CN111377428B - Method for preparing needle coke by using medium-low temperature coal tar - Google Patents

Method for preparing needle coke by using medium-low temperature coal tar Download PDF

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CN111377428B
CN111377428B CN202010159169.7A CN202010159169A CN111377428B CN 111377428 B CN111377428 B CN 111377428B CN 202010159169 A CN202010159169 A CN 202010159169A CN 111377428 B CN111377428 B CN 111377428B
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coal tar
low temperature
needle coke
medium
temperature coal
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CN111377428A (en
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李冬
田育成
刘杰
黄晔
田亚飞
高峰
崔楼伟
郑金欣
淡勇
李稳宏
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Northwest University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C1/00—Working-up tar
    • C10C1/04—Working-up tar by distillation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C10C3/005—Working-up pitch, asphalt, bitumen by mixing several fractions (also coaltar fractions with petroleum fractions)

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Abstract

The invention provides a method for preparing needle coke by using medium-low temperature coal tar, which belongs to the technical field of needle coke preparation and specifically comprises the following steps of (1) preparing a refined raw material; (2) preparing a co-carbonization ternary system; (3) preparing a semicoke mixture; (4) four steps for forming needle coke. The needle coke prepared by the method has good fiber orientation and orderliness, simultaneously avoids the influence caused by the difference of thermal reactivity by adding a homogenizing agent and a co-carbonizing agent, has good mesophase system viscosity, and improves the coke-producing quality.

Description

Method for preparing needle coke by using medium-low temperature coal tar
Technical Field
The invention belongs to the technical field of needle coke preparation, and particularly relates to a method for preparing needle coke by using medium-low temperature coal tar.
Background
The needle coke is the main raw material for manufacturing high-power or ultrahigh-power electrodes, and when high-power or ultrahigh-power electric furnaces are used for steelmaking, the smelting time can be shortened by 30-50%, the electricity can be saved by 10-50%, and the economic benefit is very obvious. In addition, the application of needle coke in the fields of lithium batteries, nuclear power, aerospace and the like is continuously developed. At present, China already masters the manufacturing method of the ultrahigh-power graphite electrode, but the industrialized production technology of the needle coke is still inferior to that of developed countries such as the United states, Japan, Britain and the like. The basic mechanism of needle coke production is that proper raw oil is used to form a mesophase substance with plastic flow and ordered molecular arrangement during thermal conversion, and the mesophase substance is solidified at a certain temperature to form anisotropic needle coke.
CN1304974A discloses a method for preparing needle coke, which comprises the steps of removing quinoline insoluble substances from coal tar through flash evaporation, mixing the coal tar with petroleum components at a ratio of 100: 3-50, carrying out thermal polymerization at 380-480 ℃ and under the pressure of 0-2 MPa, and calcining. CN1418930A discloses a needle coke which is prepared by mixing petroleum and coal in a weight ratio of 1: 0.1-10, performing heat treatment at 400-440 ℃ and 0.2-2 MPa for 0.5-8 h, and performing thermal polymerization at 490-550 ℃ and 0.2-2 MPa for 3-8 h. CN101126027 discloses a coal-series needle coke which is prepared by using coal-series soft asphalt or prepared soft asphalt as raw material, carrying out flash evaporation and polycondensation pretreatment, adding petroleum component into flash evaporation raw material or polycondensation raw material or coking raw material, carbonizing, drying and oil gas purification coking treatment.
The above needle coke preparation process, while viable, still suffers from several deficiencies: (1) because of different components of the raw material family, the thermal reactivity of the raw material family has certain difference, so that the coking reaction liquid phase system is different, and the fusion and the growth of mesophase spherule are influenced by the difference of the coking reaction system. (2) The wide area streamline mesophase is generated, so that the quality difference of the coke is large. (3) The intermediate phase is a precursor for forming needle coke and plays a decisive role in carbonization reaction, the structure of the generated carbon body, a coke forming system and the like, but the intermediate phase system prepared at present has poor viscosity, so that the quality of the finished product needle coke is poor. (4) The preparation process of the needle coke is complex and has high cost.
Disclosure of Invention
Aiming at different components of the needle coke preparation raw materials, the thermal reaction has difference, which causes the difference of coking reaction liquid phase systems and influences the fusion and growth of mesophase spherule; the quality of the finished needle coke is poor; the preparation process is complex and the cost is high. The invention provides a method for preparing needle coke by using medium-low temperature coal tar, which takes the medium-low temperature coal tar as a raw material and prepares the needle coke on the basis of a co-carbonization reaction, and the process is simple, and the prepared needle coke fiber has good structure and high orderliness. The specific technical scheme is as follows:
a method for preparing needle coke by using medium-low temperature coal tar comprises the following steps:
(1) distilling medium-low temperature coal tar in a rectification reaction kettle, and distilling medium-low temperature coal tar with the distillate of more than 300 ℃ to prepare a refined raw material;
(2) compounding the refined raw material prepared in the step (1) with a homogenizing agent according to the proportion of 1: 0.5-2, and then adding a co-carbonization agent to modify asphalt to prepare a co-carbonization ternary system;
(3) performing thermal polymerization reaction on the co-carbonized ternary system prepared in the step (2) in a high-pressure reaction kettle by taking nitrogen as a protective gas to prepare a semicoke mixture;
(4) and (3) taking nitrogen as a protective gas, heating the semicoke mixture prepared in the step (3) to 1300-1600 ℃ in a calcining furnace under the conditions of a heating rate of 2-7 ℃/min and a constant pressure, calcining for 2-5 h, and cooling to obtain the needle coke.
Further defined, the thermal polymerization step in the step (3) is: heating the co-carbonization ternary system prepared in the step (2) to 200-350 ℃ in a high-pressure reaction kettle under the conditions that the heating rate is 2-8 ℃/min, the stirring rate is 100-200 r/min and the pressure is 1-5 MPa, and keeping the constant temperature for 1-3 h; and then heating to 300-500 ℃ under the conditions that the heating rate is 0.5-3 ℃/min, the stirring rate is 50-150 r/min and the pressure is 0-3 MPa, keeping the temperature for 7-9 h at a constant temperature, and finally relieving the pressure to prepare a semicoke mixture.
Further limiting, the adding amount of the co-carbonization agent is 5-25 wt%.
Further, the co-carbonization agent is one or a mixture of two or more of divinylbenzene, polystyrene and polyethylene.
Further, the homogenizing agent is one of vacuum residue asphalt, petroleum asphalt or high-temperature tar asphalt.
Further limited, the content of asphalt in the vacuum residue asphalt, the petroleum asphalt and the high-temperature tar asphalt is 30 wt% to 50 wt%.
Further defined, the medium and low temperature coal tar of the distillate >300 ℃ is a narrow distillate medium and low temperature coal tar of the distillate between 300 ℃ and 400 ℃.
Further limiting, the softening point of the low-temperature coal tar in the narrow fraction is 20-70 ℃, and the aromatic degree fA0.3 to 0.5.
Compared with the prior art, the invention has the beneficial effects that:
1. one of vacuum residue asphalt, petroleum asphalt or high-temperature tar asphalt is used as a homogenizing agent, which can provide 2-5 cyclic aromatic hydrocarbons, and the homogenizing agent can adjust the system viscosity of an intermediate phase formed in the thermal polymerization reaction process; the co-carbonization agent can be used as a nucleating agent of the mesocarbon microbeads formed in the thermal polymerization process, and does not need to be separated after nucleation; the 80% temperature difference of the mesophase formed during the thermal polymerization is adjusted by the homogenizing agent and the co-carbonizing agent such that Δ T80℃The homogenizing agent and the co-carbonizing agent jointly promote the formation of a wide-area and ordered fibrous structure intermediate phase at the temperature of 30-60 ℃, so that the influence caused by the difference of thermal reactivity is avoided, the formed intermediate phase system has good viscosity, and the coking quality is improved.
2. The intermediate phase thermal conversion process formed in the thermal polymerization reaction process is stable and soft, gas is separated out at the later stage of calcination and coking and penetrates through the solidified needle coke layer, and the needle coke with good fiber orientation and good orderliness is favorably formed.
3. According to the invention, through the co-carbonization ternary system, asphalt preparation is not required to be carried out independently, namely, asphalt modification and thermal polymerization reaction are combined, and asphalt preparation is carried out in the thermal polymerization reaction process, so that the technical process is simple and the cost is low.
Drawings
FIG. 1 is a macroscopic SEM image of needle coke prepared in example 1;
FIG. 2 is a polarization diagram of the needle coke prepared in example 1;
FIG. 3 is a macroscopic SEM image of the needle coke prepared in example 2;
FIG. 4 the polarization diagram of the needle coke prepared in example 2.
Detailed Description
The following embodiments of the bronze drum further explain the technical aspects of the present invention, but the present invention is not limited to the embodiments explained below.
Example 1
The embodiment of the invention relates to a method for preparing needle coke by using medium-low temperature coal tar, which comprises the following specific steps:
(1) distilling 2.5 kg of medium and low temperature coal tar in a distillation reaction kettle, and distilling to obtain narrow fraction of medium and low temperature coal tar with the fraction at 300-400 ℃ to prepare a refined raw material; the softening point of the low-temperature coal tar in the narrow fraction is 40 ℃, and the aromatic degree fAIs 0.4;
(2) compounding the refined raw material prepared in the step (1) with a homogenizing agent according to the proportion of 1:1, adding a co-carbonizing agent, and modifying asphalt to prepare a co-carbonized ternary system;
(3) taking nitrogen as a protective gas, heating the co-carbonization ternary system prepared in the step (2) to 300 ℃ in a high-pressure reaction kettle under the conditions of a heating rate of 6 ℃/min, a stirring rate of 150r/min and a pressure of 3MPa, and keeping the constant temperature for 3 hours; then heating to 500 ℃ under the conditions that the heating rate is 2 ℃/min, the stirring rate is 100r/min and the pressure is 1.5MPa, keeping the temperature for 8 hours at constant temperature, and finally decompressing to prepare a semicoke mixture;
(4) and (3) taking nitrogen as a protective gas, heating the semicoke mixture prepared in the step (3) to 1600 ℃ in a calcining furnace under the conditions that the heating rate is 5 ℃/min and the constant pressure is 0.02MPa, calcining for 5h, and cooling to obtain the needle coke, wherein the reference is made in figures 1 and 2.
In the step (2) of this example, the homogenizing agent is vacuum residue asphalt, and the content of asphalt in the vacuum residue asphalt is 40 wt%; the co-carbonizing agent was divinylbenzene, and the amount of the co-carbonizing agent added was 10 wt%.
The needle coke yield of this example was 58 wt%.
Example 2
The embodiment of the invention relates to a method for preparing needle coke by using medium-low temperature coal tar, which comprises the following specific steps:
(1) distilling 2.5 kg of medium and low temperature coal tar in a distillation reaction kettle, and distilling to obtain narrow fraction of medium and low temperature coal tar with the fraction at 300-400 ℃ to prepare a refined raw material; the softening point of the low-temperature coal tar in the narrow fraction is 40 DEG CDegree of aromaticity fAIs 0.4;
(2) compounding the refined raw material prepared in the step (1) with a homogenizing agent according to the proportion of 1:1, adding a co-carbonizing agent, and modifying asphalt to prepare a co-carbonized ternary system;
(3) taking nitrogen as a protective gas, heating the co-carbonization ternary system prepared in the step (2) to 300 ℃ in a high-pressure reaction kettle under the conditions of a heating rate of 6 ℃/min, a stirring rate of 150r/min and a pressure of 3MPa, and keeping the constant temperature for 3 hours; then heating to 500 ℃ under the conditions that the heating rate is 2 ℃/min, the stirring rate is 100r/min and the pressure is 1.5MPa, keeping the temperature for 8 hours at constant temperature, and finally decompressing to prepare a semicoke mixture;
(4) and (3) taking nitrogen as a protective gas, heating the semicoke mixture prepared in the step (3) to 1500 ℃ in a calcining furnace under the conditions that the heating rate is 6 ℃/min and the constant pressure is 0.02MPa, calcining for 4h, and cooling to obtain the needle coke with reference to the figures 3 and 4.
In the step (2) of this example, the homogenizing agent is vacuum residue asphalt, and the content of asphalt in the vacuum residue asphalt is 40 wt%; the co-carbonizing agent was divinylbenzene, and the amount of the co-carbonizing agent added was 10 wt%.
The needle coke yield of this example was 56 wt%.
Example 3
The embodiment of the invention relates to a method for preparing needle coke by using medium-low temperature coal tar, which comprises the following specific steps:
(1) distilling 2.5 kg of medium and low temperature coal tar in a distillation reactor, and distilling>Preparing refined raw materials from medium-low temperature coal tar at 300 ℃; said fraction>The softening point of the medium-low temperature coal tar at 300 ℃ is 40 ℃, and the aromatic degree fAIs 0.4;
(2) compounding the refined raw material prepared in the step (1) with a homogenizing agent according to the proportion of 1:1, adding a co-carbonizing agent, and modifying asphalt to prepare a co-carbonized ternary system;
(3) taking nitrogen as a protective gas, heating the co-carbonization ternary system prepared in the step (2) to 350 ℃ in a high-pressure reaction kettle under the conditions of a heating rate of 8 ℃/min, a stirring rate of 200r/min and a pressure of 5MPa, and keeping the constant temperature for 2 hours; then heating to 500 ℃ under the conditions that the heating rate is 3 ℃/min, the stirring rate is 150r/min and the pressure is 3MPa, keeping the temperature for 9h at constant temperature, and finally decompressing to prepare a semicoke mixture;
(4) and (3) taking nitrogen as a protective gas, heating the semicoke mixture prepared in the step (3) to 1600 ℃ in a calcining furnace under the conditions that the heating rate is 5 ℃/min and the constant pressure is 0.02MPa, calcining for 5h, and cooling to obtain the needle coke.
In the step (2) of this example, the homogenizing agent is petroleum asphalt, and the content of asphalt in the petroleum asphalt is 40 wt%; the co-carbonizing agent is polystyrene, and the addition amount of the co-carbonizing agent is 15 wt%.
The needle coke yield of this example was 56 wt%.
Example 4
The embodiment of the invention relates to a method for preparing needle coke by using medium-low temperature coal tar, which comprises the following specific steps:
(1) distilling 2.5 kg of medium and low temperature coal tar in a distillation reactor, and distilling>Preparing refined raw materials from medium-low temperature coal tar at 300 ℃; said fraction>The softening point of the medium-low temperature coal tar at 300 ℃ is 70 ℃, and the aromatic degree fAIs 0.5;
(2) compounding the refined raw material prepared in the step (1) with a homogenizing agent according to the proportion of 1:0.5, adding a co-carbonizing agent, and modifying asphalt to prepare a co-carbonized ternary system;
(3) taking nitrogen as a protective gas, heating the co-carbonization ternary system prepared in the step (2) to 250 ℃ in a high-pressure reaction kettle under the conditions of a heating rate of 4 ℃/min, a stirring rate of 120r/min and a pressure of 3MPa, and keeping the constant temperature for 1 h; then under the conditions that the heating rate is 1 ℃/min, the stirring rate is 100r/min and the pressure is 1MPa, heating to 400 ℃, keeping the constant temperature for 7 hours, and finally decompressing to prepare a semicoke mixture;
(4) and (3) taking nitrogen as a protective gas, heating the semicoke mixture prepared in the step (3) to 1400 ℃ in a calcining furnace under the conditions that the heating rate is 3 ℃/min and the constant pressure is 0.02MPa, calcining for 3h, and cooling to obtain the needle coke.
In the embodiment, the homogenizing agent in the step (2) is high-temperature tar pitch, and the content of pitch in the high-temperature tar pitch is 50 wt%; the co-carbonizing agent is polystyrene, and the addition amount of the co-carbonizing agent is 15 wt%.
The yield of needle coke in this example was 50 wt%.
Example 5
The embodiment of the invention relates to a method for preparing needle coke by using medium-low temperature coal tar, which comprises the following specific steps:
(1) distilling 2.5 kg of medium and low temperature coal tar in a distillation reactor, and distilling>Preparing refined raw materials from medium-low temperature coal tar at 300 ℃; said fraction>The softening point of the medium-low temperature coal tar at 300 ℃ is 50 ℃, and the aromatic degree fAIs 0.4;
(2) compounding the refined raw material prepared in the step (1) with a homogenizing agent according to the ratio of 1:1.5, adding a co-carbonizing agent, and modifying asphalt to prepare a co-carbonized ternary system;
(3) taking nitrogen as a protective gas, heating the co-carbonization ternary system prepared in the step (2) to 300 ℃ in a high-pressure reaction kettle under the conditions of a heating rate of 5 ℃/min, a stirring rate of 180r/min and a pressure of 4MPa, and keeping the constant temperature for 1 h; then under the conditions that the heating rate is 2 ℃/min, the stirring rate is 100r/min and the pressure is 2MPa, heating to 500 ℃, keeping the constant temperature for 9h, and finally decompressing to prepare a semicoke mixture;
(4) and (3) taking nitrogen as a protective gas, heating the semicoke mixture prepared in the step (3) to 1450 ℃ in a calcining furnace under the conditions that the heating rate is 3 ℃/min and the constant pressure is 0.02MPa, calcining for 4h, and cooling to obtain the needle coke.
In the embodiment, the homogenizing agent in the step (2) is high-temperature tar pitch, and the content of pitch in the high-temperature tar pitch is 45 wt%; the co-carbonizing agent is polystyrene, and the addition amount of the co-carbonizing agent is 5 wt%.
The yield of needle coke in this example was 50 wt%.
Example 6
(1) Distilling 2.5 kg of medium and low temperature coal tar in a distillation reactor, and distilling>Preparing refined raw materials from medium-low temperature coal tar at 300 ℃; said fraction>The softening point of the medium-low temperature coal tar at 300 ℃ is 20 DEG CDegree of aromaticity fAIs 0.3;
(2) compounding the refined raw material prepared in the step (1) with a homogenizing agent according to the proportion of 1:2, adding a co-carbonizing agent, and modifying asphalt to prepare a co-carbonized ternary system;
(3) taking nitrogen as a protective gas, heating the co-carbonization ternary system prepared in the step (2) to 200 ℃ in a high-pressure reaction kettle under the conditions of a heating rate of 2 ℃/min, a stirring rate of 100r/min and a pressure of 1MPa, and keeping the constant temperature for 1 h; then heating to 300 ℃ under the conditions that the heating rate is 0.5 ℃/min, the stirring rate is 50r/min and the pressure is 0.05MPa, keeping the temperature for 7 hours at constant temperature, and finally decompressing to prepare a semicoke mixture;
(4) and (3) taking nitrogen as a protective gas, heating the semicoke mixture prepared in the step (3) to 1300 ℃ in a calcining furnace under the conditions that the heating rate is 3 ℃/min and the constant pressure is 0.02MPa, calcining for 2h, and cooling to obtain the needle coke.
In the embodiment, the homogenizing agent in the step (2) is high-temperature tar pitch, and the content of pitch in the high-temperature tar pitch is 30 wt%; the co-carbonizing agent is a mixture of polystyrene and polyethylene, and the addition amount of the co-carbonizing agent is 25 wt%.
The needle coke yield of this example was 48 wt%.
Comparative example 1
(1) Distilling 2.5 kg of medium and low temperature coal tar in a distillation reactor, and distilling>Preparing refined raw materials from medium and low temperature coal tar at 360 ℃; the softening point of the low-temperature coal tar in the narrow fraction is 40 ℃, and the aromatic degree fAIs 0.4;
(2) compounding the refined raw material prepared in the step (1) with a homogenizing agent according to the proportion of 1:1, adding a co-carbonizing agent, and modifying asphalt to prepare a co-carbonized ternary system;
(3) taking nitrogen as a protective gas, heating the co-carbonization ternary system prepared in the step (2) to 300 ℃ in a high-pressure reaction kettle under the conditions of a heating rate of 6 ℃/min, a stirring rate of 150r/min and a pressure of 3MPa, and keeping the constant temperature for 3 hours; then heating to 500 ℃ under the conditions that the heating rate is 2 ℃/min, the stirring rate is 100r/min and the pressure is 1.5MPa, keeping the temperature for 8 hours at constant temperature, and finally decompressing to prepare a semicoke mixture;
(4) and (3) calcining the semicoke mixture prepared in the step (3) in a calcining furnace for 5 hours at 1450 ℃ by taking nitrogen as a protective gas, and cooling to obtain the needle coke.
The homogenizing agent in the step (2) of the comparative example is vacuum residue asphalt, and the content of asphalt in the vacuum residue asphalt is 40 wt%; the co-carbonizing agent was divinylbenzene, and the amount of the co-carbonizing agent added was 10 wt%.
Comparative example 2
(1) Distilling 2.5 kg of medium and low temperature coal tar in a distillation reactor, and distilling>Preparing refined raw materials from medium and low temperature coal tar at 250 ℃; the softening point of the low-temperature coal tar in the narrow fraction is 40 ℃, and the aromatic degree fAIs 0.4;
(2) compounding the refined raw material prepared in the step (1) with a homogenizing agent according to the proportion of 1:1, adding a co-carbonizing agent, and modifying asphalt to prepare a co-carbonized ternary system;
(3) taking nitrogen as a protective gas, heating the co-carbonization ternary system prepared in the step (2) to 300 ℃ in a high-pressure reaction kettle under the conditions of a heating rate of 6 ℃/min, a stirring rate of 150r/min and a pressure of 3MPa, and keeping the constant temperature for 3 hours; then heating to 500 ℃ under the conditions that the heating rate is 2 ℃/min, the stirring rate is 100r/min and the pressure is 1.5MPa, keeping the temperature for 8 hours at constant temperature, and finally decompressing to prepare a semicoke mixture;
(4) and (3) calcining the semicoke mixture prepared in the step (3) in a calcining furnace for 5 hours at 1450 ℃ by taking nitrogen as a protective gas, and cooling to obtain the needle coke.
The homogenizing agent in the step (2) of the comparative example is vacuum residue asphalt, and the content of asphalt in the vacuum residue asphalt is 40 wt%; the co-carbonizing agent was divinylbenzene, and the amount of the co-carbonizing agent added was 10 wt%.
Comparative example 3
(1) Distilling 2.5 kg of medium and low temperature coal tar in a distillation reaction kettle, and distilling the medium and low temperature coal tar with the distillate at 330-420 ℃ to prepare a refined raw material; the softening point of the low-temperature coal tar in the narrow fraction is 40 ℃, and the aromatic degree fAIs 0.4;
(2) compounding the refined raw material prepared in the step (1) with a homogenizing agent according to the proportion of 1:1, adding a co-carbonizing agent, and modifying asphalt to prepare a co-carbonized ternary system;
(3) taking nitrogen as a protective gas, heating the co-carbonization ternary system prepared in the step (2) to 300 ℃ in a high-pressure reaction kettle under the conditions of a heating rate of 6 ℃/min, a stirring rate of 150r/min and a pressure of 3MPa, and keeping the constant temperature for 3 hours; then heating to 500 ℃ under the conditions that the heating rate is 2 ℃/min, the stirring rate is 100r/min and the pressure is 1.5MPa, keeping the temperature for 8 hours at constant temperature, and finally decompressing to prepare a semicoke mixture;
(4) and (3) calcining the semicoke mixture prepared in the step (3) in a calcining furnace for 5 hours at 1450 ℃ by taking nitrogen as a protective gas, and cooling to obtain the needle coke.
The homogenizing agent in the step (2) of the comparative example is vacuum residue asphalt, and the content of asphalt in the vacuum residue asphalt is 40 wt%; the co-carbonizing agent was divinylbenzene, and the amount of the co-carbonizing agent added was 2 wt%.
Comparative example 4
(1) Distilling 2.5 kg of medium and low temperature coal tar in a distillation reaction kettle, and distilling the medium and low temperature coal tar with the distillate at 330-420 ℃ to prepare a refined raw material; the softening point of the low-temperature coal tar in the narrow fraction is 40 ℃, and the aromatic degree fAIs 0.4;
(2) compounding the refined raw material prepared in the step (1) with a homogenizing agent according to the proportion of 1:1, adding a co-carbonizing agent, and modifying asphalt to prepare a co-carbonized ternary system;
(3) taking nitrogen as a protective gas, heating the co-carbonization ternary system prepared in the step (2) to 300 ℃ in a high-pressure reaction kettle under the conditions of a heating rate of 6 ℃/min, a stirring rate of 150r/min and a pressure of 3MPa, and keeping the constant temperature for 3 hours; then heating to 500 ℃ under the conditions that the heating rate is 2 ℃/min, the stirring rate is 100r/min and the pressure is 1.5MPa, keeping the temperature for 8 hours at constant temperature, and finally decompressing to prepare a semicoke mixture;
(4) and (3) calcining the semicoke mixture prepared in the step (3) in a calcining furnace for 5 hours at 1450 ℃ by taking nitrogen as a protective gas, and cooling to obtain the needle coke.
The homogenizing agent in the step (2) of the comparative example is vacuum residue asphalt, and the content of asphalt in the vacuum residue asphalt is 40 wt%; the co-carbonizing agent was divinylbenzene, and the amount of the co-carbonizing agent added was 40 wt%.
Comparative example 5
(1) Distilling 2.5 kg of medium and low temperature coal tar in a distillation reaction kettle, and distilling the medium and low temperature coal tar with the distillate at 330-420 ℃ to prepare a refined raw material; the softening point of the low-temperature coal tar in the narrow fraction is 40 ℃, and the aromatic degree fAIs 0.4;
(2) compounding the refined raw material prepared in the step (1) with a homogenizing agent according to the proportion of 1:5, adding a co-carbonizing agent, and modifying asphalt to prepare a co-carbonized ternary system;
(3) taking nitrogen as a protective gas, heating the co-carbonization ternary system prepared in the step (2) to 300 ℃ in a high-pressure reaction kettle under the conditions of a heating rate of 6 ℃/min, a stirring rate of 150r/min and a pressure of 3MPa, and keeping the constant temperature for 3 hours; then heating to 500 ℃ under the conditions that the heating rate is 2 ℃/min, the stirring rate is 100r/min and the pressure is 1.5MPa, keeping the temperature for 8 hours at constant temperature, and finally decompressing to prepare a semicoke mixture;
(4) and (3) calcining the semicoke mixture prepared in the step (3) in a calcining furnace for 5 hours at 1450 ℃ by taking nitrogen as a protective gas, and cooling to obtain the needle coke.
The homogenizing agent in the step (2) of the comparative example is vacuum residue asphalt, and the content of asphalt in the vacuum residue asphalt is 40 wt%; the co-carbonizing agent was divinylbenzene, and the amount of the co-carbonizing agent added was 10 wt%.
Comparative example 6
(1) Distilling 2.5 kg of medium and low temperature coal tar in a distillation reaction kettle, and distilling the medium and low temperature coal tar with the distillate at the temperature of between 300 and 420 ℃ to prepare a refined raw material; the softening point of the medium-low temperature coal tar of the fraction at 300-420 ℃ is 40 ℃, and the aromaticity fAIs 0.4;
(2) compounding the refined raw material prepared in the step (1) with a homogenizing agent according to the proportion of 1:1, adding a co-carbonizing agent, and modifying asphalt to prepare a co-carbonized ternary system;
(3) taking nitrogen as a protective gas, heating the co-carbonization ternary system prepared in the step (2) to 350 ℃ in a high-pressure reaction kettle under the conditions of a heating rate of 6 ℃/min, a stirring rate of 150r/min and a pressure of 4MPa, and keeping the constant temperature for 3 hours; then under the conditions that the heating rate is 2 ℃/min, the stirring rate is 100r/min and the pressure is 4MPa, heating to 500 ℃, keeping the constant temperature for 8 hours, and finally decompressing to prepare a semicoke mixture;
(4) and (3) taking nitrogen as a protective gas, heating the semicoke mixture prepared in the step (3) to 1600 ℃ in a calcining furnace under the conditions that the heating rate is 5 ℃/min and the constant pressure is 0.02MPa, calcining for 5h, and cooling to obtain the needle coke.
The homogenizing agent in the step (2) of the comparative example is vacuum residue asphalt, and the content of asphalt in the vacuum residue asphalt is 40 wt%; the co-carbonizing agent was divinylbenzene, and the amount of the co-carbonizing agent added was 10 wt%.
Table 1 shows the yield and material properties of needle coke prepared by adding different proportions of homogenizing agents and different amounts of co-carbonizing agents to examples 1-6 and comparative examples 1-6.
TABLE 1
Figure BDA0002405159630000091
According to the regulations of GB/T32158-. The data of true density, resistivity and thermal expansion coefficient of the needle coke prepared in the examples 1 to 6 in the table 1 can be obtained, the needle coke obtained in the examples 1 to 6 is qualified, and the needle coke prepared in the comparative examples 1 to 6 is unqualified.
The intermediate phase in the table is a mixture formed by mixing the homogenizing agent and medium-low temperature coal tar, and the delta T80 ℃ is the temperature difference of 80% of intermediate phase conversion.
Comparing example 1 with examples 2 to 6, refined asphalt can be obtained: the homogenizing agent is 1:1, and when the adding amount of the co-carbonizing agent is 10 wt%, the yield of the needle coke is high; will carry outExamples 1-6 compared to comparative examples 1-6, the yield of needle coke prepared using the preparation method and operating parameter ranges of the present invention was higher, and the mesophase content was 100%, Δ T80℃The temperature is 30-60 ℃, the homogenizing agent and the co-carbonizing agent jointly promote the formation of a wide-area and ordered fibrous structure intermediate phase in the thermal polymerization process, the influence caused by the difference of thermal reactivity is avoided, the viscosity of the intermediate phase system is good, and needle coke with good fiber orientation and good order can be formed.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any equivalent modifications or substitutions made by those skilled in the art within the technical scope of the present invention should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (7)

1. A method for preparing needle coke by using medium-low temperature coal tar is characterized by comprising the following steps:
(1) distilling medium-low temperature coal tar in a rectification reaction kettle, and distilling medium-low temperature coal tar with the distillate of more than 300 ℃ to prepare a refined raw material;
(2) compounding the refined raw material prepared in the step (1) with a homogenizing agent according to the proportion of 1: 0.5-2, and then adding a co-carbonization agent to modify asphalt to prepare a co-carbonization ternary system;
(3) performing thermal polymerization reaction on the co-carbonized ternary system prepared in the step (2) in a high-pressure reaction kettle by taking nitrogen as a protective gas to prepare a semicoke mixture;
(4) taking nitrogen as a protective gas, heating the semicoke mixture prepared in the step (3) to 1300-1600 ℃ in a calcining furnace under the conditions of a heating rate of 2-7 ℃/min and a constant pressure, calcining for 2-5 h, and cooling to obtain needle coke;
the co-carbonization agent is one or a mixture of two or more of divinylbenzene, polystyrene and polyethylene.
2. The method for preparing needle coke using medium and low temperature coal tar as claimed in claim 1, wherein the thermal polymerization step in the step (3) is: heating the co-carbonization ternary system prepared in the step (2) to 200-350 ℃ in a high-pressure reaction kettle under the conditions that the heating rate is 2-8 ℃/min, the stirring rate is 100-200 r/min and the pressure is 1-5 MPa, and keeping the constant temperature for 1-3 h; and then heating to 300-500 ℃ under the conditions that the heating rate is 0.5-3 ℃/min, the stirring rate is 50-150 r/min and the pressure is 0-3 MPa, keeping the temperature for 7-9 h at a constant temperature, and finally relieving the pressure to prepare a semicoke mixture.
3. The method for preparing needle coke from medium and low temperature coal tar according to claim 1, wherein the co-carbonization agent is added in an amount of 5 to 25 wt%.
4. The method for preparing needle coke from medium and low temperature coal tar as claimed in claim 1, wherein the homogenizing agent is one of vacuum residue asphalt, petroleum asphalt or high temperature tar asphalt.
5. The method for preparing needle coke using middle and low temperature coal tar according to claim 4, wherein the content of pitch in the vacuum residue pitch, petroleum pitch and high temperature tar pitch is 30 wt% to 50 wt%.
6. The method for preparing needle coke using middle and low temperature coal tar as claimed in claim 1, wherein the middle and low temperature coal tar of the fraction >300 ℃ is narrow fraction middle and low temperature coal tar of the fraction between 300 ℃ and 400 ℃.
7. The method for preparing needle coke from medium-low temperature coal tar as claimed in claim 6, wherein the softening point of the medium-low temperature coal tar in the narrow fraction is 20-70 ℃, and the aromaticity f isA0.3 to 0.5.
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