CN113004939B - Waste tire derived oil gradient high-valued utilization method - Google Patents
Waste tire derived oil gradient high-valued utilization method Download PDFInfo
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- CN113004939B CN113004939B CN202110256558.6A CN202110256558A CN113004939B CN 113004939 B CN113004939 B CN 113004939B CN 202110256558 A CN202110256558 A CN 202110256558A CN 113004939 B CN113004939 B CN 113004939B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention provides a waste tire derived oil gradient high-valued utilization method, which comprises the steps of filtering waste tire derived oil, and removing a large amount of cracking carbon black mixed in a cracking oil product due to airflow fluctuation caused by pressure change in a cracking reaction kettle in the cracking process of a waste tire; and then preliminarily distilling the filtered derived oil to obtain three components, namely a light component (IB-205 ℃), a medium component (205-.
Description
Technical Field
The invention belongs to the technical field of recycling of solid wastes, and relates to a gradient high-valued utilization method of waste tire derived oil.
Background
Rubber is an important strategic material for the safety of the national civilization and national defense, is called four basic industrial raw materials together with coal, steel and petroleum, and is widely applied to various fields of industry, agriculture, national defense, aerospace, transportation, daily production and the like. Under the strong support of national policies, the rubber industry becomes the main supporting industry of national economy, the annual domestic value is over trillion yuan, and tires account for about 70 percent. The Chinese tire yield accounts for about 40 percent of the world, 40 percent of the Chinese tire yield is exported and becomes a genuine rubber industry large country. At the same time, a large amount of scrap rubber is also produced, estimated to reach around 1600 million tons in 2019, with 3 million scrap tires approaching 1400 million tons.
The tire is a product with extremely high safety performance requirements, and in order to ensure personal safety, the tire develops towards the directions of high strength, wear resistance, stability and aging resistance, so that the tire cannot be naturally degraded for a long time (hundreds of even thousands of years) after being discarded, and how to treat the black pollution becomes a worldwide problem.
The waste tire treatment method in China mainly comprises two modes of recycling (renovation and remanufacturing, rubber regeneration and rubber powder) and final treatment (stacking, landfill, incineration, cracking and the like). The recycling of the waste tires at the present stage mainly comprises load tires and engineering tires, the recycling rate of the waste passenger tires is extremely low due to the formula and the structure, and the yield of the waste passenger tires is about half of that of the waste tires; meanwhile, rubber products such as tires after 2-3 times of recycling cannot be recycled from the safety perspective, so a large amount of waste tires are generated every year. These waste tires, which cannot be recycled, can only be disposed of by stacking, landfill, incineration, cracking, and the like.
The cracking technology can convert the waste tires into oil rich in aromatic hydrocarbon, gas with high fuel value, recyclable carbon black and recyclable steel wires, has the advantages of large treatment capacity, high economic benefit, small pollution and the like compared with other treatment methods, can realize the recycling of resources, is the most effective mode for the resource treatment of the waste tires at present, and the high-value application of cracking products is the key for realizing the resource utilization of the waste tires. At present, the quality of the waste tire cracking products is uneven, how to improve the quality of the cracking products and improve the economic added value is a key problem to be solved urgently by the waste tire cracking technology at present.
Cracked oil products have the advantages of convenience in transportation, high added value and the like, are main products (about 40-45%) of waste tire cracking all the time, and are used as fuel resources as main application channels of the cracked oil products, for example, as shown in a patent CN201811007988.9 (composite fuel oil prepared by using the cracked oil of the waste tire) method, the method for preparing the fuel oil by mixing the cracked oil of the tire and other oil products is the simplest utilization mode, but as the environmental protection requirement is higher and higher, the method for mixing the cracked oil products of the tire as the fuel is not suitable. The preparation of commercial oil by hydrofining cracked oil becomes the mainstream in the industry, and numerous patents relate to the method, such as patents CN201080053444.1 (catalytic hydrotreating method of cracked oil), CN201510385368.9 (combined hydrotreating method of tire cracked oil), CN201710670419.1 (fixed bed hydro-upgrading catalytic process of tire cracked oil fraction) and the like, which prepare commercial oil by re-catalytic cracking cracked oil, but because the cracked oil contains more than 90% of aromatic hydrocarbon, the batch-to-batch quantities are different, and elements such as silicon, fluorine and the like in the oil extremely easily poison the catalyst, so that a stable subsequent hydro-catalytic process cannot be formed, and with the requirement on the quality of finished oil in China, the cost of hydrofining the cracked oil of waste tires is increased, and meanwhile, the yield of the cracked oil of waste tires at present cannot reach the hydrofining specification, the method for hydrofining the waste tires stays in the theoretical and laboratory research stage all the time, and has no real industrial application.
The waste tire derived oil mainly comprises waste tire cracked oil obtained by the ways of waste tire cracking, waste tire catalytic cracking, microwave cracking and the like, is the category of the derived oil, and also covers a multi-component cracking process taking the waste tire as a main raw material, such as biomass and waste tire cooperative cracking, waste plastic and waste tire cooperative cracking, domestic waste and waste tire cooperative cracking and the like, and the generated cracked oil also belongs to the range of the waste tire derived oil. The oil products are suitable for the method.
Although the waste tire derived oil has high value, if the waste tire derived oil is not treated properly, new dangerous waste can be formed, the treatment cost is increased, and the industrial application of the waste tire cracking industry cannot be realized.
Disclosure of Invention
The invention aims to solve the problem of low added value of waste tire derived oil in the existing recycling of solid waste, provides a gradient high-value utilization method of the waste tire derived oil, and solves the problem of high-value utilization of the waste tire derived oil.
In order to achieve the above-mentioned effects, the present invention provides the following technical solutions:
the waste tire derived oil gradient high-valued utilization method comprises the following steps:
s1, filtering the waste tire derived oil, wherein the diameter of a screen is determined according to cracking raw materials and cracking process conditions, the impurities in the cracked oil product in the simple waste tire cracking process are mainly cracking carbon black, and the screen is selected as follows: 50-150 meshes; in the cracking process of the mixed raw materials mainly comprising waste tires, impurities in the cracked oil product not only have cracking carbon black, but also have more asphaltene components, and the screen selection is as follows: 100-200 mesh; meanwhile, in the cracking process, the cracking process of the fan migration and introduction cracking gas is adopted, and the cracking carbon black generated by cracking is light and is extremely easy to mix with cracking oil under the migration and introduction effect of the fan, and the screen selection is as follows: 100-200 meshes, therefore, the selection range of the screen is as follows: the method is mainly characterized in that 50-200 meshes are adopted, and the derived oil of the waste tire is filtered by a proper screen mesh to obtain two components of filtered derived oil and residual oil containing a large amount of cracking carbon black or asphaltene;
s2, distilling the filtered derived oil to obtain three components, and respectively adopting different high-value utilization methods according to the distribution and composition of oil products in the components;
s3, aiming at the light component, the component has lower molecular chain of oil, less molecular weight, mainly contains higher content of benzene and benzene derivatives, mainly refers to benzene, toluene, ethylbenzene, xylene, carbon nine and above benzene derivatives, the component mainly obtains the benzene and benzene derivatives in the component through extraction, the substance is a high-value chemical raw material, and the part of products can be used as high-quality chemical raw materials for further producing downstream chemical products; mixing the extracted oil product with the medium components for subsequent high-value application;
s4, aiming at the mixed medium components, the oil in the components mainly comprises aromatic hydrocarbon, the content of the aromatic hydrocarbon is over 95 percent, the aromatic hydrocarbon content of the oil is not large compared with that of commercial diesel oil, meanwhile, the yield of the tire derived oil is very little compared with that of crude oil, the aromatic hydrocarbon content of the medium components is not large compared with that of the commercial diesel oil, and the blended tire derived oil has little influence on the treatment process of the crude oil, so the components are mixed with the crude oil for preparing the commercial fuel;
s5, aiming at the heavy component, the component oil contains a large amount of components such as asphaltene and wax, the kinematic viscosity of the oil is high, and the cost is high if the hydrogenation catalysis is continued to prepare the fuel oil. Therefore, the key to the high-value application of the oil composition is to fully utilize the characteristics of macromolecular chains in the oil composition. The insufficient combustion of the fuel required by the preparation of the commercial carbon black at present is almost matched with the characteristics of the heavy components of the fuel, the kinematic viscosity of the fuel also meets the relevant requirements, and the performance preparation of the fuel after the residual oil containing a large amount of cracking carbon black after the waste tire derived oil is filtered is mixed can better meet the requirements of the raw materials for preparing the commercial carbon black;
s6, in order to further improve the economic value of the heavy component of the oil derived from the waste tires, the invention provides a method for preparing a high-performance carbon material by directly cracking the heavy component of the oil by using high-energy laser beams, which mainly utilizes the characteristics of macromolecular chains in heavy oil products, protects the heavy oil products by inert gas, and utilizes the instantaneous high temperature: 900 ℃ and 1200 ℃ under high pressure: under the condition of 1-2.5MPa, macromolecular chains in the heavy component are instantaneously carbonized, so that the carbon material similar to multilayer graphene substances is prepared.
Preferably, when the high-performance carbon material is prepared by using the heavy pyrolysis oil, the reaction environment and the carbon material growth carrier are preheated at high temperature for 10 minutes, the temperature is 400-.
Preferably, in the operation step of S6: a gap of 1-3mm is formed between a heavy pyrolysis oil conveying pipeline and a carbon material growth carrier copper foil, the heavy pyrolysis oil is controlled to have the oil amount of 2ml/s through a proportional control valve and passes through the oil conveying pipeline, when the heavy pyrolysis oil drops to the carbon material growth carrier copper foil, high-energy laser beams generated by a laser generator are directly irradiated, macromolecules in the pyrolysis oil product instantaneously undergo a pyrolysis reaction under the action of high energy, high temperature and high pressure to generate CHx free radicals, the generated free radicals have very high activity, and the high-energy beam radiation heat emitted by laser can activate copper ions in the copper foil, the part of copper ions can further catalyze the high-activity free radicals CHx to continuously undergo pyrolysis and gradually carbonize to generate stable C-C bonds, and at the moment, the embryonic form of the novel carbon material is generated and is slowly aggregated and nucleated to form discrete carbon material groups; meanwhile, when the laser high-energy beam is continuously and directly irradiated, carbon atoms of partial macromolecular chains are directly excited and attached to the active copper foil to form new growing points through nucleation, and the carbon material growing carrier continuously moves left and right and up and down to enable the carbon material to gradually grow at the nucleation positions and gradually increase the carbon materials.
Preferably, in the operation step of S2: the three components are light components: IBP-205 ℃, medium component: 205-365 ℃ and heavy components: three components at the temperature of more than 365 ℃.
Preferably, in the operation step of S1: when the cracked oil product which is simply cracked by the waste tire and does not have fan traction is used for filtering impurities, the screen is selected as follows: 50 meshes to 150 meshes are the main.
Preferably, in the operation step of S1: when the waste tire and other raw materials are mixed and cracked to filter impurities in the cracked oil, the screen selection is as follows: mainly 100 meshes to 150 meshes.
Preferably, in the operation step of S1: when the cracked oil product dragged by a fan in the cracking process filters impurities, the screen selection is as follows: mainly 100 meshes to 200 meshes.
The invention provides a waste tire derived oil gradient high-valued utilization method, which has the following beneficial effects:
the invention relates to a waste tire derived oil gradient high-valued utilization method, which comprises the steps of filtering waste tire derived oil, and removing a large amount of cracking carbon black mixed in a cracking oil product due to air flow fluctuation caused by pressure change in a cracking reaction kettle in the cracking process of the waste tire; and then primarily distilling the filtered derived oil to obtain three components, namely a light component (IB-205 ℃), a medium component (205-365 ℃) and a heavy component (>365 ℃), wherein the high-valued application process is realized by different technical means by utilizing the component characteristic difference of the three derived oil components, so that the pollution problem caused by the derived oil of the waste tires can be solved, the profit of waste tire cracking enterprises can be remarkably improved, and the development of the waste tire cracking industry is greatly promoted.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIGS. 2 and 3 are transmission electron micrographs of carbon black from example 1 of the present invention, a carbon black was prepared;
FIGS. 4 and 5 are transmission electron micrographs of carbon black from example 2 of the present invention, a carbon black was prepared;
FIGS. 6 and 7 are transmission electron micrographs of carbon black from example 3 of the present invention, a carbon black was prepared;
FIGS. 8 and 9 are transmission electron micrographs of carbon black obtained by preparation of carbon black according to example 4 of the present invention;
fig. 10 and 11 are schematic diagrams of the working principle of step 6).
Detailed Description
Referring to fig. 1-5, the cracking process conditions used in the examples were:
the pilot test experiment platform adopts a whole-tire intermittent cracking process, a burner heats a cracking device outside a furnace, a micro-positive pressure and oxygen-poor state is kept in a cracking reactor, and the experiment platform is sealed by a mechanical sealing structure to ensure that gas does not leak in the cracking process. The waste tires selected by cracking are semi-steel radial tires, the waste tires are directly loaded into a cracking furnace before the beginning of the experiment, the pretreatment procedures of crushing, steel wire drawing and the like are not needed, and the required catalyst dosage is added according to the proportion required by the experiment. The specific cracking process is as follows:
1) the pilot plant cracking reactor starts to heat up from room temperature under the action of heat provided by a burner, and the flow of fuel gas is controlled by the reactor according to a preset heating rate. When the cracking temperature range is between the normal temperature and 150 ℃, an exhaust valve of the cracking reactor is opened to slowly exhaust the air in the cracking furnace, thereby realizing the anoxic condition of the waste tire cracking process.
2) When the temperature of the cracking reactor is increased to 150 ℃, the emptying valve is closed, and the cracking gas condensation passage is opened, so that the cracking gas enters the post-treatment device after passing through the condenser. When the cracking temperature is higher than 150 ℃, the waste tires start to be gradually decomposed to generate small molecular gas, the gas is settled in the oil-gas separation and collection process to generate heavy oil, the gas which is not settled passes through a condenser to generate light oil components, and the gas which is not condensed is connected to a combustion chamber to be combusted, so that part of energy is provided for cracking.
3) And when the temperature interval of the cracking reactor is 400 ℃, collecting cracking gas for subsequent detection.
4) After the cracking temperature reaches 450 ℃, maintaining the temperature and continuing to burn for half an hour, stopping heating the cracking furnace, naturally cooling the furnace body, and collecting the cracking carbon black and the steel.
Example 1: gradient high-value utilization of waste tire cracking oil product
In this example, the waste tire pyrolysis oil product prepared under the above experimental equipment and process conditions is filtered by a filter screen (the filter screen is selected to be 60 mesh), and the filtered pyrolysis oil product is taken to be subjected to a distillation experiment.
(1) The distillation mode of the oil product selects reduced pressure distillation, and the reduced pressure distillation is strictly carried out according to the related requirements of the reduced pressure distillation in the national standard petroleum product reduced pressure distillation determination method (GB/T9168-1997), and the specific experimental data results are shown in Table 1.
TABLE 1 reduced pressure distillation data for waste tire cracked oils
(2) The light component in the above-mentioned distilled oil product is 17.1%, and the benzene, toluene, ethylbenzene, xylene and other benzene derivatives in the oil product can be extracted from said oil product by means of extraction, and the ratio of all the chemical raw materials in said component is shown in table 2:
TABLE 2 content of chemical raw materials in light components of waste tire pyrolysis oil
From the experimental data, the content of benzene and benzene derivatives in the light components of the waste tire cracked oil product exceeds 56.48%, and the light components contain a large amount of chemical raw materials, so that the economic value of the light components can be greatly improved after extraction.
(3) The light components and the medium components of the extracted waste tire cracked oil are mixed, and the component detection data is shown in table 3:
TABLE 3 determination of the components of the mass fraction in pyrolysis oil of used tires
From the experimental data, the oil product obtained by mixing the extracted light component and the medium component of the waste tire cracked oil product mainly takes aromatic hydrocarbon as the main component, and is similar to the existing diesel oil component, so that the component is mixed with the crude oil, the proportion of the component in the crude oil is small, and the influence of the waste tire cracked oil product on the subsequent processing performance is less. After experimental mixing, the prepared commercial gasoline and commercial diesel oil have little performance difference with the current market, and can completely meet the requirements of the national relevant standards.
(4) Residual oil containing a large amount of cracked carbon black after the pyrolysis oil of waste tires is filtered is mixed with heavy components and is combusted to prepare commercial carbon black, and a picture of a carbon black transmission electron microscope prepared by the method is shown in fig. 2.
As can be seen from figure 2, the structural unit of the carbon black prepared by cracking heavy oil is not an aggregate structure, but a growing chain branch structure of the carbon black, the chain branch structure is developed, the carbon black prepared on the surface has better structure degree, can be better dispersed in the mixing process, and has higher conductivity. And the prepared carbon black can also reach the nanometer grade in particle size, has larger specific surface area, and has the performance similar to that of the commercial carbon black.
(5) In order to further improve the added value of the part (mixing residual oil containing a large amount of cracked carbon black after filtering the waste tire cracked oil with heavy components), a novel carbon nano material is prepared by utilizing laser high-energy beams, and the structure of the prepared material is shown in figure 3:
the carbon materials continuously growing on the copper foil are distributed in a flocculent shape, the middle part is made of porous materials, and in the process of preparing the rubber composite material by mixing with rubber, the middle pore channel structure is beneficial to the penetration of rubber molecular chains, so that the performance of the rubber composite material can be obviously improved.
In example 1, waste tire pyrolysis oil is obtained through a common thermal cracking method, and is subjected to stepped high-value utilization, the controllability of common thermal cracking on a pyrolysis product is poor, in order to improve the proportion of chemical raw materials in a pyrolysis oil product, in example 2 and example 3, a process of catalyzing the pyrolysis of waste tires by using an acidic catalyst and a basic catalyst is respectively performed, and specific experimental data are described in the following examples.
Example 2: cascade utilization of FCC discharging agent catalytic cracking waste tyre cracking oil (acid catalyst)
In order to increase the content of chemical raw materials in the waste tire cracked oil product, the generation process of the cracked product is mainly regulated and controlled by an acid catalyst (mainly taking an FCC discharging agent as an example), so as to increase the content of benzene and benzene derivatives in the cracked oil product, and the obtained graded-grade high-value utilization method of the cracked oil product is as follows:
the FCC discharging agent prepared under the experimental equipment and the process conditions is used for catalyzing and cracking waste tire cracked oil products, the waste tire cracked oil products are filtered by a filter screen (the filter screen is selected to be 60 meshes), and the filtered cracked oil products are taken for distillation experiments.
(1) The distillation mode of the oil product selects reduced pressure distillation, and the reduced pressure distillation is strictly performed according to the related requirements of the reduced pressure distillation in the national standard, namely the method for measuring the reduced pressure distillation of petroleum products (GB/T9168-1997), and the specific experimental data results are shown in the following table 4.
TABLE 4 vacuum distillation data for cracked oils from FCC stripper catalytic cracking scrap tires
(2) The light component in the above-mentioned distilled oil product accounts for 18.5%, and this part of oil product is extracted by means of extraction to extract benzene, toluene, ethylbenzene, xylene and other benzene derivatives, and the ratio of chemical raw materials in this component is shown in table 5 below:
TABLE 5 content of chemical raw materials in light components of cracked oil products of FCC discharging agent catalytic cracking waste tires
From the experimental data, the content of benzene and benzene derivatives in the light components of the waste tire cracked oil product exceeds 63.01 percent, the total content ratio is improved compared with that of the common thermal cracking, and the economic value of the waste tire cracked oil product can be greatly improved after extraction.
(3) Mixing the extracted light components and medium components of the waste tire cracked oil, wherein the component detection data are shown in the following table 6:
TABLE 6 determination of the components of the mass fraction in the cracked oil of waste tires by catalytic cracking with FCC discharging agent
According to the experimental data, the light component and the medium component of the waste tire cracked oil product subjected to catalytic cracking by the extracted FCC discharging agent are mainly aromatic hydrocarbons and are similar to the conventional diesel oil component, so that the component is mixed with the crude oil, the proportion of the component in the crude oil is small, and the waste tire cracked oil product has little influence on the subsequent processing performance. After experimental mixing, the prepared commercial gasoline and commercial diesel oil have little performance difference with the current market, and can completely meet the requirements of the national relevant standards.
(4) The residual oil containing a large amount of cracking carbon black after filtering the cracking oil of the waste tires by the catalytic cracking of the FCC discharging agent is mixed with the heavy component, and the commercial carbon black is prepared by combustion, wherein the performance of the prepared carbon black is similar to that of the carbon black prepared by common cracking, and the picture of a projection electron microscope is shown in FIG. 4.
(5) The microstructure of the new carbon material prepared by the high-energy laser beam in the process of catalytically cracking the heavy oil in the waste tire cracked oil product by the FCC discharging agent is the same as that in the example 1.
Example 3: cascade utilization of alkaline oxide (calcium oxide) catalytic cracking waste tyre cracking oil (alkaline catalyst)
In order to increase the content of chemical raw materials in the waste tire cracked oil product, the embodiment mainly regulates and controls the generation process of the cracked product through an alkaline catalyst (mainly taking a calcium oxide discharging agent as an example), so as to increase the content of benzene and benzene derivatives in the cracked oil product, and the obtained graded-grade high-value utilization method of the cracked oil product comprises the following steps:
the calcium oxide prepared under the experimental equipment and the process conditions is used for catalyzing and cracking the waste tire cracked oil product, the waste tire cracked oil product is filtered by a filter screen (the filter screen is selected to be 60 meshes), and the filtered cracked oil product is taken for a distillation experiment.
(1) The distillation mode of the oil product selects reduced pressure distillation, and the reduced pressure distillation is strictly carried out according to the related requirements of the reduced pressure distillation in the national standard petroleum product reduced pressure distillation determination method (GB/T9168-1997), and the specific experimental data results are shown in the following table 7.
TABLE 7 reduced pressure distillation data for oils cracked from waste tires by calcium oxide catalytic cracking
(2) The light component in the above-mentioned distilled oil product accounts for 26.0%, and this part of oil product is passed through the mode of extraction to extract benzene, toluene, ethylbenzene, xylene and other benzene derivatives, and the chemical raw materials in said component account for the following table 8:
TABLE 8 content of chemical raw materials in light components of cracked oil product of calcium oxide catalytic cracking waste tire
From the experimental data, the content of benzene and benzene derivatives in the light components of the waste tire cracked oil product exceeds 60.49%, the total content is increased compared with the common thermal cracking, and the economic value of the waste tire cracked oil product can be greatly improved after extraction.
(3) The light components and the medium components of the extracted waste tire cracked oil are mixed, and the component detection data are shown in the following table 9:
TABLE 9 determination of the components of the mass fraction in the cracked oil of waste tires by calcium oxide catalytic cracking
According to the experimental data, the oil product obtained by mixing the light component and the medium component of the waste tire cracked oil product subjected to catalytic cracking by the extracted calcium oxide mainly takes aromatic hydrocarbon as the main component, and is similar to the conventional diesel oil component, so that the component is mixed with the crude oil, the proportion of the component in the crude oil is small, and the influence of the waste tire cracked oil product on the subsequent processing performance is less. After experimental mixing, the prepared commercial gasoline and commercial diesel oil have little performance difference with the current market, and can completely meet the requirements of the national relevant standards.
(4) Residual oil containing a large amount of cracking carbon black after the waste tire cracking oil is filtered through the calcium oxide catalytic cracking is mixed with heavy components, and commercial carbon black is prepared through combustion, wherein the performance of the prepared carbon black is the same as that of carbon black prepared by an FCC discharging agent.
(5) The microstructure of the new carbon material prepared by the heavy oil in the waste tire cracking oil product through calcium oxide catalytic cracking through laser high-energy beams is the same as that in the example 1.
Example 4: cascaded utilization of derived oil prepared by concerted catalytic cracking of waste tires and waste plastics
In example 4, the waste tire derived oil prepared by the cooperative pyrolysis of the waste tire and the waste plastic is mainly used in a gradient high-value manner, and the waste tire derived oil prepared under the above experimental equipment and process conditions is filtered by a filter screen (the filter screen is selected to be 100 meshes), and the filtered cracked oil is taken for distillation experiment.
(1) The distillation mode of the oil product selects reduced pressure distillation, and the reduced pressure distillation is strictly carried out according to the related requirements of the reduced pressure distillation in the national standard petroleum product reduced pressure distillation determination method (GB/T9168-1997), and the specific experimental data results are shown in the following table 10.
TABLE 10 vacuum distillation data for waste tire derived oils
| Item | Performance of |
| Initial cut point (IBP), DEG C | 75.5 |
| 5% recovery temperature, deg.C | 99.5 |
| 10% recovery temperature, deg.C | 106.5 |
| 20% recovery temperature, deg.C | 116.5 |
| 30% recovery temperature, deg.C | 126.5 |
| 40% recovery temperature, deg.C | 136.5 |
| 50% recovery temperature, deg.C | 143.5 |
| 60% recovery temperature, deg.C | 166.5 |
| 70% recovery temperature, deg.C | 186 |
| 80% recovery temperature, deg.C | 218.5 |
| 90% recovery temperature, deg.C | 290.5 |
| IBP-205 deg.C recovery volume% | 76 |
| 205- | 20 |
| >At 365 ℃ recovery volume% | 4 |
(2) The light component accounts for 76% of the above distilled oil, and the benzene, toluene, ethylbenzene, xylene and other benzene derivatives in the oil are extracted from the oil by means of extraction, wherein the ratio of the chemical raw materials in the component is shown in table 11 below:
TABLE 11 content of chemical raw materials in light components of waste tire-derived oils
From the experimental data, the content of benzene and benzene derivatives in the light components of the waste tire cracked oil product exceeds 75.18 percent, the total content ratio is improved compared with that of the common thermal cracking, and the economic value of the waste tire cracked oil product can be greatly improved after extraction.
(3) The light components and the medium components of the extracted waste tire derived oil product are mixed, and the component detection data are shown in the following table 12:
TABLE 12 determination of the Components of the Mass in oils derived from used tires
From the above experimental data, the oil product obtained by mixing the extracted light component and the medium component of the waste tire derived oil product is mainly aromatic hydrocarbon and is similar to the existing diesel oil component, so that the component is mixed with the crude oil, the proportion of the component in the crude oil is small, and the influence of the waste tire derived oil product on the subsequent processing performance is less. After experimental mixing, the prepared commercial gasoline and commercial diesel oil have little performance difference with the current market, and can completely meet the requirements of the national relevant standards.
(4) The filtered residual oil containing a large amount of cracked carbon black from the used tire derived oil was mixed with heavy components and burned to produce commercial carbon black, and the prepared carbon black was prepared as shown in fig. 5 below by a projection electron microscope.
(5) The microstructure of the new carbon material prepared by the laser high energy beam of the heavy oil in the derived oil prepared by the concerted catalytic cracking of the waste tire and the waste plastic is the same as that in the example 1.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (3)
1. The waste tire derived oil gradient high-valued utilization method is characterized by comprising the following steps of: filtering the waste tire derived oil to remove the pyrolysis carbon black in the pyrolysis oil product; then preliminarily distilling the filtered derived oil to obtain a light component, a medium component and a heavy component, and respectively realizing the high-valued application process of the three derived oil components by different technical means by utilizing the component characteristic difference of the three derived oil components; according to the distillation fraction temperature of oil products, three components are divided into light components: IBP-05 ℃ and medium composition: 205-365 ℃ and heavy components: three components at the temperature of more than 365 ℃; when the cracked oil product filters impurities, the screen selection is as follows: 50 meshes to 200 meshes; the screen selection of the asphaltene component in the filtered and cracked oil product is as follows: 100 meshes to 200 meshes;
aiming at heavy components, preparing a high-performance carbon material by directly cracking the heavy components of the oil by using high-energy laser beams, protecting by using inert gas, and using instantaneous high temperature: 900 ℃ and 1200 ℃ under high pressure: under the condition of 1-2.5MPa, macromolecular chains in the heavy components are instantaneously carbonized, so that a carbon material similar to a multilayer graphene substance is prepared;
when the heavy pyrolysis oil is used for preparing the high-performance carbon material, the reaction environment and the carbon material growth carrier are preheated at high temperature for 10 minutes at 400-500 ℃, the protective gas helium is continuously introduced, and the subsequent steps are carried out after the temperature is stable;
a1-3 mm gap is formed between the heavy pyrolysis oil conveying pipeline and the carbon material growth carrier copper foil, the heavy pyrolysis oil is controlled to have oil quantity of 2ml/s through the oil conveying pipeline by a proportional control valve, and when the heavy pyrolysis oil drops to the carbon material growth carrier copper foil, the heavy pyrolysis oil is directly irradiated by a high-energy laser beam generated by a laser generator.
2. The waste tire derived oil gradient high-value utilization method according to claim 1, characterized in that: filtering the waste tire derived oil by a proper screen mesh diameter to obtain two components of filtered derived oil and residual oil containing a large amount of cracking carbon black or asphaltene;
aiming at the light component, benzene and benzene derivatives in the component are obtained by extraction, and the extracted oil product is mixed with the medium component for subsequent high-value application.
3. The waste tire derived oil gradient high-value utilization method according to claim 1, characterized in that: aiming at the mixed medium components, the components are mixed with crude oil for preparing commercial oil products to prepare commercial fuel.
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