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CN111925816A - Production method of low CTE coal-series needle coke - Google Patents

Production method of low CTE coal-series needle coke Download PDF

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Publication number
CN111925816A
CN111925816A CN202010713695.3A CN202010713695A CN111925816A CN 111925816 A CN111925816 A CN 111925816A CN 202010713695 A CN202010713695 A CN 202010713695A CN 111925816 A CN111925816 A CN 111925816A
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CN
China
Prior art keywords
needle coke
coal
fractionating tower
tower
calcination
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202010713695.3A
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Chinese (zh)
Inventor
徐金城
彭莉
廖虎
韩照宪
岳远会
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Shandong Yida New Material Co Ltd
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Shandong Yida New Material Co Ltd
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Priority to CN202010713695.3A priority Critical patent/CN111925816A/en
Publication of CN111925816A publication Critical patent/CN111925816A/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B55/00Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Coke Industry (AREA)

Abstract

The invention belongs to the technical field of needle coke preparation, and particularly relates to a production method of low CTE coal-based needle coke, which comprises the following steps: the coal tar soft pitch enters a needle coke raw material groove, is pumped out by a pump, is heated by a raw material heating furnace and then enters a fractionating tower; heating carrier gas in a carrier gas heating furnace and then feeding the heated carrier gas into a fractionating tower; the coal tar soft pitch entering the fractionating tower exchanges heat with carrier gas, circulating oil in the fractionating tower is pumped out from the bottom of the fractionating tower by a pump and sent to a raw material heating furnace for heating, then enters a coking tower A or a coking tower B which alternately operates, generated oil gas enters the fractionating tower, and green coke is obtained at the bottom; putting the raw coke into a rotary kiln for primary calcination, and performing primary cooling after the calcination; and after cooling, the mixture enters a rotary kiln for secondary calcination, and after calcination, the mixture is cooled for the second time to obtain the finished needle coke. The whole coking production of the invention is more stable, and compared with the coal-based needle coke produced by the traditional production method, the CTE value of the coal-based needle coke of the invention is reduced by 5-10%.

Description

Production method of low CTE coal-series needle coke
Technical Field
The invention belongs to the technical field of needle coke preparation, and particularly relates to a production method of low CTE coal-based needle coke.
Background
The needle coke is a high-quality variety developed greatly in carbon materials, has optical anisotropy and a good streamline needle-shaped crystalline carbon structure, and the particles of the needle coke are slender after being crushed, so that the needle coke is mainly used as a raw material for producing high-end carbon products such as ultrahigh-power electrodes, special carbon materials, carbon fibers and composite materials thereof. The needle coke is divided into coal-based needle coke and oil-based needle coke according to the difference of raw materials for producing the needle coke, the needle coke produced by taking heavy oil generated by secondary processing of petroleum as the raw material is called petroleum-based needle coke, and the needle coke produced by taking coal tar heavy fraction and coal pitch as the raw materials is called coal-based needle coke.
In the prior art of the prior art for preparing coal-based needle coke, most of the oil gas in the front tower is used for preheating coking, and the oil gas is supposed to enter the fractionating tower and provide heat for the fractionating tower, but if the oil gas is preheated in the coking tower, the amount of the oil gas entering the fractionating tower is reduced, so that the heat balance of the fractionating tower is damaged, and the operation of the fractionating tower is fluctuated.
For the calcination of petroleum coke, the conventional rotary kiln calcination process is as follows: the green coke is quickly fed into the kiln body at 1200 deg.C from normal temp. by means of feeding slide pipe, and its time only needs several seconds, then it is rotated along with kiln body, and reaches calcining zone, and continuously transferred to kiln head, and fed into cooling kiln, and the water is sprayed in the cooling kiln to directly cool it. The traditional rotary kiln calcination has the problems of low yield of needle coke, such as the yield of 70-75 percent, poor granularity of calcined coke and the like.
In addition, the preparation process of the coal-based needle coke of each manufacturer belongs to a confidential state or is protected by a patent, and the preparation cost is relatively high, the yield is relatively low, so that the preparation process is not beneficial to the current intense market competition.
Disclosure of Invention
The invention provides a method for producing low CTE coal-series needle coke, aiming at the problems that the pressure and temperature of a fractionating tower are easy to fluctuate, the collection rate of the coal-series needle coke is low, and the granularity of calcined coke is poor in the prior art.
The invention provides a production method of low CTE coal-series needle coke, comprising the following steps:
a. the refined coal tar soft pitch enters a needle coke raw material tank, is pumped out by a pump, is heated by a convection section at the upper part of a raw material heating furnace and then enters the bottom of a fractionating tower; heating carrier gas in a carrier gas heating furnace and then feeding the heated carrier gas into a fractionating tower;
b. the refined coal tar soft pitch entering the fractionating tower exchanges heat with carrier gas entering the fractionating tower, circulating oil at the bottom of the fractionating tower is pumped out from the bottom of the fractionating tower by a pump and is sent to a raw material heating furnace, the circulating oil is heated by a middle radiation section of the raw material heating furnace and then enters a coking tower A or a coking tower B, the coking tower A and the coking tower B alternately operate, generated oil gas enters the fractionating tower, and raw coke is obtained at the bottom of the fractionating tower;
c. putting the raw coke into a rotary kiln for primary calcination, and performing primary cooling after the calcination; and after cooling, the mixture enters the rotary kiln again for secondary calcination, and after calcination, the mixture is cooled for the second time to obtain the finished needle coke.
Further, the carrier gas is one of dry coking gas, steam and inert gas.
Further, the heating furnace is a gas furnace or an electric furnace.
Further, the primary cooling and the secondary cooling are both cooled in a built-in water-cooled wall mode.
Further, in the step a, the temperature of the raw material heating furnace is 450-550 ℃.
Further, in the step b, the temperature of the top of the fractionating tower is 150-; the temperature of the top of the coking tower A or B is 420-480 ℃, and the pressure of the top of the coking tower A or B is 0.2-1.0 MPa.
Further, in the step c, the indoor calcining temperature is 750-850 ℃ and the indoor pressure is-20 to-50 Pa when the rotary kiln is used for primary calcining; when the rotary kiln is used for secondary calcination, the indoor calcination temperature is 1350-; the discharge temperature after the secondary cooling is less than 80 ℃.
A low CTE coal-based needle coke produced by the above production processDensity > 2.13g/cm3
The invention has the beneficial effects that:
compared with the prior art, the production method of the coal-based needle coke adds the carrier gas and the carrier gas heating furnace, the carrier gas is used for preheating the coking tower at the initial stage and controlling the heat treatment at the later stage of coke formation, the pressure and temperature fluctuation of the fractionating tower is reduced, the temperature fluctuation of the raw material fed into the coking tower is reduced, and the coking production is stabilized; compared with the one-time calcination in the prior art, the method provided by the invention has the advantages that the green coke is calcined twice, the first-stage medium-temperature calcination mainly removes volatile components, the first-stage cooling is favorable for the construction of a microcrystal basic structure, and the second-stage high-temperature calcination mainly removes partial heteroatoms, so that the rearrangement of the coke interlayer structure is favorable.
The coal-based needle coke obtained by the method has good coke granularity and the true density is more than 2.13g/cm3The CTE value is 0.6E-6/DEG C-1.1E-6/DEG C, compared with the coal-based needle coke produced by the traditional production method, the CTE value of the coal-based needle coke is reduced by 5-10%, and the technical requirement for manufacturing high-power electrodes is met.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The production method of the low CTE coal-based needle coke provided by the embodiment of the invention comprises the following steps:
a. the refined coal tar soft pitch enters a needle coke raw material tank, is pumped out by a pump, is heated by a convection section at the upper part of a raw material heating furnace and then enters the bottom of a fractionating tower; and the carrier gas is heated by a carrier gas heating furnace and then enters the fractionating tower. Wherein the temperature of the raw material heating furnace is 500 ℃; the heating furnace is an electric furnace, and the carrier gas is coking dry gas.
b. The refined coal tar soft pitch entering the fractionating tower exchanges heat with the carrier gas entering the fractionating tower, the circulating oil at the bottom of the fractionating tower is pumped out from the bottom of the fractionating tower by a pump and is sent to the raw material heating furnace, the circulating oil is heated by the middle radiation section of the raw material heating furnace and then enters the coking tower A or the coking tower B, the coking tower A and the coking tower B alternately operate, the generated oil gas enters the fractionating tower, and the raw coke is obtained at the bottom. Wherein the top temperature of the fractionating tower is 180 ℃, and the top pressure of the fractionating tower is 0.4 MPa; the temperature of the top of the coking tower A or B is 450 ℃, and the pressure of the top of the coking tower A or B is 0.7 MPa.
c. Putting the raw coke into a rotary kiln for primary calcination, and performing primary cooling after the calcination; and after cooling, the mixture enters the rotary kiln again for secondary calcination, and after calcination, the mixture is cooled for the second time to obtain the finished needle coke. Wherein, the indoor calcining temperature is 790 ℃ and the indoor pressure is-30 Pa during the primary calcining of the rotary kiln; when the rotary kiln is used for secondary calcination, the indoor calcination temperature is 1380 ℃, and the indoor pressure is-13 Pa; the primary cooling and the secondary cooling are both cooled in a built-in water-cooled wall mode, and the discharge temperature after the secondary cooling is 75 ℃.
The low CTE coal-series needle coke prepared by the production method has the true density of 2.14g/cm through detection3The CTE value is 0.8E-6/DEG C, the technical index of the superior coal-based needle coke is met, and the technical requirement for manufacturing a high-power electrode is met.
Example 2
The production method of the low CTE coal-based needle coke provided by the embodiment of the invention comprises the following steps:
a. the refined coal tar soft pitch enters a needle coke raw material tank, is pumped out by a pump, is heated by a convection section at the upper part of a raw material heating furnace and then enters the bottom of a fractionating tower; and the carrier gas is heated by a carrier gas heating furnace and then enters the fractionating tower. Wherein the temperature of the raw material heating furnace is 490 ℃; the heating furnace is an electric furnace, and the carrier gas is steam.
b. The refined coal tar soft pitch entering the fractionating tower exchanges heat with the carrier gas entering the fractionating tower, the circulating oil at the bottom of the fractionating tower is pumped out from the bottom of the fractionating tower by a pump and is sent to the raw material heating furnace, the circulating oil is heated by the middle radiation section of the raw material heating furnace and then enters the coking tower A or the coking tower B, the coking tower A and the coking tower B alternately operate, the generated oil gas enters the fractionating tower, and the raw coke is obtained at the bottom. Wherein the temperature at the top of the fractionating tower is 200 ℃, and the top pressure of the fractionating tower is 0.3 MPa; the top temperature of the coking tower A or B is 460 ℃, and the top pressure of the coking tower A or B is 0.6 MPa.
c. Putting the raw coke into a rotary kiln for primary calcination, and performing primary cooling after the calcination; and after cooling, the mixture enters the rotary kiln again for secondary calcination, and after calcination, the mixture is cooled for the second time to obtain the finished needle coke. Wherein, the indoor calcining temperature is 800 ℃ and the indoor pressure is-35 Pa during the primary calcining of the rotary kiln; when the rotary kiln is used for secondary calcination, the indoor calcination temperature is 1400 ℃, and the indoor pressure is-15 Pa; the primary cooling and the secondary cooling are both cooled in a built-in water-cooled wall mode, and the discharge temperature after the secondary cooling is 78 ℃.
The low CTE coal-series needle coke prepared by the production method has the true density of 2.14g/cm through detection3The CTE value is 0.9E-6/DEG C, the technical index of the superior coal-based needle coke is met, and the technical requirement for manufacturing a high-power electrode is met.
Although the present invention has been described in detail by way of preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and the spirit of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (8)

1. A method for producing low CTE coal-based needle coke, characterized by comprising the following steps:
a. the refined coal tar soft pitch enters a needle coke raw material tank, is pumped out by a pump, is heated by a convection section at the upper part of a raw material heating furnace and then enters the bottom of a fractionating tower; heating carrier gas in a carrier gas heating furnace and then feeding the heated carrier gas into a fractionating tower;
b. the refined coal tar soft pitch entering the fractionating tower exchanges heat with carrier gas entering the fractionating tower, circulating oil at the bottom of the fractionating tower is pumped out from the bottom of the fractionating tower by a pump and is sent to a raw material heating furnace, the circulating oil is heated by a middle radiation section of the raw material heating furnace and then enters a coking tower A or a coking tower B, the coking tower A and the coking tower B alternately operate, generated oil gas enters the fractionating tower, and raw coke is obtained at the bottom of the fractionating tower;
c. putting the raw coke into a rotary kiln for primary calcination, and performing primary cooling after the calcination; and after cooling, the mixture enters the rotary kiln again for secondary calcination, and after calcination, the mixture is cooled for the second time to obtain the finished needle coke.
2. The method of claim 1, wherein the carrier gas is one of dry coke gas, steam, and inert gas.
3. The method of claim 1, wherein said furnace is a gas furnace or an electric furnace.
4. The method of claim 1, wherein the primary cooling and the secondary cooling are both cooled by built-in water walls.
5. The method for producing low CTE coal-based needle coke as claimed in claim 1, wherein the temperature of the raw material heating furnace in the step a is 450 ℃ to 550 ℃.
6. The method for producing coal-based needle coke with low CTE according to claim 1, wherein in the step b, the temperature at the top of the fractionating tower is 150 ℃ and 200 ℃, and the pressure at the top of the fractionating tower is 0.1-0.5 MPa; the temperature of the top of the coking tower A or B is 420-480 ℃, and the pressure of the top of the coking tower A or B is 0.2-1.0 MPa.
7. The method for producing coal-based needle coke with low CTE according to claim 1, wherein in the step c, the indoor calcining temperature is 750-850 ℃ and the indoor pressure is-20 to-50 Pa during the primary calcining in the rotary kiln; when the rotary kiln is used for secondary calcination, the indoor calcination temperature is 1350-; after secondary cooling, the discharge temperature is less than 80 ℃.
8. The low CTE coal-based needle coke produced by the production process of claim 1, wherein the coal-based needle coke has a true density of > 2.13g/cm3
CN202010713695.3A 2020-07-22 2020-07-22 Production method of low CTE coal-series needle coke Pending CN111925816A (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1290234A (en) * 1969-05-26 1972-09-20
CN1145089A (en) * 1994-04-07 1997-03-12 新日铁化学株式会社 Needle coke for graphite electrode and production method thereof
CN101254444A (en) * 2007-12-05 2008-09-03 南京大学 A catalytic reaction, rectification integrated process and its special equipment
CN101724419A (en) * 2008-10-28 2010-06-09 中国石油化工股份有限公司 Method for producing needle coke by utilizing delay coking of coal tar
CN104383704A (en) * 2014-09-19 2015-03-04 燕山大学 Step heating method and heating system for preheating of gas fractionating tower inlet material
CN105778957A (en) * 2014-12-17 2016-07-20 上海宝钢化工有限公司 Charring method for coal-based needle coke production
CN106635102A (en) * 2016-12-09 2017-05-10 山东益大新材料有限公司 Process for producing negative electrode material coke by taking supercritical extraction oil slurry as raw material and application of process
CN108587661A (en) * 2018-07-09 2018-09-28 鞍山兴德工程技术有限公司 A kind of device and method preparing needle coke based on delay coking process

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1290234A (en) * 1969-05-26 1972-09-20
CN1145089A (en) * 1994-04-07 1997-03-12 新日铁化学株式会社 Needle coke for graphite electrode and production method thereof
CN101254444A (en) * 2007-12-05 2008-09-03 南京大学 A catalytic reaction, rectification integrated process and its special equipment
CN101724419A (en) * 2008-10-28 2010-06-09 中国石油化工股份有限公司 Method for producing needle coke by utilizing delay coking of coal tar
CN104383704A (en) * 2014-09-19 2015-03-04 燕山大学 Step heating method and heating system for preheating of gas fractionating tower inlet material
CN105778957A (en) * 2014-12-17 2016-07-20 上海宝钢化工有限公司 Charring method for coal-based needle coke production
CN106635102A (en) * 2016-12-09 2017-05-10 山东益大新材料有限公司 Process for producing negative electrode material coke by taking supercritical extraction oil slurry as raw material and application of process
CN108587661A (en) * 2018-07-09 2018-09-28 鞍山兴德工程技术有限公司 A kind of device and method preparing needle coke based on delay coking process

Non-Patent Citations (1)

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Title
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