CN111534128A - Low-hysteresis carbon black and production method thereof - Google Patents
Low-hysteresis carbon black and production method thereof Download PDFInfo
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- CN111534128A CN111534128A CN202010451713.5A CN202010451713A CN111534128A CN 111534128 A CN111534128 A CN 111534128A CN 202010451713 A CN202010451713 A CN 202010451713A CN 111534128 A CN111534128 A CN 111534128A
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- carbon black
- low hysteresis
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/48—Carbon black
- C09C1/50—Furnace black ; Preparation thereof
Abstract
The invention provides a low hysteresis carbon black and a production method thereof, wherein the low hysteresis carbon black has the following characteristics: the oil absorption value is 131-145 ml/100g, the compressed oil absorption value is 102-114 ml/100g, the iodine absorption value is 115-131 mg/g, and the nitrogen adsorption specific surface area is 119-130 m2(ii) in terms of/g. Tires made using the low hysteresis carbon black have low rolling resistance and low heat build-up under service conditions.
Description
Technical Field
The invention relates to carbon black and a preparation method thereof, in particular to hard carbon black with balanced wear resistance and low heat generation and a production method thereof.
Background
Carbon black is currently known as the darkest material in the world, and is widely applied to products such as rubber, ink, plastics, pigments and the like to endow the products with required reinforcing, dyeing or electric conductivity. Carbon black is produced by incomplete combustion or cracking of hydrocarbon compounds, and is essentially composed of elemental carbon (95-99%), is in the form of a very fine powder, and has a very high specific surface area.
Carbon black has been widely used in the rubber industry as a reinforcing material for rubber. However, there are many problems to be solved with the current commercial carbon blacks, such as how to further reduce the rolling resistance, improve the wet skid resistance, further reduce the dynamic heat generation of the compound, and the like. To solve these problems, foreign large carbon black companies developed low hysteresis carbon black and conversion carbon black, but mechanical properties (including tensile strength, elongation at break, 300% tensile strength of rubber, etc.) were somewhat affected. In order to eliminate the contradiction between the abrasion resistance and the low heat buildup, some patent documents propose methods such as maintaining the distribution width of the diameter of the carbon black aggregates at a certain value or more, making a high structure and controlling the distribution of the aggregates, and controlling the void volume and the void volume diameter of the carbon black aggregates at a certain value or more. These methods, although reducing the dynamic heat generation of the compound, have a problem that the strength is reduced and there is no concern about improving the rolling resistance.
Disclosure of Invention
The invention provides low-hysteresis carbon black and a production method thereof, aiming at solving the problems of high wear resistance and low fuel consumption of the existing carbon black.
The invention provides low-hysteresis carbon black, which has the following characteristics:
the oil absorption value (DBP absorption value) is 131-145 ml/100 g;
the compressed oil absorption value (CDBP absorption value) is 102-114 ml/100 g;
the iodine absorption value is 115-131 mg/g;
specific surface area for nitrogen adsorption (N)2SA) of 119 to 130m2/g。
The microscopic surface morphology of the low-hysteresis carbon black can be observed by a high-power transmission electron microscope, wherein the microscopic surface morphology of the low-hysteresis carbon black has tiny carbon black particles (nodule) growing on the surface of large carbon black particles, and the diameters of the tiny carbon black particles are 3-7 nm (preferably 5nm), as shown in fig. 1.
The low hysteresis carbon black has a broader aggregate size distribution and a Span (Span) of 1.08 to 1.410 compared to the same grade of carbon black. Wherein the calculation formula of the span is as follows:
Span＝(D90-D10)/D50
in the formula, D90 is the particle size corresponding to the cumulative percentage of distribution of 90%, D50 is the particle size corresponding to the cumulative percentage of distribution of 50%, and D10 is the particle size corresponding to the cumulative percentage of distribution of 10%.
The production method of the low-hysteresis carbon black comprises the following steps:
introducing air and fuel into a carbon black reaction furnace comprising a combustion section, a throat section and a reaction section to enable the fuel to be combusted in the combustion section, and controlling the temperature in the combustion section to be 1820-2220 ℃;
spraying auxiliary raw oil from a combustion section of the carbon black reaction furnace, and carrying out cracking reaction on the auxiliary raw oil at high temperature to generate small-particle carbon black; spraying main raw oil from a throat section of the carbon black reaction furnace, and carrying out cracking reaction on the main raw oil at high temperature to generate large-particle carbon black; the small particle carbon black is fused with the large particle carbon black to form the low hysteresis carbon black.
Preferably, the flow rate of air introduced into the carbon black reaction furnace is 9600-20000 Nm3And/h, wherein the flow rate of fuel introduced into the carbon black reaction furnace is 1370-3120 kg/h.
Preferably, the flow rate of the auxiliary raw oil sprayed from the combustion section of the carbon black reaction furnace is 750-1850 kg/h, and the flow rate of the main raw oil sprayed from the throat section of the carbon black reaction furnace is 2240-4300 kg/h.
The invention has the beneficial effects that:
(1) the low-hysteresis carbon black has the characteristics of low rolling resistance, low heat generation and high strength, and meets the requirements of developing green tires and high-performance rubber (high rebound resilience, wet-skid resistance and the like) products with dynamic fatigue resistance;
(2) the low-hysteresis carbon black has certain rigidity of particles, can overcome the pollution caused by flying carbon black, and greatly improves the production and application environment;
(3) the low-hysteresis carbon black has good processing performance, fast material taking in the rubber mixing process, reduced mixing temperature and improved mixing efficiency;
(4) from the dynamic performance test of the tire, compared with the N234 traditional carbon black, the measurement method of the national standard GB/T18861-2012 rolling resistance tan @60 ℃ reduces 9.1% at tan @60 ℃ by the low-hysteresis carbon black, and the consumption of 1.36% of gasoline can be reduced by reckoning from that the rolling resistance is reduced by about 1.5% when the rolling resistance is reduced by 10%.
Drawings
FIG. 1 is a TEM image of a low hysteresis carbon black prepared in inventive examples 1 and 2 and a conventional N234 carbon black.
FIG. 2 is a schematic view of the production process of the present invention.
FIG. 3 is a graph of the dynamic mechanical properties of vulcanized natural rubber of the low hysteresis carbon blacks of example 1 of the present invention (labeled LN 1-), and of the conventional N234 carbon blacks.
The reference signs explain: 1. air, 2, fuel, 3, a combustion furnace, 4, a main stock oil spraying system, 5, a main stock oil spray gun, 6, a main stock oil spraying state, 7, a reaction furnace, 8, an auxiliary stock oil spraying system, 9, an auxiliary stock oil spray gun, 10, an auxiliary stock oil spraying state.
Detailed Description
The invention is further illustrated with reference to the following figures and examples. The following examples and comparative examples are given only to further illustrate the present invention, and the present invention is not limited to the following examples.
The low hysteresis carbon blacks of the present invention may be prepared using a carbon black reactor. The carbon black reaction furnace is common equipment in the prior art and generally comprises a combustion section, a throat section, a reaction section and a quenching section; wherein the throat section is provided with a raw oil spraying system (main raw oil spraying system) which can be used for spraying main raw oil. In order to spray auxiliary raw oil, a set of auxiliary raw oil spraying system is added at the rear part of a combustion section in front of the main raw oil spraying system.
As shown in fig. 2, fuel 2 is injected from the central axis position of the front end of the carbon black reaction furnace, air 1 is injected from the side surface of the front end of the carbon black reaction furnace through an air distributor, and the fuel 2 and the air 1 are mixed and then combusted to generate high temperature; at the rear of the combustion section, auxiliary raw oil is sprayed by an auxiliary raw oil spray gun (LNTD end) 9, and the auxiliary raw oil is cracked into small-particle carbon black at high temperature; in the choke section, the main raw oil is sprayed by a main raw oil spray gun (SNTD end) 5, and the main raw oil is cracked into large-particle carbon black; the small particle carbon black is fused with the large particle carbon black to form the low hysteresis carbon black of the present invention. The two sets of raw oil spraying systems are respectively provided with eight spray guns, the two sets of raw oil conveying systems are respectively used, the front-end auxiliary raw oil can receive a heat value firstly, is cracked into small-particle carbon black, and then is fused with the carbon black generated by the main raw oil, so that the elasticity and the range for controlling the generation form of the carbon black are greatly increased.
The main raw oil and the auxiliary raw oil both adopt coal tar with the specific gravity of 1.145(100/4 ℃), BMCI 168 and 0.02 percent of toluene insoluble substances, the fuel is clean coal gas, and the supply amount of the raw materials is changed through different operating conditions, thereby completing the preparation of the target carbon black. Table 1 shows the operating conditions of two embodiments of the present invention.
Table 1 operating conditions for example 1 and example 2 of the present invention
Table 2 shows the physical properties of the carbon blacks prepared in inventive examples 1 and 2, as well as the physical properties of the conventional N234 carbon black.
TABLE 2 comparison of physical Properties of the carbon blacks prepared in inventive examples 1 and 2 with conventional N234 carbon blacks
In the present embodiment, D90 is the particle size corresponding to the cumulative number of aggregates distributed by the disc-type centrifugal sedimentation method reaching 90%, D50 is the particle size corresponding to the cumulative number of aggregates distributed by the disc-type centrifugal sedimentation method reaching 50%, and D10 is the particle size corresponding to the cumulative number of aggregates distributed by the disc-type centrifugal sedimentation method reaching 10%.
As can be seen from the above table, the carbon blacks prepared in examples 1 and 2 of the present invention have a broader aggregate size distribution as compared in span.
When the oil absorption number (DBP) is less than 132ml/100g, a satisfactory modulus may not be obtained; on the other hand, when the DBP exceeds 142ml/100g, the viscosity of the carbon black in the rubber component increases and the processability may be deteriorated.
Specific surface area for nitrogen adsorption (N)2SA) less than 119m2At the time of the reaction,/g, the abrasion resistance of the rubber may be lowered; on the other hand, when N is2SA greater than 130m2At the time of the reaction,/g, the dispersibility of the carbon black in the rubber component may be lowered, and the hysteresis performance may be lowered.
The carbon black prepared in example 1 of the present invention was tested for sizing properties according to the test methods provided by the latest national standards, with reference to commercially available N234 carbon black.
The data presented in Table 3 is a comparison of the physical and mechanical properties of the carbon blacks prepared in example 1 of the present invention and a commercial N234 carbon black natural rubber compound, where the tan data corresponds to FIG. 3.
The basic formula of the sizing material is as follows: 100 parts of natural rubber, 4 parts of zinc oxide, 50 parts of carbon black, 2 parts of stearic acid, 1.4 parts of accelerator, 2.0 parts of anti-aging agent 402 and 0.85 part of sulfur.
TABLE 3 comparison of the physical and mechanical Properties of Natural rubber Compounds of carbon Black prepared in inventive example 1 with commercially available N234 carbon Black
| Carbon black varieties | LN1～ | N234 |
| Tensile strength, MPa | 29.6 | 29.2 |
| Elongation at break, 100% | 485.4 | 495.7 |
| Tear Strength, KN/m | 87.2 | 86.6 |
| 300% M tensile Strength at definite elongation, MPa | 17.38 | 16.93 |
| Temperature rise/. degree.C | 31.9 | 34.3 |
| Tanδ(-20℃) | 0.3367 | 0.3356 |
| Tanδ(0℃) | 0.2203 | 0.2233 |
| Tanδ(60℃) | 0.1532(90.9％) | 0.1685(100％) |
Wherein Tan ═ E "/E'; tan represents a loss factor; e' represents loss modulus; e' represents an elastic modulus.
Tan at 0 ℃ represents the wet skid resistance of the sizing material, and the larger tan is, the better the wet skid resistance is; the tan at 60 ℃ represents the rolling resistance of the tire, the smaller the tan, the smaller the rolling resistance of the compound.
Claims (9)
1. A low hysteresis carbon black having the following characteristics:
the oil absorption value is 131-145 ml/100 g;
the compressed oil absorption value is 102-114 ml/100 g;
the iodine absorption value is 115-131 mg/g;
the specific surface area of nitrogen adsorption is 119-130 m2/g。
2. The low hysteresis carbon black of claim 1, wherein: the microscopic surface of the low-hysteresis carbon black is characterized in that tiny carbon black particles grow on the surfaces of large carbon black particles, and the diameters of the tiny carbon black particles are 3-7 nm.
3. The low hysteresis carbon black of claim 2, wherein: the diameter of the fine carbon black particles is 5 nm.
4. The low hysteresis carbon black of claim 1, wherein: the span of the low hysteresis carbon black is 1.08-1.410.
5. The process for the production of low hysteresis carbon black of claim 1, comprising the steps of:
introducing air and fuel into a carbon black reaction furnace comprising a combustion section, a throat section and a reaction section to enable the fuel to be combusted in the combustion section, and controlling the temperature in the combustion section to be 1820-2200 ℃;
spraying auxiliary raw oil from a combustion section of the carbon black reaction furnace, and carrying out cracking reaction on the auxiliary raw oil at high temperature to generate small-particle carbon black; spraying main raw oil from a throat section of the carbon black reaction furnace, and carrying out cracking reaction on the main raw oil at high temperature to generate large-particle carbon black; the small particle carbon black and the large particle carbon black are fused and then embedded with each other, so that the low hysteresis carbon black is formed.
6. The method of claim 5, wherein: to the carbonThe flow of air introduced into the black reaction furnace is 9600-20000 Nm3And/h, wherein the flow rate of fuel introduced into the carbon black reaction furnace is 1370-3120 kg/h.
7. The method of claim 5, wherein: the flow rate of the auxiliary raw oil sprayed from the combustion section of the carbon black reaction furnace is 750-1850 kg/h, and the flow rate of the main raw oil sprayed from the throat section of the carbon black reaction furnace is 2240-4300 kg/h.
8. Use of a low hysteresis carbon black according to any one of claims 1 to 4.
9. Use of a low hysteresis carbon black according to claim 8, characterized in that: the low hysteresis carbon black is used in the field of rubber products.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114181546A (en) * | 2021-12-01 | 2022-03-15 | 青岛黑猫炭黑科技有限责任公司 | Method and system for adjusting carbon black production process based on powdery carbon black sampling result |
| CN114361457A (en) * | 2022-01-25 | 2022-04-15 | 湖北亿纬动力有限公司 | Negative pole piece and secondary battery comprising same |
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Cited By (3)
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| CN114181546A (en) * | 2021-12-01 | 2022-03-15 | 青岛黑猫炭黑科技有限责任公司 | Method and system for adjusting carbon black production process based on powdery carbon black sampling result |
| CN114181546B (en) * | 2021-12-01 | 2023-01-10 | 青岛黑猫炭黑科技有限责任公司 | Method and system for adjusting carbon black production process based on powdery carbon black sampling result |
| CN114361457A (en) * | 2022-01-25 | 2022-04-15 | 湖北亿纬动力有限公司 | Negative pole piece and secondary battery comprising same |
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Application publication date: 20200814 |