Search

CN-118620644-B - Production method of high-strength high-specific-capacitance cathode material needle coke

CN118620644BCN 118620644 BCN118620644 BCN 118620644BCN-118620644-B

Abstract

The invention discloses a production method of high-strength high-specific-capacitance cathode material needle coke, which at least comprises the following steps of introducing four different materials into a coke tower in sequence, namely a material A, a material B, a material C and a material D, wherein the material A has the characteristics of PDQI percent of value, less than 7, sulfur content less than 1.0 percent, preferably 0-0.5 percent, 5 percent of distillation point temperature of 350-430 ℃, preferably 360-400 ℃,95 percent of distillation point temperature of 450-550 ℃, preferably 480-530 ℃, the material B has the characteristics of PDQI percent of value of 3-6,5 percent of distillation point temperature of 340-400 ℃, preferably 350-380 ℃, and 95 percent of distillation point temperature of 440-540 ℃, preferably 460-500 ℃, and sulfur content less than 1.0%, preferably 0-0.5 percent. The method can prepare the needle coke of the high-strength high-specific-capacitance cathode material.

Inventors

  • CHU RENQING
  • HOU SHUANDI
  • GUO DAN
  • WU YUN
  • ZHANG YUANYUAN

Assignees

  • 中国石油化工股份有限公司
  • 中石化（大连）石油化工研究院有限公司

Dates

Publication Date
20260505
Application Date
20230308

Claims (19)

  1. 1. A production method of high-strength high-specific capacitance cathode material needle coke is characterized by at least introducing four different materials into a coke tower in sequence, namely a material A, a material B and a material D, wherein the material A has the properties of PDQI percent of temperature ranging from about 7 to about 1.0 percent, 5 percent of distillation temperature ranging from about 350 ℃ to about 430 ℃ and 95 percent of distillation temperature ranging from about 450 ℃ to about 550 ℃, the material B has the properties of PDQI percent of temperature ranging from about 3 to about 6,5 percent of distillation temperature ranging from about 340 ℃ to about 400 ℃,95 percent of distillation temperature ranging from about 440 ℃ to about 540 ℃, the material has the properties of sulfur content ranging from about 1.0 percent, PDQI percent of distillation temperature ranging from about 300 ℃ to about 380 ℃,95 percent of distillation temperature ranging from about 400 ℃ to about 520 ℃, the sulfur content no more than about 1.0 percent, and the material D has the properties of PDQI percent of temperature ranging from about 1 to about 3,5 percent of distillation temperature ranging from about 400 ℃ to about 350 ℃ and no more than about 450 ℃, and the material D has the properties of sulfur content ranging from about PDQI percent of temperature ranging from about 1 to about 3,5 percent of distillation temperature ranging from about 250 ℃ to about 350 ℃ to about 5 ℃ to about 450 ℃. The operation conditions of introducing the material A are as follows, the outlet temperature of the heating furnace is 450-580 ℃, and the pressure of the coke tower is 0.1-2.0MPa; the operation conditions of introducing the material B are that the outlet temperature of the heating furnace is 440-550 ℃, and the pressure of the coke tower is 0.1-2.0MPa; the outlet temperature of a heating furnace of the coking device for introducing the material B is 5-80 ℃ lower than that of a heating furnace of the coking device for introducing the material A; the material A is obtained by hydrotreating a fresh raw material, the material B is a low-sulfur and low-nitrogen raw material which is not hydrotreated, the material C is coked heavy distillate oil, and the material D is coked light distillate oil.
  2. 2. The process of claim 1, wherein the material A has a sulfur content of 0 to 0.5%, a 5% distillation temperature of 360 to 400 ℃ and a 95% distillation temperature of 480 to 530 ℃, the material B has a 5% distillation temperature of 350 to 380 ℃ and a 95% distillation temperature of 460 to 500 ℃ and a sulfur content of 0 to 0.5%, the material C has a 5% distillation temperature of 340 to 360 ℃, a 95% distillation temperature of 410 to 460 ℃ and a sulfur content of 0 to 0.5%, and the material D has a PDQI value of 1 to 3 and a 5% distillation temperature of 250 to 300 ℃ and a 95% distillation temperature of 350 to 400 ℃ and a sulfur content of 0 to 1.0%.
  3. 3. The method of claim 1, wherein the solids content of the materials A, B, C and D is 0-500 μg/g.
  4. 4. The method of claim 3, wherein the solid content of the material A, the material B, the material C and the material D is 0-200 mug/g.
  5. 5. The method of claim 3, wherein the solid content of the material A, the material B, the material C and the material D is 0-100 mug/g.
  6. 6. The method according to claim 1, wherein the total time for introducing four different materials is T, T ranges from 24 to 72 hours, the time for introducing material A is 10 to 50 percent of the total time, the time for introducing material B is 15 to 50 percent of the total time, the time for introducing material C is 10 to 40 percent of the total time, and the time for introducing material D is 5 to 30 percent of the total time.
  7. 7. The method of claim 6, wherein the total time for introducing four different materials is T, T ranges from 36 to 56 hours, the time for introducing material A is 30 to 50 percent of the total time, the time for introducing material B is 15 to 40 percent of the total time, the time for introducing material C is 15 to 35 percent of the total time, and the time for introducing material D is 5 to 15 percent of the total time.
  8. 8. The process of claim 1, wherein the feed A is introduced at a furnace exit temperature of from 460℃to 550℃and a coke drum pressure of from 0.5 to 1.0MPa.
  9. 9. The process according to claim 1, wherein the feed B is introduced under such operating conditions that the furnace outlet temperature is from 450 to 530℃and the coke drum pressure is from 0.5 to 1.0MPa.
  10. 10. The method of claim 1 wherein the outlet temperature of the furnace from which material B is introduced into the coker is 10-50 ℃ lower than the outlet temperature of the furnace from which material A is introduced into the coker.
  11. 11. The process of claim 1, wherein the feed C is introduced at a furnace exit temperature of 450 ℃ to 550 ℃ and a coke drum pressure of 0.1 MPa to 1.0MPa.
  12. 12. The method of claim 11, wherein the feed C is introduced at a furnace exit temperature of 480 ℃ to 530 ℃ and a coke drum pressure of 0.3MPa to 0.6MPa.
  13. 13. The process of claim 1, wherein the feed D is introduced at a furnace exit temperature of 450-550℃and a coke drum pressure of 0.1-0.6MPa.
  14. 14. The method of claim 13, wherein the feed D is introduced at a furnace exit temperature of 480 ℃ to 530 ℃ and a coke drum pressure of 0.1 MPa to 0.3MPa.
  15. 15. The method of claim 1, wherein the sequencing is performed sequentially or at intervals, the sequencing means that in one operation period of a certain coke, the operation period means that the raw materials are introduced until the coke is removed, and four different materials are repeatedly introduced sequentially in the next period.
  16. 16. The method according to claim 1, wherein the mass ratio of the material A, the material B, the material C and the material D introduced in one operation period is 1:0.5-1.5:0.5-4.0:0.1-0.6.
  17. 17. The method of claim 1, wherein one or more coke drums are arranged alternately, in particular N coke drums, N being an integer greater than 1.
  18. 18. The method of claim 1, wherein the specific preparation method of the needle coke of the high-strength high-specific-capacitance anode material comprises the following steps: (1) The fresh raw materials enter a hydrogenation fractionating tower after passing through a hydrogenation treatment device, and at least a material A is separated; (2) The material A is heated by a heating furnace and then enters a coke tower for charging, oil gas generated by the reaction is discharged from the top of the coke tower and enters a coking fractionation tower, and at least heavy distillate oil of coking of the material C and light distillate oil of coking of the material D are separated; (3) Switching the material A in the step (2) into the material B to continuously charge the coke tower; (4) In the step (3), the material B is switched to the material C in the step (2), and the heavy distillate oil is coked to continuously charge the coke tower; (5) In the step (4), the coking heavy distillate oil is switched into the material D in the step (2), and the coking light distillate oil is continuously charged into the coke tower; (6) And (3) after the coke tower is charged with the coking light distillate, carrying out small blowing, large blowing and decoking operation on the coke tower, and discharging needle coke products from the tower bottom.
  19. 19. The method according to claim 1 or 18, wherein the mass ratio of the material A, the material B, the material C and the material D introduced in one operation period is 1:0.5-1.5:0.5-4.0:0.1-0.6.

Description

Production method of high-strength high-specific-capacitance cathode material needle coke Technical Field The invention relates to a method for producing high-strength high-specific-capacitance cathode material needle coke, in particular to a method for producing high-strength high-specific-capacitance cathode material needle coke by adopting petroleum or coal raw materials. Background Needle coke is an excellent carbon product, has obvious streamline texture structure when seen from the outside, and is a main raw material for manufacturing the ultra-high power graphite electrode for steelmaking due to good electric conductivity, orientation and heat conduction performance. The ultra-high power electrode is adopted for steelmaking, the smelting time can be shortened by about 2/3, the electricity consumption can be reduced by about 50%, and the economic benefit is obvious. With the rapid development of new energy automobiles in recent years, the requirements of power batteries are greatly increased, the negative electrode materials of lithium batteries are divided into carbon materials and non-carbon materials, the carbon materials mainly comprise artificial graphite materials, and the artificial graphite negative electrode materials produced by needle coke have excellent graphitization degree and first discharge specific capacity index, so that the negative electrode materials are widely applied to high-end graphite negative electrode material products. CN202011305509.9 discloses a method and a process system for producing needle coke by using heavy oil, wherein the method comprises a component cutting process, a hydrogenation process, a mixing process and a delayed coking process, wherein the heavy oil is used as a raw material and is cut into light distillate, heavy distillate and tailings, the heavy distillate is subjected to hydrogenation treatment to obtain hydrogenation heavy distillate, the hydrogenation heavy distillate is mixed with the light distillate to obtain mixed oil, and the mixed oil is subjected to delayed coking treatment to obtain the needle coke. US4894144 discloses a method for preparing needle coke and high sulfur petroleum coke simultaneously, which adopts a hydrotreating process to pretreat straight-run heavy oil, the hydrogenated residual oil is divided into two parts, and the two parts are respectively coked and then satin fired to prepare the needle coke and the high sulfur petroleum coke US5286371 also discloses a straight-run residuum hydrotreating process, wherein the hydrogenation reaction temperature is 379-480 ℃, the reaction pressure is 6.8MPa-34.4MPa, the treated heavy residuum and the catalytically cracked clear oil are mixed and enter a solvent deasphalting device, and the material flow after asphalt removal is used as the raw material of needle coke. US4178229 discloses a method for producing high quality petroleum coke from straight-run vacuum residuum by converting the vacuum residuum into distillate oil and asphalt, and further cracking the asphalt and hydrogen donor to produce raw materials of high quality coke. The invention discloses a method for preparing needle coke for ultra-high power electrode by using heavy oil, which comprises the steps of taking heavy oil as a raw material, adopting a size exclusion separation method, taking polystyrene as a packing of a separation column, separating out components with specific molecular volume with relative molecular mass distribution of 400-1000, respectively removing acidic components and alkaline components in the components by ion exchange chromatography to obtain neutral raw materials, and preparing the needle coke by two sections of continuous carbonization processes of the treated raw materials. Before 2017, needle coke is mainly used as graphite electrode aggregate to produce HP and UHP graphite electrodes, the main indexes pursued by needle coke products are low thermal expansion coefficients and ordered structures, along with the rapid development of the electric automobile industry in recent years, the needle coke is widely applied to the lithium ion battery anode material industry, the pursued goal is that the needle coke products have higher first discharge specific capacity, the needle coke preparation process in the prior art is mostly designed for the purpose of producing graphite electrode needle coke, and if the needle coke is required to be produced as the anode material, the strength coefficient of the needle coke products needs to be further improved and optimized in the aspect of the first discharge specific capacity. Disclosure of Invention Aiming at the defects of the prior art, the invention provides a production method of high-strength high-specific capacitance cathode material needle coke. A process for preparing needle coke with high strength and high specific capacitance includes such steps as sequentially introducing four different materials including material A, material B, and material D,