A high-structure low-heat high-safety performance carbon black production method

Abstract

The present application relates to a kind of high structure low heat generation high safety performance carbon black production method, it is mainly related to carbon black production field.It includes the control of raw material, raw material oil pretreatment, fuel oil pretreatment, carbon black pyrolysis preparation, production process improvement, carbon black collection, carbon black granulation, carbon black drying, carbon black conveying storage and carbon black application test in rubber tire.The beneficial effects of the present application are that the carbon black product has a wide aggregate distribution, medium particle size and high structure, which can reduce heat generation, and high structure can compensate for the loss of wear caused by larger particle size, so the product has low rolling resistance and good wet skid resistance.

Description

Technical Field

[0001] This invention relates to a method for producing carbon black with high structure, low heat generation, and high safety performance. Background Technology

[0002] This product is an important reinforcing filler in the rubber industry. With the development of the automotive industry, both production and sales have increased significantly. Tire product structure is transforming towards tubeless, wide-section, large rim, wear-resistant, wet-skid resistant, low-noise, lightweight, and high-end products. In essence, this requires the search for carbon black varieties with low rolling resistance, low heat generation, and low hysteresis. Summary of the Invention

[0003] This invention provides a method for producing high-structure, low-heat-generating, and high-safety-performance carbon black. The technical problem solved is developing a high-structure, low-heat-generating carbon black that, compared to conventional carbon black, exhibits higher structure, lower rolling resistance, lower heat generation, and higher abrasion resistance. It is widely used in the treads of high-performance radial tires for high-speed, high-load bias-ply tires, and also in rubber / plastic products with low heat generation requirements. The low-heat-generating carbon black is characterized by medium particle size, wide aggregate distribution, lower tinting strength, and higher structure. This new carbon black can improve the quality of tire tread rubber, including higher tread abrasion resistance, lower rolling resistance, lower heat generation, and better tear resistance. Carbon black with these properties and indicators has not yet been found on the market. When used in rubber, it possesses the high abrasion resistance of N234 carbon black while having lower heat generation than N234 carbon black. This newly developed carbon black is particularly useful for improving the quality of tires for heavy-duty and passenger vehicles and high-performance cars.

[0004] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0005] A method for producing carbon black with high structure, low heat generation, and high safety performance includes the following steps:

[0006] 1) Raw material control: The feedstock oil used is anthracene oil with a specific gravity of 1.14 or higher, an initial boiling point of 260°C or higher, and an aromatic content of 60% or higher; ethylene tar is used as fuel oil.

[0007] 2) Pretreatment of crude oil: The crude oil is heated to 70-90°C in the storage tank, and after sedimentation and filtration to remove residue, it is transported by crude oil pump and crude oil pipeline to the crude oil preheater for preheating to 210-230°C, and then sprayed into the reactor through oil nozzles.

[0008] 3) Fuel oil pretreatment: The fuel oil is heated to 70-90°C in the storage tank, and after sedimentation and filtration to remove residue, it is transported by fuel oil pump and fuel oil pipeline to the fuel oil preheater for preheating to 100-130°C.

[0009] 4) Carbon black pyrolysis preparation: Air and fuel oil are introduced into the combustion chamber of the reactor at a volume ratio of 17 to 20:1 for combustion. The pretreated feed oil is injected from the feed oil gun in the throat section. Carbon black is prepared under the conditions of feed oil flow rate of 400 to 440 m / s, combustion temperature of 2000 to 2100℃, and reaction time of 5 to 7 ms.

[0010] 5) Carbon black collection: The carbon black flue gas produced after the reaction and cracking in the multi-stage reactor is sent to the high-temperature air preheater. When passing through the air preheater, it exchanges heat with the air supplied by the fan outside the internal heat exchange tubes before entering the combustion chamber. The air outside the heat exchange tubes is heated to 850°C. Then it enters the waste heat boiler and then enters the Venturi tube. At the Venturi tube, it undergoes secondary soft water rapid cooling to reduce the temperature to 260°C and enters the bag filter collection device to separate carbon black and tail gas, collecting powdered carbon black. The tail gas passes through the filter bag and is sent to the tail gas combustion furnace for combustion by the tail gas fan, and the other part is sent to the thermal power boiler for power generation.

[0011] 6) Granulation of carbon black: After the powdered carbon black is homogenized by a conveying auger, it is added to a granulator. A mixture of binder and granulation water is sprayed into the granulator through five evenly distributed granulation water guns at the inlet. The mass ratio of binder to granulation water in the mixture is 1:25-30. Before entering the granulator, both binder and granulation water are first mixed evenly in a static mixer. The injection pressure of the granulation water into the granulator is 1.5-2.3 MPa.

[0012] 7) Drying of carbon black: The granulated carbon black is dried in a dryer. The moisture after drying is extracted by an exhaust fan. The temperature of the dried carbon black reaches 160-230℃. The dehydrated and dried carbon black enters the conveying and storage device from the dryer outlet. The moisture content of the dried carbon black is ≤0.5%.

[0013] 8) Carbon black conveying and storage: After drying, the carbon black is lifted by the first and second stage elevators, the screening machine removes impurities and carbon black lumps, the air separator extracts the fine carbon black powder and further reduces the temperature of the carbon black material, and the magnetic separator removes the rust, thus obtaining carbon black with high structure, low heat generation and high safety performance.

[0014] The anthracene oil in the feedstock is characterized by: toluene-insoluble matter ≤ 0.5%, density d20 of 1.14–1.16 g / cm3, and viscosity E80 ≤

[0015] 2.0, moisture ≤1%, fraction before 210℃ ≤5%, fraction before 360℃ ≥55%; the characteristics of ethylene tar in the feedstock oil are: toluene insoluble matter ≤1.0%, density ρ20 is 1.04~1.1g / cm3, viscosity E80≤9, moisture ≤0.5%, fraction before 210℃ ≤20%, fraction before 360℃ ≥70%.

[0016] The pretreatment of the feedstock oil in step 2) also includes the addition of a platinum-tin bimetallic catalyst supported on Al2O3. The amount of catalyst used is 5-10 kg per month. The catalyst is installed at the outlet of the feedstock oil preheater in a sealed catalytic device.

[0017] It also includes magnetizing the fuel oil before it enters the furnace; the magnetization process involves surrounding the outer surface of the fuel oil gun used in production with a magnet with a magnetic force of 15,000 to 20,000 gauss.

[0018] The inner diameter of the raw material oil gun nozzle in the throat section of the reactor is 255mm; there are a total of 14 oil guns for the raw material oil to enter the furnace, divided into 3 rows, with 4 guns in the first row, 2 guns in the second row, and 8 guns in the third row.

[0019] The first row has two adjacent oil guns arranged radially with a 90° angular interval; the second row has two adjacent oil guns arranged radially diagonally with a 180° angular interval; and the third row has two adjacent oil guns arranged radially with a 45° angular interval.

[0020] The invention has the following beneficial technical effects:

[0021] 1. This application achieves this by pre-screening and controlling anthracene oil and ethylene tar, ensuring that the anthracene oil meets the following criteria: toluene-insoluble matter ≤0.5%, density d20 of 1.14~1.16 g / cm3, viscosity E80 ≤2.0, moisture ≤1%, fraction before 210℃ ≤5%, and fraction before 360℃ ≥55%; and that the ethylene tar meets the following criteria: toluene-insoluble matter ≤1.0%, density ρ20 of 1.04~1.1 g / cm3, viscosity E80 ≤9, moisture ≤0.5%, fraction before 210℃ ≤20%, and fraction before 360℃ ≥70%. By controlling these criteria, the impact of raw materials on the product structure is minimized, and the benefits are maximized.

[0022] 2. This application utilizes a platinum-tin bimetallic catalyst and Al2O3 as the support for anthracene oil catalytic reforming by catalytic cracking of feedstock oil. The catalyst is placed inside a feedstock oil preheater, and the reaction process is set. At a certain temperature, when the feedstock oil is preheated in the feedstock oil preheater, the catalyst and feedstock oil come into full contact and a catalytic reforming reaction occurs, converting acyclic aromatics in the feedstock oil into cyclic aromatics. This increases the aromatic content of the feedstock oil entering the furnace, thereby increasing the structure degree (DBP value) of the carbon black during production. This is equivalent to increasing the crosslinking speed of carbon black and rubber in the later application, reducing the Mooney viscosity of the compound, and thus reducing the energy consumption and power of the compounding process.

[0023] 3. This application utilizes pretreatment of fuel oil. This project requires the activation of the fuel oil. We selected a method of coating the fuel oil spray gun with a permanent magnet with a magnetic field strength of up to 20,000 Gauss. When the fuel oil is preheated to (100-130℃), it is pumped to the fuel oil gun. Under the influence of the magnetic field, the surface of the fuel oil becomes magnetized, reducing its surface tension. Therefore, when the fuel oil is sprayed out of the nozzle, the droplets formed under the action of atomized air are finer, making it easier to ignite the fuel. Simultaneously, due to the reduced surface tension, the fuel oil burns more easily, with a stronger and more complete combustion effect and higher combustion efficiency. This results in more heat being provided for the cracking of the feedstock oil, and a higher reactor temperature. Before and after the magnetization and activation of the fuel oil, at the same combustion temperature, the fuel oil consumption is reduced by 40-60 kg / h, equivalent to a 5% saving of fuel oil.

[0024] 4. This application improves some production processes. The reactor throat is an important component of the reactor, serving as the channel for feedstock oil to enter the reaction system. The gas properties of the throat, and the hybrid characteristics of the feedstock oil flow and gas flow, significantly affect the properties of the carbon black. The inner diameter of the constriction section of the reactor throat in the production line is ≤255mm to ensure a flow velocity of ≥340m / s, thereby shortening the cracking reaction time of the feedstock oil. To regulate the type and quality of carbon black, a three-row oil nozzle is designed. The first row is arranged radially at 90° intervals, the second row is arranged radially diagonally at 180° intervals, and the third row is arranged radially at 45° intervals. The oil nozzles are solid oil column nozzles, requiring precision machining of the inner bore during manufacturing to ensure perpendicularity and surface finish. At the throat, raw material oil is sprayed into the high-speed flowing high-temperature gas. The oil flow is subjected to intense shearing, atomized by the airflow, and mixed at high speed to form a uniform reaction mixture that enters the reaction chamber. The number of oil guns and the flow rate of raw material oil at different positions have a significant impact on the iodine absorption value and oil absorption value. The higher the flow rate of raw material oil sprayed into the first and second rows of oil guns, the lower the iodine absorption value and the higher the oil absorption value under the same conditions. If the iodine absorption is kept within the control range, the higher the flow rate of raw material oil sprayed into the first and second rows of oil guns, the smaller the total amount of oil used. Therefore, the number of raw material oil guns used can be adjusted according to the product structure. Two rows of water guns are installed at the rear of the reaction section of the production line reactor, with a total of 8 water guns (4 in the negative first row and 4 in the negative second row). The center distance between the two rows of water guns is ≥200mm. This is used to adjust the surface area of ​​the product in multiple ways and produce carbon black products with suitable particle size. The heat generation temperature of the product in application is adjusted by the particle size.

[0025] 5. The low-heat-generating, high-abrasion-resistant carbon black product produced by this invention has a nitrogen adsorption specific surface area of ​​95-100*103m2 / Kg, tinting strength of 88-92, iodine adsorption value of 90-100g / kg, DBP absorption value of 131-141ml / 100g (dibutyl phthalate method), loss on heating <0.5%, average particle strength of 25-35cN, residue on a 325-mesh water-washed sieve ≤100ppm, ash content ≤0.5%, sulfur content ≤0.5%, and toluene transmittance ≥85%. Because its particle size is slightly larger than that of traditional carbon black, it indicates lower heat generation and better dispersibility. Its higher product structure indicates higher 100% tensile stress and 300% tensile stress, resulting in higher DIN abrasion data in applications and better wear resistance in tire treads. The high structure of the carbon black compensates for the disadvantage of increased particle size. Attached Figure Description

[0026] Figure 1 This is a structural diagram of the carbon black from Example 1;

[0027] Figure 2 This is a structural diagram of the carbon black from Example 2;

[0028] Figure 3 This is a structural diagram of the carbon black in Example 3;

[0029] Figure 4 This is a structural diagram of the carbon black in Example 4;

[0030] Figure 5 This is a structural diagram of the carbon black in Example 5;

[0031] Figure 6 This is a structural diagram of the carbon black in Example 6;

[0032] Figure 7 This is a structural diagram of the carbon black in Example 7. Detailed Implementation

[0033] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined in this application.

[0034] Example 1: A method for producing carbon black with high structure, low heat generation, and high safety performance, comprising the following steps:

[0035] 1) Raw material control: The feedstock oil used is high-quality anthracene oil with a specific gravity of 1.14 or higher, an initial boiling point of 260°C or higher, and a high aromatic content; the fuel oil used is ethylene tar; the characteristics of the anthracene oil in the feedstock oil are: toluene-insoluble matter ≤0.5%, density d20 of 1.14~1.16 g / cm3, viscosity E80≤2.0, moisture ≤1%, fraction before 210°C ≤5%, fraction before 360°C ≥55%; the characteristics of the ethylene tar in the feedstock oil are: toluene-insoluble matter ≤1.0%, density ρ20 of 1.04~1.1 g / cm3, viscosity E80≤9, moisture ≤0.5%, fraction before 210°C ≤20%, fraction before 360°C ≥70%; the anthracene oil is extracted from coal tar, and the ethylene tar is a product of high-temperature condensation of feedstock and product during the steam cracking process of ethylene cracking feedstock.

[0036] 2) Pretreatment of feedstock oil: The feedstock oil is heated to 70-90℃ in the storage tank, and after sedimentation and filtration to remove residues, it is transported by feedstock oil pump and feedstock oil pipeline to the feedstock oil preheater for preheating to 210-230℃. Then it passes through a closed catalytic device at the outlet of the feedstock oil preheater. The device contains a platinum-tin bimetallic catalyst with Al2O3 as the carrier, which can catalytically recombine the feedstock oil. After catalytic recombination, the feedstock oil is injected into the reactor through the feedstock oil injector, and the injection pressure is controlled at 2.8-3.4 MPa.

[0037] 3) Fuel oil pretreatment: The fuel oil is heated to 70-90℃ in the storage tank, and after preheating, settling, and filtration to remove residues, it is transported by fuel oil pump and fuel oil pipeline to the fuel oil preheater for preheating to 100-130℃. Then, it is injected into the combustion chamber of the reactor through the fuel oil gun to provide heat for the reaction and cracking of the feedstock oil. Before the fuel oil enters the furnace for combustion, it needs to be magnetized. Specifically, a high-strength magnet of 15,000-20,000 Gauss is placed around the outer surface of the fuel oil gun. The fuel oil is magnetized as it passes through the fuel oil gun, reducing the surface tension of the fuel oil. When the fuel oil is sprayed out of the nozzle, the droplets formed by the atomized air are finer and easier to ignite and burn. At the same time, due to the reduction in surface tension, the fuel oil burns more easily, with a stronger combustion effect, more complete combustion, and higher combustion efficiency. Therefore, more heat is provided for the cracking of the feedstock oil, and the reactor temperature is also higher.

[0038] 4) Carbon black pyrolysis preparation: In a multi-stage reactor, the temperature of the preheated air entering the furnace is raised to 850℃, the air flow rate is set to 16000 Nm³ / h, the feed oil flow rate is set to 5200 kg / h, the fuel oil flow rate is set according to the combustion temperature of 2000-2100℃, the flow velocity of the flue gas at the feed oil gun injection position in the throat section is 400-440 m / s, and the reaction time is 5-7 ms, so that carbon black is prepared under the conditions of feed oil flow rate of 400-440 m / s and 2000-2100℃. The inner diameter of the constriction at the nozzle of the feed oil spray gun in the throat section of the reactor is 255mm. The feed oil is fed into the furnace in three rows, with two guns in the first row (feed oil flow rate set to 400kg / h), four guns in the second row (feed oil flow rate set to 2200kg / h), and six guns in the third row (feed oil flow rate set to 2600kg / h). The crude oil is preheated to 210-230℃ before entering the furnace. The positions of the quench water guns are changed to four in the fifth row and two in the sixth row. All water guns use 4.5mm nozzles.

[0039] 5) Carbon black collection: The carbon black flue gas produced after the reaction and cracking in the reactor is sent to the high-temperature air preheater. When passing through the air preheater, it exchanges heat with the air supplied by the fan outside the internal heat exchange tubes before entering the combustion chamber, heating the air outside the heat exchange tubes to 850°C. Then it enters the waste heat boiler and then the Venturi tube. At the Venturi tube, it undergoes secondary soft water rapid cooling to reduce the temperature to 260°C and enters the bag filter collection device to separate the carbon black and the tail gas, collecting the carbon black. The tail gas passes through the filter bag and is sent to the tail gas combustion furnace for combustion by the tail gas fan, and the rest is sent to the thermal power boiler for power generation. The filtration effect of the filter bag filters and collects the carbon black. The carbon black falling into the conical hopper of the box is sent to the air conveying pipeline through the airtight valve toothed teeth, and then to the micron pulverizer for pulverization. Finally, it is transported to the carbon black powder storage tank by the air conveying fan.

[0040] 6) Carbon black granulation: The carbon black in the powdered carbon black storage tank is conveyed by the air blower and the airtight valve of the powdered carbon black storage tank to the powdered carbon black conveying auger for material homogenization treatment before being added to the granulator. A mixed solution of binder and granulation water is sprayed in through 5 evenly distributed granulation water guns at the inlet of the granulator. The mass ratio of binder to granulation water in the mixed solution sprayed into the granulator is 1:25-30. Before entering the granulator, the binder and granulation water are first mixed evenly in a static mixer. The injection pressure of granulation water into the granulator is 1.5-2.3 MPa.

[0041] 7) Drying of carbon black: The granulated carbon black is dried by a dryer. The moisture after drying is drawn off by an exhaust fan. The temperature of the dried carbon black reaches 160-230℃. The dehydrated and dried carbon black enters the conveying and storage device from the outlet of the dryer. The moisture content of the dried carbon black is ≤0.5%.

[0042] 8) Carbon black conveying and storage: After drying, the carbon black is lifted by the first and second stage elevators, the screening machine removes impurities and carbon black lumps, the air separator extracts the fine carbon black powder and reduces the temperature of the carbon black material to 60-85℃, and the magnetic separator removes the rust, leaving a pure carbon black finished product with no impurities and uniform particles, which is then put into the product storage tank.

[0043] Example 2: Compared with Example 1, the main difference lies in the pyrolysis preparation of the carbon black: In a multi-stage reactor, the temperature of the preheated air entering the furnace is increased to 850°C, the air flow rate is set to 16000 Nm³ / h, the feed oil flow rate is changed to 5300 kg / h, the fuel oil flow rate is set according to the combustion temperature of 2000-2100°C, the flow velocity of the flue gas at the feed oil gun injection position in the throat section is 400-440 m / s, and the reaction time is 5-7 ms, so that the feed oil is prepared under the conditions of a flow velocity of 400-440 m / s and a temperature of 2000-2100°C. The inner diameter of the constriction at the nozzle of the feed oil spray gun in the throat section of the reactor is 255mm. The feed oil is fed into the furnace in three rows, with the number of guns changed to 2 in the first row (feed oil flow rate set to 800kg / h), 2 in the second row (feed oil flow rate set to 800kg / h), and 6 in the third row (feed oil flow rate set to 3700kg / h). The crude oil is preheated to 210-230℃ before entering the furnace. The position of the quench water gun is changed to 2 in the fourth row and 4 in the fifth row. All water guns use 4.5mm nozzles.

[0044] Example 3: Compared with Example 1, the main difference lies in the pyrolysis preparation of the carbon black: In a multi-stage reactor, the temperature of the preheated air entering the furnace is increased to 850℃, the air flow rate is set to 16000 Nm³ / h, the feed oil flow rate is changed to 5500 kg / h, the fuel oil flow rate is set according to the combustion temperature of 2000-2100℃, the flow velocity of the flue gas at the feed oil gun injection position in the throat section is 400-440 m / s, and the reaction time is 5-7 ms, so that the feed oil is prepared under the conditions of a flow velocity of 400-440 m / s and a temperature of 2000-2100℃. The inner diameter of the constriction point of the feed oil spray gun in the throat section of the reactor is 255mm; the feed oil inlet gun positions are divided into 3 rows, and the number of guns is changed to 0 in the first row, 4 in the second row (feed oil flow rate set to 1100kg / h), and 8 in the third row (feed oil flow rate set to 4400kg / h). The crude oil is preheated to 210-230℃ before entering the furnace. The quench water gun positions are 2 in the 5th row and 4 in the 6th row. All water guns use 4.5mm nozzles.

[0045] Example 4: Compared with Example 1, the main difference lies in the pretreatment of the feedstock oil: The feedstock oil is heated to 70-90°C in a storage tank, and after sedimentation and filtration to remove residues, it is transported by a feedstock oil pump and feedstock oil pipeline to a feedstock oil preheater for preheating to 210-230°C. Then, it passes through a closed catalytic device at the outlet of the feedstock oil preheater. Here, a platinum-tin bimetallic catalyst with Al2O3 as the carrier, which can catalytically recombine the feedstock oil, is added to the closed catalytic device. The catalyst is changed from Al2O3 to Cr2O3 / Al2O3 to catalytically recombine the feedstock oil. After catalytic recombination, the feedstock oil is injected into the reactor through a feedstock oil injector. The injection pressure here is controlled at 2.8-3.4 MPa.

[0046] Carbon black pyrolysis preparation: In a multi-stage reactor, the temperature of the preheated air entering the furnace is increased to 850℃, the air flow rate is set to 16000 Nm³ / h, the feed oil flow rate is changed to 5100 kg / h, the fuel oil flow rate is set according to the combustion temperature of 2000-2100℃, the flow velocity of the flue gas at the feed oil gun injection position in the throat section is 400-440 m / s, and the reaction time is 5-7 ms, so that carbon black is prepared under the conditions of feed oil flow rate of 400-440 m / s and 2000-2100℃. The inner diameter of the constriction at the nozzle of the feed oil spray gun in the throat section of the reactor is 255mm. The feed oil inlet guns are divided into 3 rows, with the number of guns changed to 0 in the first row, 4 in the second row (feed oil flow rate setting changed to 800kg / h), and 8 in the third row (feed oil flow rate setting changed to 4300kg / h). The crude oil is preheated to 230℃ before entering the furnace. The quench water guns are 2 in the 5th row and 4 in the 6th row. All water guns use 4.5mm nozzles.

[0047] Example 5: Compared with Example 1, the main difference lies in the pretreatment of the feedstock oil: the feedstock oil is heated to 70-90°C in a storage tank, and after sedimentation and filtration to remove residues, it is transported by a feedstock oil pump and feedstock oil pipeline to a feedstock oil preheater for preheating to 210-230°C. Then, it passes through a closed catalytic device at the outlet of the feedstock oil preheater. Here, a platinum-tin bimetallic catalyst with Al2O3 as the carrier, which can catalytically recombine the feedstock oil, is added to the closed catalytic device. The catalyst is changed from Al2O3 to Cr2O3 / Al2O3 to catalytically recombine the feedstock oil. After catalytic recombination, the feedstock oil is injected into the reactor through a feedstock oil injector. The injection pressure here is controlled at 2.8-3.4 MPa.

[0048] Carbon black pyrolysis preparation: In a multi-stage reactor, the temperature of the preheated air entering the furnace is increased to 850℃, the air flow rate is set to 16000 Nm³ / h, the feed oil flow rate is changed to 4900 kg / h, the fuel oil flow rate is set according to the M4 model, the flow velocity of the flue gas at the feed oil gun injection position in the throat section is 400-440 m / s, and the reaction time is 5-7 ms, so that carbon black is prepared under the conditions of feed oil flow rate of 400-440 m / s and 2000-2100℃. The inner diameter of the constriction at the nozzle of the feed oil spray gun in the throat section of the reactor is 255mm. The feed oil is fed into the furnace in three rows, with the number of guns changed to 2 in the first row (feed oil flow rate setting changed to 600kg / h), 2 in the second row (feed oil flow rate setting changed to 800kg / h), and 6 in the third row (feed oil flow rate setting changed to 3500kg / h). The crude oil is preheated to 230℃ before entering the furnace. The positions of the quench water guns are changed to 2 in the fourth row and 4 in the fifth row. All water guns use 4.5mm nozzles.

[0049] Example 6: Compared with Example 1, the main difference lies in the pretreatment of the feedstock oil: the feedstock oil is heated to 70-90°C in a storage tank, and after sedimentation and filtration to remove residues, it is transported by a feedstock oil pump and feedstock oil pipeline to a feedstock oil preheater for preheating to 210-230°C. Then, it passes through a closed catalytic device at the outlet of the feedstock oil preheater. Here, a platinum-tin bimetallic catalyst with Al2O3 as the carrier, which can catalytically recombine the feedstock oil, is added to the closed catalytic device. The catalyst is changed to Cr2O3 / Al2O3 to catalytically recombine the feedstock oil. After catalytic recombination, the feedstock oil is injected into the reactor through a feedstock oil injector. The injection pressure here is controlled at 2.8-3.4 MPa.

[0050] Carbon black pyrolysis preparation: In a multi-stage reactor, the temperature of the preheated air entering the furnace is increased to 850℃, the air flow rate is set to 16000 Nm³ / h, the feed oil flow rate is changed to 4800 kg / h, the fuel oil flow rate is set according to the M4 model, the flow velocity of the flue gas at the feed oil gun injection position in the throat section is 400-440 m / s, and the reaction time is 5-7 ms, so that carbon black is prepared under the conditions of feed oil flow rate of 400-440 m / s and 2000-2100℃. The inner diameter of the constriction at the nozzle of the feed oil spray gun in the reactor throat section is 255mm. The feed oil inlet guns are divided into 3 rows, with the number of guns changed to 2 in the first row (feed oil flow rate setting changed to 600kg / h), 4 in the second row (feed oil flow rate setting changed to 2100kg / h), and 4 in the third row (feed oil flow rate setting changed to 2100kg / h). The crude oil is preheated to 230℃ before entering the furnace. The quench water gun positions are changed to 2 in the 4th row and 4 in the 5th row. All water guns use 4.5mm nozzles.

[0051] Example 7: Compared with Example 1, the main difference lies in the pretreatment of the feedstock oil: the feedstock oil is heated to 70-90°C in the storage tank, and after sedimentation and filtration to remove residues, it is transported by the feedstock oil pump and feedstock oil pipeline to the feedstock oil preheater for preheating to 210-230°C. Instead of adding any catalyst, it is directly injected into the reactor through the feedstock oil nozzle, and the injection pressure here is controlled at 2.8-3.4 MPa.

[0052] Table 1. Process parameters for examples 1-3 using platinum-tin bimetallic catalysts and Al2O3 as support.

[0053]

[0054] Table 2. Process parameters for anthracene oil catalytic reforming catalysts used in Examples 4-6

[0055]

[0056] Table 3. Process parameters for Example 7 without any anthracene oil catalytic reforming catalyst.

[0057]

[0058] The data from the above seven examples show that the injection position and amount of raw oil in the oil gun affect the iodine absorption value and oil absorption value. Simultaneously, the aromatic content of the raw oil also influences these values. To ensure stable iodine and oil absorption values, a higher aromatic content and injection volume of the raw oil are desirable. The number of oil guns at different positions and the flow rate of the raw oil significantly impact both iodine and oil absorption values. A higher flow rate of raw oil injected from the first and second rows of oil guns results in a lower iodine absorption value and a higher oil absorption value under the same conditions. If iodine absorption remains within controllable limits, a higher flow rate of raw oil injected from the first and second rows of oil guns requires a smaller total amount of oil. Regarding the aromatic content in anthracene oil, a higher aromatic content leads to a higher iodine absorption value and a higher oil absorption value.

[0059] Table 4. Particle analysis data at the dryer outlet of Examples 1-7

[0060]

[0061] As can be seen from the table above:

[0062] 1. As the number of oil guns at different locations varies and the flow rate of the injected raw material oil varies, the iodine absorption and oil absorption values ​​of carbon black differ significantly.

[0063] 2. Different catalysts used for catalytic reforming have varying efficiencies in increasing the aromatic content of anthracene oil during reforming.

[0064] 3. Magnetizing and activating fuel oil can significantly improve its combustion efficiency and save approximately 5% of fuel consumption.

[0065] 4. The aromatic content in the feedstock oil has a significant impact on the oil absorption value of carbon black. The higher the aromatic content in the feedstock oil, the higher the structure of the produced carbon black, and vice versa.

[0066] The microscopic structure of the carbon black particles produced by experiments 1-7:

[0067] Analysis of the carbon black structure under an electron microscope revealed differences in the microstructure of carbon black produced under different conditions. Examples (1-3) show the carbon black structure produced by using a platinum-tin bimetallic catalyst and Al2O3 as a support to increase the aromatic content of anthracene oil. Examples (4-6) show the carbon black structure produced by using Cr2O3 / Al2O3 as a catalyst to increase the aromatic content of anthracene oil. Example 7 shows the carbon black structure produced by using no catalyst to increase the aromatic content of anthracene oil. See attached figures for details.

[0068] The following experimental data further illustrates the beneficial effects of the present invention:

[0069] Test materials

[0070] 1. Materials and Methods:

[0071] 1.1 Test location: National-level laboratory of Shandong Nester Carbon Black Co., Ltd.

[0072] 1.2 Experimental Testing: Comparison of the performance indicators of the material of this invention with those of traditional carbon black products;

[0073] 1.3 Test materials: Example 1 of this invention and traditional carbon black used in the carbon black industry;

[0074] 1.4 Experimental Implementation: All sampling and testing were conducted in accordance with national carbon black testing standards. Iodine absorption value was tested according to GB / T 3780.1~2006 standards; oil absorption value according to GB / T 3780.2~2007 standards; compression oil absorption value according to GB / T 3780.4~2008 standards; nitrogen adsorption specific surface area according to GB / T 3780.5~2008 standards; coloring strength according to GB / T 3780.6~2007 standards; loss on heating according to GB / T 3780.8~2008 standards; particle strength according to GB / T 14853.6~2002 standards; ash content according to GB / T 3780.10~2009 standards; impurities according to GB / T 3780.12~2007 standards; and toluene transmittance according to GB / T 3780.15~2006 standards.

[0075] 2 Results and Analysis

[0076] The experimental results are shown in the table below.

[0077] Table 5

[0078]

[0079] Experiment 2

[0080] Test materials

[0081] 1. Materials and Methods:

[0082] 1.1 Test location: Qingdao Sentury Tire Co., Ltd. laboratory;

[0083] 1.2 Experimental Testing: Comparison of performance data of the carbon black of this invention and traditional N234 carbon black before and after aging of rubber compounds;

[0084] 1.3 Test materials: Traditional N234 carbon black and Example 1 of this invention, as shown in the table;

[0085] 1.4 Experimental Implementation: The application standard for carbon black was tested according to GB / T 3778~2019.

[0086] Comparison of rubber compound properties:

[0087] 1.5 Formula Experiment: To investigate the performance differences between the carbon black of this invention and the comparative carbon black, we used the formulation of an all-steel radial tire tread compound to study the two types of carbon black separately. The experimental formulations are shown in the table below.

[0088] Comparison of the performance of industrially formulated tread rubber compounds for all-steel radial tires before and after aging

[0089] Table 6

[0090]

[0091]

[0092] The data in the table above shows that there is no significant difference in the performance of the two carbon blacks, Example 1 and N234, in the tread compound of all-steel radial tires before aging. However, the bottom temperature rise ratio is significantly lower, the heat generation is reduced, the wear resistance (DIN abrasion index) is improved, the scorch time is extended, and the processing safety is improved. The tanδ measurement value of the carbon black in Example 1 at 0℃ is higher than that of the carbon black in N234, while the tanδ measurement value of the carbon black in Example 1 at 60℃ is lower than that of the carbon black in N234. This indicates that the hysteresis performance of the carbon black in Example 1 is better than that of the carbon black in N234, and it has lower rolling resistance and higher anti-lubrication performance. After aging, comparing the performance of the two carbon black vulcanizates, the vulcanizate filled with carbon black in Example 1 has higher tensile stress and wear resistance than the vulcanizate filled with carbon black in N234.

Claims

1. A method for producing carbon black with high structure, low heat generation, and high safety performance, characterized in that, Includes the following steps: 1) Raw material control: The feedstock oil used is anthracene oil with a specific gravity of 1.14 or higher, an initial boiling point of 260℃ or higher, and an aromatic content of 75% or higher; ethylene tar is used as fuel oil. 2) Pretreatment of crude oil: The crude oil is heated to 70-90°C in the storage tank, and after sedimentation and filtration to remove residue, it is transported by crude oil pump and crude oil pipeline to the crude oil preheater for preheating to 210-230°C, and then sprayed into the reactor through oil nozzles. 3) Fuel oil pretreatment: The fuel oil is heated to 70-90°C in the storage tank, and after sedimentation and filtration to remove residue, it is transported by fuel oil pump and fuel oil pipeline to the fuel oil preheater for preheating to 100-130°C. 4) Carbon black pyrolysis preparation: Air and fuel oil are introduced into the combustion chamber of the reactor at a volume ratio of 17 to 20:1 for combustion. The pretreated feed oil is injected from the feed oil gun in the throat section. Carbon black is prepared under the conditions of feed oil flow rate of 400 to 440 m / s, combustion temperature of 2000 to 2100℃, and reaction time of 5 to 7 ms. 5) Carbon black collection: The carbon black flue gas produced after the reaction and cracking in the multi-stage reactor is sent to the high-temperature air preheater. When passing through the air preheater, it exchanges heat with the air supplied by the fan outside the internal heat exchange tubes before entering the combustion chamber. The air outside the heat exchange tubes is heated to 850°C. Then it enters the waste heat boiler and then enters the Venturi tube. At the Venturi tube, it undergoes secondary soft water rapid cooling to reduce the temperature to 260°C and enters the bag filter collection device to separate carbon black and tail gas, collecting powdered carbon black. The tail gas passes through the filter bag and is sent to the tail gas combustion furnace for combustion by the tail gas fan, and the other part is sent to the thermal power boiler for power generation. 6) Granulation of carbon black: After the powdered carbon black is homogenized by a conveying auger, it is added to a granulator. A mixture of binder and granulation water is sprayed into the granulator through five evenly distributed granulation water guns at the inlet. The mass ratio of binder to granulation water in the mixture is 1:25-30. Before entering the granulator, both binder and granulation water are first mixed evenly in a static mixer. The injection pressure of the granulation water into the granulator is 1.5-2.3 MPa. 7) Drying of carbon black: The granulated carbon black is dried in a dryer. The moisture after drying is extracted by an exhaust fan. The temperature of the dried carbon black reaches 160-230℃. The dehydrated and dried carbon black enters the conveying and storage device from the dryer outlet. The moisture content of the dried carbon black is ≤0.5%. 8) Carbon black conveying and storage: After drying, the carbon black is lifted by the first and second stage elevators, the screening machine removes impurities, the air separator extracts the fine carbon black powder and further reduces the temperature of the carbon black material, and the magnetic separator removes the rust, thus obtaining carbon black with high structure, low heat generation and high safety performance. Step 4) also includes magnetizing the fuel oil before it enters the furnace; the magnetization process involves surrounding the outer surface of the fuel oil gun used in production with a magnet with a magnetic force of 15,000 to 20,000 gauss. The inner diameter of the raw material oil gun nozzle in the throat section of the reactor is 255mm; there are a total of 12 oil guns for the raw material oil entering the furnace, divided into 3 rows, with 2 guns in the first row, 4 guns in the second row, and 6 guns in the third row; the oil guns in the first row are arranged radially with a 90° angular diameter interval between adjacent oil guns, the oil guns in the second row are arranged diagonally with a 180° angular diameter interval between adjacent oil guns, and the oil guns in the third row are arranged radially with a 45° angular diameter interval between adjacent oil guns; The pretreatment of the feedstock oil in step 2) also includes the addition of a platinum-tin bimetallic catalyst supported on Al2O3.

2. The method for producing carbon black with high structure, low heat generation, and high safety performance according to claim 1, characterized in that: said anthracene oil is characterized by toluene insolubles ≤ 0.5%, density d20 1.14-1.16 g / cm 3 , viscosity E80 ≤ 2.0, moisture ≤ 1%, fraction before 210°C ≤ 5%, fraction before 360°C ≥ 55%; said ethylene tar is characterized by toluene insolubles ≤ 1.0%, density p20 1.04-1.1 g / cm 3 , viscosity E80 ≤ 9, moisture ≤ 0.5%, fraction before 210°C ≤ 20%, fraction before 360°C ≥ 70%.

3. The method for producing carbon black with high structure, low heat generation, and high safety performance according to claim 1, characterized in that: In step 2), the amount of catalyst used is 5-10 kg per month, and a sealed catalytic device is installed at the outlet of the feed oil preheater.

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