CN112322076B - Method for preparing carbon black - Google Patents
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/48—Carbon black
- C09C1/54—Acetylene black; thermal black ; Preparation thereof
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/48—Carbon black
- C09C1/56—Treatment of carbon black ; Purification
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- 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
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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- 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
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C3/041—Grinding
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- 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
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
Abstract
The invention relates to a preparation method of carbon black, in particular to a method for preparing carbon black for tires by using carbon solid waste as a raw material, and belongs to the technical field of comprehensive utilization of industrial solid waste resources. The method for preparing the carbon black comprises the following steps: s1, crushing the carbon solid waste, leaching in a mixed solution of acid and hydrogen peroxide, filtering, washing and drying to obtain carbon powder; s2, soaking the carbon powder obtained in the step S1 in an alkali solution, evaporating water, thermally cracking, activating, expanding pores and modifying to obtain carbon black; the carbon content in the carbon solid waste is more than 60 wt%. The carbon black obtained by the invention has excellent properties in all aspects compared with the N330 carbon black on the market, and the physical properties of the carbon black are greatly improved after the carbon black is filled into tire rubber.
Description
Technical Field
The invention relates to a preparation method of carbon black, in particular to a method for preparing carbon black for tires by using carbon solid waste as a raw material, and belongs to the technical field of comprehensive utilization of industrial solid waste resources.
Background
Carbon black is the main filler and reinforcing agent in the rubber industry, and the consumption of carbon black in the rubber industry accounts for 94% of the total consumption, of which 60% is used for manufacturing tires. The addition of the carbon black can endow the rubber product with a series of excellent properties, such as improvement of tensile strength, hardness and wear resistance. At present, the main preparation processes of carbon black comprise a tank method, a furnace method, a thermal cracking method and the like, most of raw materials required by the methods for preparing the carbon black comprise natural gas, coal tar, anthracene oil, calcium carbide, heavy oil and the like, a large amount of non-renewable resources are consumed, the production cost is high, and the price of the carbon black is high. In order to solve the contradiction between the supply and the demand of carbon black in China, the production of carbon black by replacing oil and natural gas with some cheap raw materials is a new way to be developed.
The carbon product is widely applied in various fields, so that a large amount of carbon solid waste is generated every year, and the carbon solid waste mainly comprises an aluminum electrolysis waste cathode, a waste battery cathode and waste activated carbon. The carbon solid waste contains harmful substances such as heavy metals, toxic organic matters, fluorides, cyanides and the like, and can pollute the atmosphere, water resources and soil on a large scale. The stockpiling or the landfill can not only eliminate the toxicity and the corrosive hazard of the aluminum electrolysis waste cathode material fundamentally, but also cause the resource waste. The carbon solid waste carbon content is generally higher, part of the carbon solid waste carbon has higher surface activity, and the carbon black can easily reach the standard of the carbon black for the tire through treatment, and has larger potential when replacing oil and natural gas as raw materials for producing the carbon black for the tire.
Disclosure of Invention
The invention aims to produce the carbon black for the tire by utilizing carbon solid wastes so as to realize the reutilization of industrial excess materials, reduce the cost problem of carbon black production and meet the requirement of comprehensive performance.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a method of making a carbon black comprising the steps of:
s1, crushing the carbon solid waste, leaching in a mixed solution of acid and hydrogen peroxide, filtering, washing and drying to obtain carbon powder;
s2, soaking the carbon powder obtained in the step S1 in an alkali solution, volatilizing water, thermally cracking, activating, expanding pores, and modifying to obtain carbon black; the carbon content in the carbon solid waste is more than 60 wt%.
Preferably, the carbon solid waste is selected from one or more of aluminum electrolysis waste cathodes, waste battery cathodes and waste activated carbon.
Preferably, in S1, the carbon solid waste is crushed into particles, and the particle size distribution of the particles is: the granules with the particle size less than 200 meshes account for 60-90% of the total mass of the spare granules.
The particles are crushed until the particle size of most particles is below 200 meshes, so that the particles are fully reacted in the subsequent treatment process, and the particles larger than 200 meshes are not beneficial to fully reacting.
Preferably, the acid in the mixed solution in S1 is an oxyacid.
The oxygen-containing functional group such as carboxyl, hydroxyl and the like can obviously improve the hydrophilicity of the carbon black. The adoption of the oxyacid can also prevent the reaction of other non-oxyacid anion groups and carbon skeleton macromolecules from substituting for redundant functional groups.
By adopting the oxidizing acid leaching, not only the better effects of removing ash impurities and desulfurizing are achieved, but also oxygen-containing functional groups, such as carboxyl, hydroxyl and the like, of a carbon sheet layer in a microstructure are increased, and the groups are hydrophilic, so that the polarity of the carbon black and the dispersion and stability in a saturated rubber system, such as a butyl rubber system, are ensured.
Preferably, the acid in the mixed solution in S1 is nitric acid.
The nitric acid has strong acidity, is beneficial to the reaction speed, and the nitrate radical is easy to dissolve in water and wash.
Preferably, the concentration of the nitric acid in the mixed solution is 1-8 mol/L.
Further preferably, the concentration of the nitric acid in the mixed solution is 6-8 mol/L.
Preferably, the concentration of the hydrogen peroxide in the mixed solution is 1-4 mol/L.
Further preferably, the concentration of hydrogen peroxide in the mixed solution is 2 mol/L.
Preferably, the liquid-solid ratio of the mixed solution of the acid and the hydrogen peroxide to the carbon particles is 10-30mL/g, the leaching temperature is 60-80 ℃, the leaching time is 8-10h, and the stirring speed is 150-200 r/min.
In the leaching process, the acid and the hydrogen peroxide have synergistic effect, so that the desulfurization and impurity removal effects of the concentrated acid can be achieved, and the amount of the concentrated acid required for achieving the same effect when only the concentrated acid is used can be reduced. And the hydrogen peroxide does not destroy the structure of the carbon skeleton as extensively as the concentrated acid with high concentration so that the hydrogen peroxide cannot be further processed into waste. Within the range of the concentration and the liquid-solid ratio, the requirements of desulfurization and impurity removal can be met, the improvement of polarity can be ensured, and the comprehensive performance of the catalyst can reach the optimum.
Preferably, in S2, the alkali solution is at least one selected from NaOH, KOH, LiOH, and RbOH solutions.
More preferably, in S2, the alkali solution is NaOH, the concentration of the alkali solution is 2mol/L, and the liquid-solid ratio is 30 ml/g.
Preferably, the carbon powder obtained in S1 is soaked in an alkali solution for 12-24 h.
The carbon powder and the alkali solution are mixed uniformly to evaporate water and then are cracked and carbonized, so that organic impurities, metal impurities, sulfur, aluminosilicate, cyanide, volatile components and the like can be effectively removed, the added alkali can be used as a catalyst for thermal cracking, in addition, the roasting process in the traditional alkali fusion method can be omitted, the process is simplified, and the cost is reduced.
Preferably, in the S2, the thermal cracking temperature is 500-800 ℃.
The thermal cracking temperature is higher than the boiling point of the organic matters of the impurities, the higher the temperature is, the more complete the impurities removal is, but after the temperature is over 800 ℃, the micropores of the carbon particles can shrink, so that the specific surface area is reduced.
At this temperature, the cracking products of the carbon solid waste are cracking gas, a small amount of cracking oil and alkali fusion carbon black.
Preferably, in S2, the activation reaming is performed in an activation reaming furnace with parameters of 550-.
In the activation hole expanding process, the 550-DEG C high-temperature steam is used for condensing and taking out the organic matter cracking substance residue in the carbon black, and dissolving and taking out the inorganic salt which is easy to dissolve in water and a part of alkali, so that the number of micropores in the carbon black is increased, the original atrophic micropores are expanded, and the specific surface area and the activity are effectively increased.
Preferably, the method further comprises the steps of washing, drying and grinding after the pore expansion is activated.
The water washing is to wash the alkali fusion carbon black to be alkalescent.
The pH value of the carbon black is adjusted to be alkalescent, so that the vulcanization speed in the tire production is improved, and the economic benefit of the tire industry is improved.
Preferably, the carbon black obtained by the grinding has a particle size distribution such that the carbon black having a particle size of less than 500 mesh accounts for 99.999% of the total mass of the carbon black.
The particle size distribution is the national standard requirement, and the smaller particle size is also beneficial to improving the specific surface area, thereby improving the tire filling effect.
Preferably, the modifier is titanate, and the mass of the titanate is 0.2-1.4% of the original mass of the carbon black.
The modification mechanism of titanate is as follows: the hydrophilic group and the hydrophobic group form a hydrophilic group, one end of the hydrophilic group can be compatible with the polymer, the other end of the hydrophilic group is combined with the carbon black through the effect of a chemical bond, the connection effect is realized between the polymer and the carbon black, the purpose of combining two substances with different properties is achieved, and the surface activity of the product is improved.
Preferably, the modifying process of the modifying agent is to mix the carbon black and the modifying agent by a high-speed mixer, wherein the rotating speed of the high-speed mixer is 1000-1200r/min, the stirring temperature is 75-85 ℃, and the stirring time is 10-15 min.
The invention is further explained below:
according to the invention, the carbon solid waste is crushed into fine particles and then leached by oxidizing acid, so that the ash removal effect and the desulfurization effect are better, the oxygen-containing functional groups of the carbon sheet layer in the microstructure are increased, and then the carbon sheet layer is fully mixed with alkali and then subjected to thermal cracking, so that the alkali melting and the thermal cracking are simultaneously carried out, the energy consumption is reduced, the process is simplified, alkali metal elements can also catalyze the thermal cracking, and the obtained carbon black has good structure and higher DBP value. After thermal cracking, activating and reaming are carried out, thus leading micropores in the carbon particles to be further expanded and activated, increasing the specific surface area, finally carrying out deep processing on the product, adding a modifier for kneading, improving the surface activity of the product, and improving the specific surface area of the product by superfine grinding. The obtained carbon black has excellent properties in all aspects compared with the N330 carbon black on the market, and the physical properties of the carbon black are greatly improved after the carbon black is filled into tire rubber.
The invention has the beneficial effects that:
1. the carbon black of the present invention has good polarity and dispersion and stability in saturated rubber systems such as butyl rubber systems.
2. The carbon black of the invention is alkalescent, and can improve the vulcanization speed in the production of tires, thereby improving the economic benefit of the tire industry. Rear end
3. According to the invention, the carbon black particles are activated, expanded and kneaded by adding the modifier, so that the surface activity of the carbon black is realized, and the adsorption specific surface area of CTAB is increased.
4. The invention adopts the simultaneous alkali fusion and thermal cracking, reduces the energy consumption, simplifies the process, and can catalyze the thermal cracking of alkali metal elements, and the obtained carbon black has good structure and higher DBP value.
5. The invention utilizes carbon solid waste to produce carbon black, saves non-renewable resources required in the traditional carbon black production process, and reduces the production cost of the carbon black. The method for preparing the carbon black is simple and easy to implement and high in preparation efficiency.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited thereto. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Example 1
Taking 1kg of waste cathode carbon blocks of aluminum electrolysis cells in a certain factory in China, wherein the contents of main elements (wt.%): 70.9 percent of C, 8.23 percent of Al, 9.55 percent of O, 5.38 percent of F, 2.57 percent of Na and 1.21 percent of Fe, crushing the mixture to 90 percent of minus 200 meshes, adding 30L of mixed solution of 8mol/L nitric acid and 2mol/L hydrogen peroxide, and leaching for 10 hours at the leaching temperature of 80 ℃ and the stirring rate of 200 r/min.
Washing to neutral after acid leaching and drying to obtain carbon powder, wherein the mass ratio of the carbon powder to NaOH is 1: 1.7, uniformly mixing, sequentially adding 20g of deionized water, standing and impregnating for 4 hours, putting the mixture obtained by drying and dehydrating the ore pulp after standing and impregnating into a thermal cracking furnace, and carrying out cracking carbonization at 800 ℃; then transferring the mixture to an activation furnace for activation and hole expansion, wherein the temperature of water vapor is 600 ℃, and obtaining alkali fusion carbon black; and cooling, washing with water to alkalescence, drying to obtain powdered carbon black, carrying out superfine grinding on the obtained carbon black, adding titanate with the mass being 1% of the original mass of the carbon black, stirring in a high-speed mixer at the rotating speed of 1200r/min at the stirring temperature of 85 ℃ for 15min, and cooling to obtain the modified carbon black.
The obtained modified carbon black 500-mesh residue is 0.001 percent, the ash content is less than 0.5 percent, the iodine absorption value is 84g/kg, the DBP value is 112 multiplied by 10 to 5m3/kg, the CTAB adsorption specific surface area is 80 multiplied by 103m3/kg, and the pouring density is 410kg/m 3. After the modified carbon black is filled into the tire rubber, the tensile strength of the tire rubber is 21.8MPa, the tearing strength is 50.6kN/m, the 300 percent stress at definite elongation is 7.5MPa, and the elongation at break is 508 percent.
Example 2
Taking 1kg of waste battery cathode carbon residue from a certain domestic factory, wherein the content of main elements (wt.%): c87.11, Al 2.24, O3.50, Zr 1.64, Ca 1.60, Fe 0.42, P1.44, S0.09, Si 0.38 and Ti 0.34, crushing to 90 percent of minus 200 meshes, adding 25L of mixed solution of 6mol/L nitric acid and 2mol/L hydrogen peroxide, and leaching for 9 hours under the conditions that the leaching temperature is 75 ℃ and the stirring rate is 180 r/min.
Washing to neutral after acid leaching and drying to obtain carbon powder, wherein the mass ratio of the carbon powder to NaOH is 1: 1.5, uniformly mixing, sequentially adding 20g of deionized water, standing and impregnating for 4 hours, putting the mixture obtained by drying and dehydrating the ore pulp after standing and impregnating into a thermal cracking furnace, and carrying out cracking carbonization at 700 ℃; then transferring the mixture to an activation furnace for activation and hole expansion, wherein the temperature of water vapor is 550 ℃, and obtaining alkali fusion carbon black; and cooling, washing with water to alkalescence, drying to obtain powdered carbon black, carrying out superfine grinding on the obtained carbon black, adding titanate with the mass being 1% of the original mass of the carbon black, stirring in a high-speed mixer at the rotating speed of 1100r/min at the stirring temperature of 80 ℃ for 15min, and cooling to obtain the modified carbon black.
The obtained modified carbon black 500-mesh residue is 0.001% smaller, the ash content is less than 0.5%, the iodine absorption value is 86g/kg, the DBP value is 113 x 10-5m3/kg, the CTAB adsorption specific surface area is 81 x 103m3/kg, and the pouring density is 412kg/m 3. After the modified carbon black is filled into the tire rubber, the tensile strength of the tire rubber is 21.9MPa, the tear strength is 51.2kN/m, the 300% stress at definite elongation is 7.4MPa, and the elongation at break is 515%.
Embodiment 3
1kg of waste activated carbon of a certain domestic plant with 94 wt% of carbon element is taken, the waste activated carbon is crushed to 90% of minus 200 meshes, 10L of mixed solution of 6mol/L nitric acid and 1mol/L hydrogen peroxide is added, and leaching is carried out for 8 hours under the conditions that the leaching temperature is 60 ℃ and the stirring speed is 150 r/min.
Washing to neutral after acid leaching and drying to obtain carbon powder, wherein the mass ratio of the carbon powder to NaOH is 1: 1.5, uniformly mixing, sequentially adding 20g of deionized water, standing and impregnating for 4 hours, putting the mixture obtained by drying and dehydrating the ore pulp after standing and impregnating into a thermal cracking furnace, and carrying out cracking carbonization at 600 ℃; then transferring the mixture to an activation furnace for activation and hole expansion, wherein the temperature of water vapor is 550 ℃, and obtaining alkali fusion carbon black; and cooling, washing with water to alkalescence, drying to obtain powdered carbon black, carrying out superfine grinding on the obtained carbon black, adding titanate with the mass being 1% of the original mass of the carbon black, stirring in a high-speed mixer at the rotating speed of 1000r/min and the stirring temperature of 75 ℃ for 10min, and cooling to obtain the modified carbon black.
The obtained modified carbon black 500-mesh residue is 0.001 percent, the ash content is less than 0.5 percent, the iodine absorption value is 87g/kg, the DBP value is 109 x 10-5m3/kg, the CTAB adsorption specific surface area is 88 x 103m3/kg, and the pouring density is 408kg/m 3. After the modified carbon black is filled into the tire rubber, the tensile strength of the tire rubber is 23.2MPa, the tearing strength is 52.3kN/m, the 300 percent stress at definite elongation is 7.1MPa, and the elongation at break is 512 percent.
Example 4
Taking 1kg of waste cathode carbon blocks, waste battery cathode carbon residues and waste activated carbon of aluminum electrolysis cells of certain factories in China respectively to form 3kg of mixed carbon solid waste, crushing the mixed carbon solid waste until the mixed carbon solid waste is 90 percent of minus 200 meshes, adding 30L of mixed solution of 8mol/L nitric acid and 2mol/L hydrogen peroxide, and leaching for 10 hours at the leaching temperature of 80 ℃ and the stirring speed of 200 r/min.
Washing to neutral after acid leaching and drying to obtain carbon powder, wherein the mass ratio of the carbon powder to NaOH is 1: 1.7, uniformly mixing, sequentially adding 20g of deionized water, standing and impregnating for 4 hours, putting the mixture obtained by drying and dehydrating the ore pulp after standing and impregnating into a thermal cracking furnace, and carrying out cracking carbonization at 800 ℃; then transferring the mixture to an activation furnace for activation and hole expansion, wherein the temperature of water vapor is 600 ℃, and obtaining alkali fusion carbon black; and cooling, washing with water to alkalescence, drying to obtain powdered carbon black, carrying out superfine grinding on the obtained carbon black, adding titanate with the mass being 1% of the original mass of the carbon black, stirring in a high-speed mixer at the rotating speed of 1200r/min at the stirring temperature of 85 ℃ for 15min, and cooling to obtain the modified carbon black.
The obtained modified carbon black 500-mesh residue is 0.001 percent, the ash content is less than 0.5 percent, the iodine absorption value is 85g/kg, the DBP value is 112 multiplied by 10 to 5m3/kg, the CTAB adsorption specific surface area is 85 multiplied by 103m3/kg, and the pouring density is 410kg/m 3. After the modified carbon black is filled into the tire rubber, the tensile strength of the tire rubber is 22.4MPa, the tear strength is 51.3kN/m, the 300% stress at definite elongation is 7.2MPa, and the elongation at break is 511%.
Example 5
Taking 1kg of waste cathode carbon blocks, waste battery cathode carbon residues and waste activated carbon of aluminum electrolysis cells of certain factories in China respectively to form 3kg of mixed carbon solid waste, crushing the mixed carbon solid waste to-200 meshes accounting for 90 percent, and drying to obtain carbon powder, wherein the mass ratio of the carbon powder to NaOH is 1: 1.7, uniformly mixing, sequentially adding 20g of deionized water, standing and impregnating for 4 hours, putting the mixture obtained by drying and dehydrating the ore pulp after standing and impregnating into a thermal cracking furnace, and carrying out cracking carbonization at 800 ℃; then transferring the mixture to an activation furnace for activation and hole expansion, wherein the temperature of water vapor is 600 ℃, and obtaining alkali fusion carbon black; and cooling, washing with water to alkalescence, drying to obtain powdered carbon black, carrying out superfine grinding on the obtained carbon black, adding titanate with the mass being 1% of the original mass of the carbon black, stirring in a high-speed mixer at the rotating speed of 1200r/min at the stirring temperature of 85 ℃ for 15min, and cooling to obtain the modified carbon black. The ash content of the modified carbon black is more than 4 percent, and the modified carbon black does not meet the national standard.
Example 6
Taking 1kg of waste cathode carbon blocks, waste battery cathode carbon residues and waste activated carbon of aluminum electrolysis cells of certain factories in China respectively to form 3kg of mixed carbon solid waste, crushing the mixed carbon solid waste until the mixed carbon solid waste is 90 percent of minus 200 meshes, adding 30L of mixed solution of 8mol/L nitric acid and 2mol/L hydrogen peroxide, and leaching for 10 hours at the leaching temperature of 80 ℃ and the stirring speed of 200 r/min. And washing to neutral after acid leaching to obtain carbon powder, drying to obtain carbon powder, carrying out superfine grinding on the obtained carbon black, adding titanate with the mass being 1% of the original mass of the carbon black, stirring in a high-speed mixer at the rotating speed of 1200r/min at the stirring temperature of 85 ℃, and cooling for 15min to obtain the modified carbon black. The ash content of the modified carbon black is more than 10 percent, and the modified carbon black does not meet the national standard.
Example 7
Taking 1kg of waste cathode carbon blocks, waste battery cathode carbon residues and waste activated carbon of aluminum electrolysis cells of certain factories in China respectively to form 3kg of mixed carbon solid waste, crushing the mixed carbon solid waste until the mixed carbon solid waste is 90 percent of minus 200 meshes, adding 30L of mixed solution of 8mol/L nitric acid and 2mol/L hydrogen peroxide, and leaching for 10 hours at the leaching temperature of 80 ℃ and the stirring speed of 200 r/min. Washing to neutral after acid leaching and drying to obtain carbon powder, wherein the mass ratio of the carbon powder to NaOH is 1: 1.7, uniformly mixing, sequentially adding 20g of deionized water, standing and impregnating for 4 hours, putting the mixture obtained by drying and dehydrating the ore pulp after standing and impregnating into a thermal cracking furnace, and carrying out cracking carbonization at 800 ℃; cooling, washing with water to alkalescence, drying to obtain powdered carbon black, and carrying out superfine grinding on the obtained carbon black.
The obtained carbon black 500 mesh screen residue is 0.001% smaller, ash content is less than 0.5%, iodine absorption value is 70g/kg, DBP value is 99 x 10-5m3Per kg, CTAB adsorption specific surface area of 70X 103m3Kg, pour density 410kg/m 3. After the modified carbon black is filled into the tire rubber, the tensile strength of the tire rubber is 19.8MPa, the tear strength is 39.4kN/m, the 300% stress at definite elongation is 5.1MPa, and the elongation at break is 392%.
Example 8
Taking 1kg of waste cathode carbon blocks of aluminum electrolysis cells in a certain factory in China, wherein the contents of main elements (wt.%): 70.9 of C, 8.23 of Al, 9.55 of O, 5.38 of F, 2.57 of Na and 1.21 of Fe, crushing the mixture to 90 percent of minus 200 meshes, adding 30L of 14mol/L nitric acid solution, and leaching for 10 hours at the leaching temperature of 80 ℃ and the stirring rate of 200 r/min.
Washing to neutral after acid leaching and drying to obtain carbon powder, wherein the mass ratio of the carbon powder to NaOH is 1: 1.7, uniformly mixing, sequentially adding 20g of deionized water, standing and impregnating for 4 hours, putting the mixture obtained by drying and dehydrating the ore pulp after standing and impregnating into a thermal cracking furnace, and carrying out cracking carbonization at 800 ℃; then transferring the mixture to an activation furnace for activation and hole expansion, wherein the temperature of water vapor is 600 ℃, and obtaining alkali fusion carbon black; and cooling, washing with water to alkalescence, drying to obtain powdered carbon black, carrying out superfine grinding on the obtained carbon black, adding titanate with the mass being 1% of the original mass of the carbon black, stirring in a high-speed mixer at the rotating speed of 1200r/min at the stirring temperature of 85 ℃ for 15min, and cooling to obtain the modified carbon black.
The obtained modified carbon black 500-mesh residue is 0.001 percent, the ash content is less than 0.5 percent, the iodine absorption value is 40g/kg, the DBP value is 70 multiplied by 10 to 5m3/kg, the CTAB adsorption specific surface area is 48 multiplied by 103m3/kg, and the pouring density is 399kg/m 3. The national standard requirements are not met.
Example 9
After the tire rubber is filled with the carbon black meeting the national standard according to the mass ratio of the carbon black to the rubber of 3:10, the performances of the tire rubber are tested in a comparison manner, and the performances are shown in table 1.
TABLE 1 physical Properties of various carbon Black-reinforced tire rubbers
And (4) analyzing results: from the comparison of the data in the examples, the carbon blacks obtained in examples 1, 2, 3 and 4, which were prepared according to the normal procedure, were better in tensile strength, tear strength, 300% stress at break and elongation at break than the commercial N330 carbon black-filled rubber after filling the rubber in a tire. The factors determining the physical properties of the rubber after carbon black filling are as follows: specific surface area, structure and surface activity of the carbon black; the specific surface area and the surface activity can be represented by CTAB adsorption specific surface area values, the structure can be represented by DBP values, the DPB values of the products obtained by the implementation cases 1, 2, 3 and 4 are all higher than those of N330 carbon black on the market, so the physical properties of the rubber after being filled are better than those of the rubber after being filled with the N330 carbon black, and in the embodiment 7 without a modifier modification step, the obtained carbon black has weak surface activity, low CTAB value and no effect better than that of the N330 carbon black.
Claims (7)
1. A method of making a carbon black comprising the steps of:
s1, crushing the carbon solid waste, leaching the crushed carbon solid waste in a mixed solution of acid and hydrogen peroxide, and sequentially filtering, washing and drying the leached carbon solid waste to obtain carbon powder;
s2, soaking the carbon powder obtained in the step S1 in an alkali solution, evaporating water, thermally cracking, activating, expanding pores and modifying to obtain carbon black;
the carbon content in the carbon solid waste is more than 60 wt%;
the acid in the mixed solution in the S1 is nitric acid; the concentration of the nitric acid is 1-8mol/L, and the concentration of the hydrogen peroxide in the mixed solution is 1-4 mol/L;
in the S2, the modifier for modification is titanate, and the mass of the modifier is 0.2-1.4% of the mass of the carbon black;
in the S2, the thermal cracking temperature is 500-800 ℃;
in the step S2, the activation reaming is performed in an activation reaming furnace with the parameters of 550 and 600 ℃ for 2-4 h.
2. The method for preparing carbon black according to claim 1, wherein the carbon solid waste is selected from one or more of aluminum electrolysis waste cathodes, waste battery cathodes and waste activated carbon.
3. The method for preparing carbon black according to claim 1, wherein in S1, the carbon solid waste is crushed into particles having a particle size distribution of: the granules with the particle size less than 200 meshes account for 60-90% of the total mass of the spare granules.
4. The method for preparing carbon black according to claim 1, wherein the liquid-solid ratio of the mixed solution of acid and hydrogen peroxide to the carbon solid waste is 10-30mL/g, the leaching temperature is 60-80 ℃, the leaching time is 8-10h, and the stirring rate is 150-200 r/min.
5. The method for preparing carbon black according to claim 1, wherein in S2, the alkali solution is at least one selected from NaOH, KOH, LiOH and RbOH solutions.
6. The method for preparing carbon black according to claim 1, wherein in S2, the alkali solution is NaOH solution, the concentration of the alkali solution is 2mol/L, and the liquid-solid ratio of the alkali solution to the carbon powder is 30 ml/g.
7. The method of claim 1, further comprising the steps of washing, drying, and grinding after pore expansion activation; the particle size distribution of the carbon black obtained by grinding is that the carbon black with the particle size of less than 500 meshes accounts for 99.999 percent of the total mass of the carbon black.
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| CN113429809A (en) * | 2021-05-31 | 2021-09-24 | 安徽德瑞新材料科技有限公司 | Processing technology of carbon black for ultrablue phase color matching |
| CN114634722A (en) * | 2022-04-06 | 2022-06-17 | 安徽固瑞特新材料科技有限公司 | Method for improving structure of regenerated carbon black |
| CN115073940B (en) * | 2022-06-21 | 2023-09-19 | 安徽固瑞特新材料科技有限公司 | Production process flow for improving dispersion performance of cracking carbon black for rubber |
| CN115746628A (en) * | 2022-11-18 | 2023-03-07 | 安徽固瑞特新材料科技有限公司 | Thermal cracking carbon black aqueous suspension of waste tires, and preparation method and application thereof |
Citations (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1934268A1 (en) * | 1968-07-01 | 1970-02-12 | Comalco Alu | Process for the recovery of cryolite from spent cathodes |
| TW200827390A (en) * | 2006-12-28 | 2008-07-01 | Hsiu-Wei Chen | Method for preparation of high-purity carbon black recycled from a waste tire |
| CN101811695A (en) * | 2010-04-02 | 2010-08-25 | 北京矿冶研究总院 | Method for recovering graphite from electrolytic aluminum waste cathode carbon block |
| CN103280611A (en) * | 2013-03-29 | 2013-09-04 | 江西省电力科学研究院 | Method for recovering waste lithium iron phosphate battery negative electrode pieces |
| CN103623816A (en) * | 2013-11-08 | 2014-03-12 | 浙江大学 | Method for preparing ruthenium catalyst from biomass pyrolysis carbon, ruthenium catalyst and application thereof |
| CN105295452A (en) * | 2015-10-28 | 2016-02-03 | 贵州安泰再生资源科技有限公司 | Method for preparing low-ash-content carbon black through waste tire |
| CN105964659A (en) * | 2016-05-27 | 2016-09-28 | 中南大学 | Comprehensive resource recycling method for waste cathode carbon blocks of aluminum cells |
| CN106082213A (en) * | 2016-06-20 | 2016-11-09 | 山东欧铂新材料有限公司 | A kind of compound petroleum coke matrix activated carbon and preparation method thereof, ultracapacitor |
| CN106077040A (en) * | 2016-06-30 | 2016-11-09 | 中南大学 | A kind of method of ultrasonic assistant alkali leaching process aluminum electrolytic waste and old cathode carbon block |
| CN106180118A (en) * | 2016-06-30 | 2016-12-07 | 中南大学 | A kind of ultrasonic assistant pressurized acid leaching reclaims the method for charcoal in aluminum electrolysis waste cathode |
| CN106345440A (en) * | 2016-11-10 | 2017-01-25 | 中南大学 | Method for regenerating activated carbon |
| CN106512974A (en) * | 2016-11-10 | 2017-03-22 | 中南大学 | Regeneration method of activated carbon |
| CN107474310A (en) * | 2017-08-03 | 2017-12-15 | 中创奕龙科技股份有限公司 | A kind of environment-friendly type tire material manufacture method |
| CN108439405A (en) * | 2018-04-19 | 2018-08-24 | 句容市盛达环保净化材料有限公司 | A kind of preparation method of modified activated carbon |
| CN108728867A (en) * | 2018-06-19 | 2018-11-02 | 东北大学 | A kind of innoxious separation method of aluminium electroloysis waste cathode carbon block |
| CN110240162A (en) * | 2019-08-05 | 2019-09-17 | 绿业中试低碳科技（镇江）有限公司 | The preparation method of aluminium electroloysis waste carbon-based porous charcoal |
| CN110407190A (en) * | 2019-07-25 | 2019-11-05 | 中南大学 | A kind of method of the useless cathode recycling charcoal of aluminium electroloysis |
| CN111170299A (en) * | 2020-01-19 | 2020-05-19 | 中南大学 | Method for recovering waste cathode carbon blocks from aluminum electrolysis |
| CN111232947A (en) * | 2020-01-19 | 2020-06-05 | 中南大学 | Method for recovering waste cathode carbon blocks in aluminum electrolysis |
| CN111302753A (en) * | 2020-03-13 | 2020-06-19 | 江苏嘉明碳素新材料有限公司 | Production process for preparing novel carburant from carbon solid waste material |
| CN111410975A (en) * | 2020-04-27 | 2020-07-14 | 北京万向新元科技有限公司 | Scrap tire pyrolysis processing method and system for tire manufacturing by changing carbon black structure |
| CN111423163A (en) * | 2020-03-30 | 2020-07-17 | 广东邦普循环科技有限公司 | Regenerated graphite-cement mortar composite material and preparation method thereof |
| CN111662576A (en) * | 2019-03-07 | 2020-09-15 | 青岛四维化工有限公司 | Preparation method of quasi-in-situ modified pyrolytic carbon black |
| CN111792644A (en) * | 2020-07-31 | 2020-10-20 | 郑州大学 | Method for preparing porous carbon material by using aluminum electrolysis waste cathode carbon |
-
2020
- 2020-11-04 CN CN202011215551.1A patent/CN112322076B/en active Active
Patent Citations (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1934268A1 (en) * | 1968-07-01 | 1970-02-12 | Comalco Alu | Process for the recovery of cryolite from spent cathodes |
| TW200827390A (en) * | 2006-12-28 | 2008-07-01 | Hsiu-Wei Chen | Method for preparation of high-purity carbon black recycled from a waste tire |
| CN101811695A (en) * | 2010-04-02 | 2010-08-25 | 北京矿冶研究总院 | Method for recovering graphite from electrolytic aluminum waste cathode carbon block |
| CN103280611A (en) * | 2013-03-29 | 2013-09-04 | 江西省电力科学研究院 | Method for recovering waste lithium iron phosphate battery negative electrode pieces |
| CN103623816A (en) * | 2013-11-08 | 2014-03-12 | 浙江大学 | Method for preparing ruthenium catalyst from biomass pyrolysis carbon, ruthenium catalyst and application thereof |
| CN105295452A (en) * | 2015-10-28 | 2016-02-03 | 贵州安泰再生资源科技有限公司 | Method for preparing low-ash-content carbon black through waste tire |
| CN105964659A (en) * | 2016-05-27 | 2016-09-28 | 中南大学 | Comprehensive resource recycling method for waste cathode carbon blocks of aluminum cells |
| CN106082213A (en) * | 2016-06-20 | 2016-11-09 | 山东欧铂新材料有限公司 | A kind of compound petroleum coke matrix activated carbon and preparation method thereof, ultracapacitor |
| CN106077040A (en) * | 2016-06-30 | 2016-11-09 | 中南大学 | A kind of method of ultrasonic assistant alkali leaching process aluminum electrolytic waste and old cathode carbon block |
| CN106180118A (en) * | 2016-06-30 | 2016-12-07 | 中南大学 | A kind of ultrasonic assistant pressurized acid leaching reclaims the method for charcoal in aluminum electrolysis waste cathode |
| CN106345440A (en) * | 2016-11-10 | 2017-01-25 | 中南大学 | Method for regenerating activated carbon |
| CN106512974A (en) * | 2016-11-10 | 2017-03-22 | 中南大学 | Regeneration method of activated carbon |
| CN107474310A (en) * | 2017-08-03 | 2017-12-15 | 中创奕龙科技股份有限公司 | A kind of environment-friendly type tire material manufacture method |
| CN108439405A (en) * | 2018-04-19 | 2018-08-24 | 句容市盛达环保净化材料有限公司 | A kind of preparation method of modified activated carbon |
| CN108728867A (en) * | 2018-06-19 | 2018-11-02 | 东北大学 | A kind of innoxious separation method of aluminium electroloysis waste cathode carbon block |
| CN111662576A (en) * | 2019-03-07 | 2020-09-15 | 青岛四维化工有限公司 | Preparation method of quasi-in-situ modified pyrolytic carbon black |
| CN110407190A (en) * | 2019-07-25 | 2019-11-05 | 中南大学 | A kind of method of the useless cathode recycling charcoal of aluminium electroloysis |
| CN110240162A (en) * | 2019-08-05 | 2019-09-17 | 绿业中试低碳科技（镇江）有限公司 | The preparation method of aluminium electroloysis waste carbon-based porous charcoal |
| CN111170299A (en) * | 2020-01-19 | 2020-05-19 | 中南大学 | Method for recovering waste cathode carbon blocks from aluminum electrolysis |
| CN111232947A (en) * | 2020-01-19 | 2020-06-05 | 中南大学 | Method for recovering waste cathode carbon blocks in aluminum electrolysis |
| CN111302753A (en) * | 2020-03-13 | 2020-06-19 | 江苏嘉明碳素新材料有限公司 | Production process for preparing novel carburant from carbon solid waste material |
| CN111423163A (en) * | 2020-03-30 | 2020-07-17 | 广东邦普循环科技有限公司 | Regenerated graphite-cement mortar composite material and preparation method thereof |
| CN111410975A (en) * | 2020-04-27 | 2020-07-14 | 北京万向新元科技有限公司 | Scrap tire pyrolysis processing method and system for tire manufacturing by changing carbon black structure |
| CN111792644A (en) * | 2020-07-31 | 2020-10-20 | 郑州大学 | Method for preparing porous carbon material by using aluminum electrolysis waste cathode carbon |
Non-Patent Citations (5)
| Title |
|---|
| An environmental-friendly process for dissociating toxic substances and recovering valuable components from spent carbon cathode;Zhen Yao et al.;《Journal of Hazardous Materials》;20200928;1-15 * |
| Efficient reuse of anode scrap from lithium-ion batteries as cathode for pollutant degradation in electro-Fenton process: Role of different recovery processes;Zhiqin Cao et al.;《Chemical Engineering Journal》;20171224;256-264 * |
| 废旧橡胶轮胎制备燃料油和活性炭;唐光阳;《云南民族大学学报(自然科学版)》;20030730;第12卷(第03期);186-188 * |
| 浮选法综合利用铝电解槽废阴极炭块的工艺研究;卢惠民等;《金属矿山》;19970615(第06期);32-34 * |
| 铝电解废阴极炭块无害化综合利用工业实践;詹磊等;《轻金属》;20131020(第10期);59-62 * |
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