim 2, characterized in that, When the carbon source is gaseous hydrocarbon, the gaseous hydrocarbon is continuously introduced at an inlet amount of 20 ml / min, under the argon protective atmosphere, at a temperature rising rate of 10-15 K / min, and at a final temperature of 900-950 DEG C, the gaseous hydrocarbon, the pyrolysis carbon black and the reaction active carrier are fully contacted for 5-10 seconds; When the carbon source is high-carbon-content polymer, the mass ratio of the high-carbon-content polymer to the pyrolysis carbon black is 1.5-2:100, under the argon protective atmosphere, at a temperature rising rate of 5-10 K / min, and at a final temperature of 830-880 DEG C, the pyrolysis carbon black and the decomposition product of the high-carbon-content polymer and the reaction active carrier are fully contacted for 8-12 seconds; When the carbon source is thermosetting resin, the mass ratio of the thermosetting resin to the pyrolysis carbon black is 2.5-3.5:100, under the nitrogen protective atmosphere, at a temperature rising rate of 2-5 K / min, and at a final temperature of 950-980 DEG C, the pyrolysis carbon black and the decomposition product of the thermosetting resin and the reaction active carrier are fully contacted for 5-8 seconds.

4. The production method according to claim 3, characterized by, In step S1, the additional carbon source is solidified to the surface of the pyrolysis carbon black to form chemical functional groups; when the gaseous hydrocarbon is used as the carbon source, the functional groups are mainly hydroxyl groups; when the high-carbon-content polymer is used as the carbon source, the functional groups are mainly hydroxyl groups and amide groups; when the thermosetting resin is used as the carbon source, the functional groups are mainly hydroxyl groups and aromatic groups.

5. The preparation method according to claim 1, characterized in that, In step S2, the modified pyrolysis carbon black is partially oxidized, that is, the modified pyrolysis carbon black is used to strengthen the structure of the surface carbon source under certain temperature by plasma; including: the modified pyrolysis carbon black is treated by the discharge power of 200 W plasma for 3 min at 450 DEG C; or, The modified pyrolysis carbon black is treated by 300W plasma discharge power for 2min at 500℃. The modified pyrolysis carbon black is treated by 400W plasma discharge power for 1min at 550℃.

6. The method of claim 1, wherein, The step S3 etches the modified pyrolysis carbon black, and the acid solution is one or both of sulfuric acid and hydrofluoric acid. In the sulfuric acid condition, the concentration is 5-9mol / L, and the soaking time is 10-15min. In the hydrofluoric acid condition, the concentration is 4-7mol / L, and the soaking time is 5-10min.

7. The structural reconstituted pyrolysis carbon black prepared by the preparation method in any one of claims 1-6.

8. The structurally re- engineered pyrolysis carbon black of claim 7, wherein, The structural reconstituted pyrolysis carbon black is mixed with rubber to prepare a structural reconstituted pyrolysis carbon black rubber composite material.

9. An apparatus for carrying out the process according to any one of claims 1 to 6, characterized in that The device comprises a continuous feeding extruder, a device body and a continuous discharging extruder connected in sequence, and a transmission assembly and a bearing assembly are fixedly installed on the device body; the device body comprises a shell, an electric heating coil is installed on the shell, a conveying assembly and a protective gas channel are arranged in the shell, the conveying assembly is made of copper foil material, and the protective gas channel is installed at a position 20% above the middle of the conveying assembly; the continuous feeding extruder is inserted into the device body and extends to directly above the conveying assembly; conveying assembly main drive wheels and conveying assembly driven drive wheels are arranged at the two ends of the conveying assembly respectively, the transmission assembly drives the bearing assembly and the conveying assembly main drive wheels to rotate, thereby driving the conveying assembly and the conveying assembly driven drive wheels to rotate at a constant speed; and the device is further provided with a sealing assembly.

10. The apparatus of claim 9, wherein, The continuous discharging extruder is fixedly connected with the device body and forms a 45-degree angle with the shell; The shell is further provided with a protective gas inlet and a protective gas outlet which are respectively connected with the two ends of the protective gas channel; The protective gas channel is installed at a position 20% above the middle of the conveying assembly; The position where the shell cooperates with the conveying assembly main drive wheels and the conveying assembly driven drive wheels is provided with a sealing assembly, the sealing assembly comprises a shell sidewall, a transmission wheel center shaft and a sealing movable ring in interference fit with the transmission wheel center shaft, the sealing movable ring is in U-shaped structure, the sealing working plane of the sealing movable ring exceeds the working surface of the transmission wheel center shaft by 1-2mm, the position where the shell sidewall cooperates with the sealing movable ring is provided with a static seal upper ring and a static seal lower ring, the static seal upper ring and the static seal lower ring are both circular rings, the static seal upper ring is 10mm longer than the static seal lower ring, a sealing ring is arranged between the sealing movable ring and the static seal upper ring and the static seal lower ring, and the sealing assembly further comprises a lubricating oil port. The continuous discharging extruder is fixedly connected with the device body and forms a 45-degree angle with the shell; The shell is further provided with a protective gas inlet and a protective gas outlet which are respectively connected with the two ends of the protective gas channel; The protective gas channel is installed at a position 20% above the middle of the conveying assembly; The position where the shell cooperates with the conveying assembly main drive wheels and the conveying assembly driven drive wheels is provided with a sealing assembly, the sealing assembly comprises a shell sidewall, a transmission wheel center shaft and a sealing movable ring in interference fit with the transmission wheel center shaft, the sealing movable ring is in U-shaped structure, the sealing working plane of the sealing movable ring exceeds the working surface of the transmission wheel center shaft by 1-2mm, the position where the shell sidewall cooperates with the sealing movable ring is provided with a static seal upper ring and a static seal lower ring, the static seal upper ring and the static seal lower ring are both circular rings, the static seal upper ring is 10mm longer than the static seal lower ring, a sealing ring is arranged between the sealing movable ring and the static seal upper ring and the static seal lower ring, and the sealing assembly further comprises a lubricating oil port.

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