CN104232143A - Process of producing needle coke - Google Patents
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- CN104232143A CN104232143A CN201310231391.3A CN201310231391A CN104232143A CN 104232143 A CN104232143 A CN 104232143A CN 201310231391 A CN201310231391 A CN 201310231391A CN 104232143 A CN104232143 A CN 104232143A
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Abstract
The invention provides a process of producing needle coke and belongs to the technical field of needle coke preparation. The method includes following steps of: (1) uniformly mixing coal tar pitch and free carbon or a component containing the free carbon, and heating and reacting at 320-360 DEG C to obtain modified pitch; (2) uniformly mixing the modified pitch and a solvent to obtain a mixed solution, and removing insoluble substances in the mixed solution by utilization of a physical separation method; (3) separating the clear solution obtained after the insoluble substances are removed, and separating the solvent in the clear liquid to obtain a heavy distillate with low QI; (4) hydrogenating the heavy distillate under existence of a hydrogenating catalyst to obtain pitch that is a raw material of the needle coke; (5) subjecting the pitch that is the raw material of the needle coke to delayed coking to obtain green needle coke; and (6) calcinating the green needle coke in the step (5) to prepare the needle coke. The prepared needle coke has advantages of high yield and low coefficient of thermal expansion. The coefficient of thermal expansion of the prepared needle coke can be 0.8*10<-6>-1.3*10<-6> /DEG C.
Description
Technical field
The present invention relates to a kind of technique of producing needle coke, belong to needle coke preparing technical field.
Background technology
Needle coke is mainly used in the fields such as Electric furnace steel making Graphite Electrodes, lithium cell, nuclear power, space flight.Raw material difference according to producing needle coke is divided into coal-based needle coke and oil system needle coke needle coke.Wherein, coal-based needle coke raw material has coal tar, coal-tar pitch and by the obtained product liquid etc. of direct hydrogenation cracking coal.Containing a certain amount of quinoline insolubles in coal-based needle coke raw material, it is not only the decolorizing carbon that some macromolecule resin shape materials generate by thermopolymerization, also has the coal dust that brings with coal gas from carbonization chamber in coke furnace and coke powder etc., belongs to the impurity in needle-shape coke raw material.According to needle coke mechanism of coke formation, the formation of needle coke must the unstable mesophasespherule of experience formation, spherular growth and melt and be the formation of coalescence mesophase, the formation of fibrous texture form, namely generate needle coke.But containing in the raw material of impurity, after unstable mesophasespherule is formed, it runs into impurity carbon granules and just can not grow up and melt also, can not form the fibrous texture form of needle coke, and form the pattern structure of common Jiao, have a strong impact on needle coke quality after coking.
In order to production high-quality needle coke, purifying treatment must be carried out to coal-based needle coke raw material, to remove the objectionable impuritiess such as the quinoline insolubles of wherein obstruction microsphere growth.In current removing coal-based needle coke raw material, the method for the detrimental impurity such as quinoline insolubles mainly contains: solvent method, distillation method, centrifuging, upgrading method etc.Such as, Chinese patent literature CN1912053A discloses a kind of preparation method of coal-based needle coke, and specifically comprise with coal-tar pitch, coal tar, coal tar heavy duty fraction for raw material, first described raw material is modulated through mixed solvent groove; Again by tubular oven and refining plant, after making heating raw materials, through sedimentation, centrifugal, removed by filtration quinoline insolubles, be purified raw material; Described purification raw material in jug heater, 0.5 ~ 3.0MPa, at 350 ~ 530 DEG C through circulation polycondensation, react 5 ~ 18 hours, obtain polycondensation fine fodder; Described polycondensation fine fodder heats laggard coking tower again in tubular oven, under 0.5 ~ 3.5MPa, and coking 5 ~ 18h; Calcine in the needle coke heat release pot furnace of coking, form finished product.
Above-mentioned technology, in the process preparing needle coke, owing to adopting the method for solvent and thermal polycondensation to purify to raw material, eliminates the quinoline insolubles in raw material, makes the polycondensation fine fodder obtained have the low advantage of quinoline insolubles content.And then the quality product of the needle coke to prepare for raw material with this polycondensation fine fodder is also higher.But in above-mentioned technology, when purification raw material being carried out under 0.5 ~ 3.0MPa, 350 ~ 530 DEG C of conditions thermal polycondensation reaction, because the pressure and temperature of thermal polycondensation is higher, part benzene insoluble quinoline solvend (i.e. β resin) in raw material further polycondensation can form new quinoline insolubles, that is adopt the amount of β resin in the polycondensation fine fodder for preparing of aforesaid method can corresponding minimizing, and β resin is pitch prepares the effective constituent of needle coke, it not only can improve the yield of needle coke, can also reduce needle coke thermal expansivity.Because in the polycondensation fine fodder that aforesaid method prepares, the amount of β resin reduces relatively, and then make the yield of the needle coke adopting above-mentioned polycondensation fine fodder to prepare as raw material low, and the thermal expansivity of the needle coke prepared is large, has a strong impact on performance when needle coke uses as electrode.
Summary of the invention
Technical problem to be solved by this invention often adopts in needle coke preparation process in prior art under high-temperature condition, to carry out thermal polycondensation reaction to remove the quinoline insolubles in raw material, and the temperature of polycondensation is high that part β resin generation polycondensation in raw material can be caused to generate new quinoline insolubles, thus when causing using this polycondensation fine fodder to prepare needle coke, the productive rate of needle coke is low, the problem that thermal expansivity is large, and then a kind of technique of producing needle coke is provided, it is high that the needle coke using technique of the present invention to prepare has yield, the advantage that thermal expansivity is low.
In order to solve the problems of the technologies described above, the invention provides a kind of technique of producing needle coke, comprising the steps:
(1) coal-tar pitch is mixed with uncombined carbon or containing the component of uncombined carbon, under 320 ~ 360 DEG C of conditions, obtain modified pitch after reacting by heating;
(2) above-mentioned modified pitch and solvent are evenly obtained mixed solution, the method for employing physical sepn removes the insolubles in described mixed solution;
(3) clear liquor obtained after removing insolubles is separated, isolates the solvent in clear liquor, obtain the heavy ends of low QI;
(4) under hydrogenation catalyst existent condition, hydrotreatment is carried out to described heavy ends, obtain needle-shape coke raw material pitch;
(5) by delayed for above-mentioned needle-shape coke raw material pitch coking process, needle-like green coke is obtained;
(6) the needle-like green coke in step (5) is prepared needle coke through calcining.
In described step (1), in the quality of uncombined carbon, described uncombined carbon or containing the addition of the component of uncombined carbon and described coal-tar pitch than being 3:100 ~ 20:100.
In the quality of uncombined carbon, described uncombined carbon or containing the addition of the component of uncombined carbon and described coal-tar pitch than being 5:100 ~ 12:100.
In described step (1), the content of the described component Free Carbon containing uncombined carbon is 15 ~ 95wt%, and surplus is impurity.
In described step (1), the described component containing uncombined carbon obtains mixed solution after fully being mixed with solvent by coal-tar pitch, and then employing physical separation method removes the insolubles in described mixed solution, and this insolubles is the component containing uncombined carbon;
Wherein, described solvent is washing oil, absorb in oil, carbolineum or quinoline any one or a few, the mass ratio of described solvent and coal-tar pitch is 3 ~ 6.
In described step (1), described uncombined carbon is at 50 ~ 70 DEG C, obtain mixed solution by coal-tar pitch or after fully mixing with solvent containing the component of uncombined carbon, under 2000 ~ 3000G centrifugal force, be then separated the insolubles in the described mixed solution of removing, this insolubles is uncombined carbon;
Wherein, described solvent is washing oil, absorb in oil, carbolineum or quinoline one or more, described solvent and described coal-tar pitch or the mass ratio containing free carbon component are 8 ~ 10.
In described step (1), the described reacting by heating time is 5 ~ 8h.
In described step (2), described solvent is the mixture of coal measures lightweight oil and coal measures aromatic oil, or the mixture of BTX and coal measures aromatic oil, and the mass ratio of described coal measures lightweight oil or BTX and coal measures aromatic oil is 0.25-19; The mass ratio of described solvent and described pitch is 0.5-10.
Described coal measures lightweight oil is one or more in gas light oil, tar light oil, petroleum naphtha light oil, and described coal measures aromatic oil is washing oil, absorb oil, cresols is oily, one or more in carbolineum.
Hydrogenation catalyst in described step (4) is any one in Ni-Mo series catalysts or Ni-W series catalysts; The condition of described hydrotreatment is: temperature is 300 ~ 450 DEG C, and pressure is 5 ~ 20Mpa.
The present invention compared with prior art tool has the following advantages:
(1) technique of production needle coke of the present invention, first by adding uncombined carbon or the component containing uncombined carbon in feed coal tar-bitumen, heat-treat under the lower temperature conditions of 320 ~ 360 DEG C again, owing to adding uncombined carbon or the component containing uncombined carbon in raw material, make feed coal tar-bitumen can upgrading at a lower temperature, thus to make in raw material only xylene solubles generation polycondensation generate β resin, and polycondensation can not be there is further in β resin, be equivalent to the content that increase only β resin in the modified pitch obtained, when avoiding the pitch polycondensation upgrading occurred in prior art, β resin can form the shortcoming of new quinoline insolubles further, when again the modified pitch of this high β resin content being carried out separated from solvent, original quinoline insolubles in modified pitch and the uncombined carbon added or the component containing uncombined carbon can be removed, again hydrotreatment is carried out to the heavy ends after being separated and removing solvent and prepare needle coke material asphalt, in this material asphalt, β resin content is up to 32.19 ~ 35.93wt%, QI is low to moderate 0.01 ~ 0.06%, and the yield of material asphalt is up to 62.83 ~ 92.93wt%.With this material asphalt for after the delayed coking process of raw material, then carry out calcination processing, prepare needle coke finished product, this needle coke has the advantage that productive rate is high, thermal expansivity is low, and its thermal expansivity can be low to moderate 0.8 × 10
-6~ 1.3 × 10
-6/ DEG C.
(2) technique of production needle coke of the present invention, preferred in the quality of uncombined carbon further, described uncombined carbon or the component containing uncombined carbon are 3:100 ~ 20:100 with the ratio of described coal-tar pitch addition, the yield of the needle-shape coke raw material pitch prepared under this addition can reach 63.21 ~ 67.93wt%, in material asphalt, β resin content can up to 32.41 ~ 35.92wt%, and QI value can be reduced to 0.01 ~ 0.04wt%, with this material asphalt for after the delayed coking process of raw material, carry out calcination processing again, prepare needle coke finished product, it is high that this needle coke has productive rate, the advantage that thermal expansivity is low, and the thermal expansivity of needle coke can be low to moderate 0.8 × 10
-6~ 1.2 × 10
-6/ DEG C.
(3) technique of production needle coke of the present invention, preferred in the quality of uncombined carbon further, described uncombined carbon or the component containing uncombined carbon are 5:100 ~ 12:100 with the ratio of described coal-tar pitch addition, the yield of the needle-shape coke raw material pitch prepared under this addition can reach 66.58 ~ 67.93wt%, in material asphalt, β resin content can up to 35.34 ~ 35.92wt%, and QI value can be reduced to 0.01 ~ 0.02wt%, with this material asphalt for after the delayed coking process of raw material, carry out calcination processing again, prepare needle coke finished product, this needle coke has high productive rate, and thermal expansivity can be low to moderate 0.8 × 10
-6~ 1.0 × 10
-6/ DEG C, can 0.4 × 10 be reduced compared with the thermal expansivity of needle coke in prior art
-6~ 0.6 × 10
-6/ DEG C, there is the advantage of extremely low thermal expansivity.
Embodiment
Below in conjunction with embodiment, the present invention is further described in detail, but is not limited to this.
embodiment 1
(1) coal tar of 1000g is mixed with the uncombined carbon of 30g, under 360 DEG C of conditions, obtain modified pitch after reacting by heating 8h;
(2) above-mentioned modified pitch and solvent are evenly obtained mixed solution, under the centrifugal force of 1000g, carry out centrifugation remove insolubles in described mixed solution, wherein said solvent is gas light oil and the mixture absorbing oil, and described gas light oil is 19 with the mass ratio of absorption oil; The mass ratio of described solvent and described modified pitch is 10;
(3) clear liquor obtained after removing insolubles is sent into separator, isolate the light solvent in clear liquor, obtain the heavy ends of low QI;
(4) under hydrogenation catalyst existent condition, hydrotreatment is carried out to described heavy ends, obtain needle-shape coke raw material pitch; Wherein, the temperature condition of hydrotreatment is 450 DEG C, pressure is 5MPa, and the hydrogenation catalyst described in the present embodiment is Ni-W series catalysts;
(5) by delayed for above-mentioned needle-shape coke raw material pitch coking process, needle-like green coke is obtained;
(6) the needle-like green coke in step (5) is carried out calcination processing, prepare needle coke A.
The preparation method of uncombined carbon described in the present invention is as follows:
Under 70 DEG C of conditions, coal tar is fully mixed with solvent, obtains mixed solution, under the centrifugal force of 2000g, then carry out centrifugation remove insolubles in described mixed solution, the insolubles obtained is uncombined carbon, and the viscosity of carrying out the described mixed solution of centrifugation is 40mpas;
Described solvent is quinoline, and the mass ratio of described quinoline and described coal tar is 8.
embodiment 2
(1) coal tar of 1000g is mixed with the uncombined carbon of 40g, under 350 DEG C of conditions, obtain modified pitch after reacting by heating 10h;
(2) above-mentioned modified pitch and solvent are evenly obtained mixed solution, under the centrifugal force of 1200g, carry out centrifugation remove insolubles in described mixed solution, wherein said solvent is the mixture of tar light oil and washing oil, and the mass ratio of described tar light oil and washing oil is 15; The mass ratio of described solvent and described modified pitch is 8;
(3) clear liquor obtained after removing insolubles is sent into separator, isolate the light solvent in clear liquor, obtain the heavy ends of low QI;
(4) under hydrogenation catalyst existent condition, hydrotreatment is carried out to described heavy ends, obtain needle-shape coke raw material pitch; Wherein, the temperature condition of hydrotreatment is 430 DEG C, pressure is 7MPa, and the hydrogenation catalyst described in the present embodiment is Ni-Mo series catalysts;
(5) by delayed for above-mentioned needle-shape coke raw material pitch coking process, needle-like green coke is obtained;
(6) the needle-like green coke in step (5) is carried out calcination processing, prepare needle coke B.
The preparation method of uncombined carbon described in the present invention is as follows:
Under 60 DEG C of conditions, coal-tar pitch is fully mixed with solvent, obtains mixed solution, under the centrifugal force of 2000g, then carry out centrifugation remove insolubles in described mixed solution, the insolubles obtained is uncombined carbon, and the viscosity of carrying out the described mixed solution of centrifugation is 40mpas;
Described solvent is for absorbing oil, and described absorption oil is 9 with the mass ratio of described coal-tar pitch.
embodiment 3
(1) coal tar of 1000g is mixed with the uncombined carbon of 50g, under 360 DEG C of conditions, obtain modified pitch after reacting by heating 8h;
(2) above-mentioned modified pitch and solvent are evenly obtained mixed solution, under the centrifugal force of 1300g, carry out centrifugation remove insolubles in described mixed solution, wherein said solvent is the mixture of tar light oil, petroleum naphtha light oil and washing oil, described tar light oil can be any with the mixing quality ratio of petroleum naphtha light oil, the mass ratio of the preferred tar light oil of the present embodiment and petroleum naphtha is 5:5, in addition, the total mass of mixture and the mass ratio of washing oil that control tar light oil and petroleum naphtha are further 15; The mass ratio of described solvent and described modified pitch is 8;
(3) clear liquor obtained after removing insolubles is sent into separator, isolate the light solvent in clear liquor, obtain the heavy ends of low QI;
(4) under hydrogenation catalyst existent condition, hydrotreatment is carried out to described heavy ends, obtain needle-shape coke raw material pitch, wherein the temperature condition of hydrotreatment is 420 DEG C, pressure is 8MPa, and the hydrogenation catalyst described in the present embodiment is Ni-Mo series catalysts;
(5) by delayed for above-mentioned needle-shape coke raw material pitch coking process, needle-like green coke is obtained;
(6) the needle-like green coke in step (5) is carried out calcination processing, prepare needle coke C.
The preparation method of uncombined carbon described in the present invention is as follows:
Under 50 DEG C of conditions, be fully mixing with solvent containing the component of uncombined carbon of 80wt% by free carbon content, obtain mixed solution, then under the centrifugal force of 2000g, carry out centrifugation remove insolubles in described mixed solution, the insolubles obtained is uncombined carbon, and the viscosity of carrying out the described mixed solution of centrifugation is 40mpas;
Described solvent can be the mixture of the carbolineum that obtains with any proportioning and washing oil, selects the mass ratio of carbolineum and washing oil to be 3:7 in the present embodiment, and described carbolineum and washing oil mixture and the described mass ratio containing the component of uncombined carbon are 10; Described in the present embodiment containing the component of uncombined carbon for by prepare containing the preparation method of uncombined carbon described in embodiment in the present invention 7.
embodiment 4
(1) mixed with the component containing uncombined carbon of 500g by the coal tar of 1000g, the content of the wherein said component Free Carbon containing uncombined carbon is 15wt%, under 350 DEG C of conditions, obtain modified pitch after reacting by heating 10h;
(2) above-mentioned modified pitch and solvent are evenly obtained mixed solution, under the centrifugal force of 1300g, carry out centrifugation remove insolubles in described mixed solution, wherein said solvent is the mixture of petroleum naphtha light oil and cresols oil, and the mass ratio of described petroleum naphtha light oil and cresols oil is 12; The mass ratio of described solvent and described modified pitch is 6;
(3) clear liquor obtained after removing insolubles is sent into separator, isolate the light solvent in clear liquor, obtain the heavy ends of low QI;
(4) under hydrogenation catalyst existent condition, hydrotreatment is carried out to described heavy ends, obtain needle-shape coke raw material pitch, wherein the temperature condition of hydrotreatment is 400 DEG C, pressure is 12MPa, and the hydrogenation catalyst described in the present embodiment is Ni-Mo series catalysts;
(5) by delayed for above-mentioned needle-shape coke raw material pitch coking process, needle-like green coke is obtained;
(6) the needle-like green coke in step (5) is carried out calcination processing, prepare needle coke D.
The preparation method of the component containing uncombined carbon described in the present invention is as follows:
Fully mixed with solvent by coal-tar pitch, obtain mixed solution, under the centrifugal force of 1200g, carry out centrifugation remove insolubles in described mixed solution, the viscosity of carrying out the described mixed solution of centrifugation is 74mpas;
Described solvent is washing oil; The mass ratio of described solvent and described coal-tar pitch is 3.
embodiment 5
(1) mixed with the component containing uncombined carbon of 400g by the coal tar of 1000g, the content of the wherein said component Free Carbon containing uncombined carbon is 25.1wt%, under 340 DEG C of conditions, obtain modified pitch after reacting by heating 12h;
(2) above-mentioned modified pitch and solvent are evenly obtained mixed solution, under the centrifugal force of 1400g, carry out centrifugation remove insolubles in described mixed solution, wherein said solvent is the mixture of petroleum naphtha light oil and carbolineum, and the mass ratio of described petroleum naphtha light oil and carbolineum is 10; The mass ratio of described solvent and described modified pitch is 5;
(3) clear liquor obtained after removing insolubles is sent into separator, isolate the light solvent in clear liquor, obtain the heavy ends of low QI;
(4) under hydrogenation catalyst existent condition, hydrotreatment is carried out to described heavy ends, obtain needle-shape coke raw material pitch, wherein the temperature condition of hydrotreatment is 380 DEG C, pressure is 14MPa, and the hydrogenation catalyst described in the present embodiment is Ni-W series catalysts;
(5) by delayed for above-mentioned needle-shape coke raw material pitch coking process, needle-like green coke is obtained;
(6) the needle-like green coke in step (5) is carried out calcination processing, prepare needle coke E.
The preparation method of the component containing uncombined carbon described in the present invention is as follows:
Fully mixed with solvent by coal tar, obtain mixed solution, the method for employing filtering separation removes the insolubles in described mixed solution, and the viscosity of carrying out the described mixed solution of filtering separation is 81mpas;
Described solvent is for absorbing oil; The mass ratio of described solvent and described coal tar is 3.5.
embodiment 6
(1) coal tar of 1000g is mixed with the uncombined carbon of 120g, under 360 DEG C of conditions, obtain modified pitch after reacting by heating 8h;
(2) above-mentioned modified pitch and solvent are evenly obtained mixed solution, remove the insolubles in mixed solution after filtration, wherein said solvent is the mixture of BTX and carbolineum, and the mass ratio of described BTX and carbolineum is 8; The mass ratio of described solvent and described modified pitch is 4;
(3) clear liquor obtained after removing insolubles is sent into separator, isolate the light solvent in clear liquor, obtain the heavy ends of low QI;
(4) under hydrogenation catalyst existent condition, hydrotreatment is carried out to described heavy ends, obtain needle-shape coke raw material pitch, wherein the temperature condition of hydrotreatment is 350 DEG C, pressure is 16MPa, and the hydrogenation catalyst described in the present embodiment is Ni-W series catalysts;
(5) by delayed for above-mentioned needle-shape coke raw material pitch coking process, needle-like green coke is obtained;
(6) the needle-like green coke in step (5) is carried out calcination processing, prepare needle coke finished product F
Preparation method is as follows for uncombined carbon described in the present invention:
Under 70 DEG C of conditions, fully mixed by coal tar with solvent, obtain mixed solution, under the centrifugal force of 2000g, carry out centrifugation remove insolubles in described mixed solution, the viscosity of carrying out the described mixed solution of centrifugation is 83mpas;
Described solvent is quinoline; The mass ratio of described solvent and described coal tar is 7.5.
embodiment 7
(1) mixed with the component containing uncombined carbon of 200g by the coal tar of 1000g, the content of the wherein said component Free Carbon containing uncombined carbon is 71.3wt%, under 330 DEG C of conditions, obtain modified pitch after reacting by heating 12h;
(2) above-mentioned modified pitch and solvent are evenly obtained mixed solution, remove the insolubles in described mixed solution through cyclonic separation; Wherein said solvent is the mixture of BTX and carbolineum, and the mass ratio of described BTX and carbolineum is 6; The mass ratio of described solvent and described modified pitch is 3;
(3) clear liquor obtained after removing insolubles is sent into separator, isolate the light solvent in clear liquor, obtain the heavy ends of low QI;
(4) under hydrogenation catalyst existent condition, hydrotreatment is carried out to described heavy ends, obtain needle-shape coke raw material pitch, wherein the temperature condition of hydrotreatment is 330 DEG C, pressure is 19MPa, and the hydrogenation catalyst described in the present embodiment is Ni-W series catalysts;
(5) by delayed for above-mentioned needle-shape coke raw material pitch coking process, needle-like green coke is obtained;
(6) the needle-like green coke in step (5) is carried out calcination processing, prepare needle coke G.
The preparation method of the component containing uncombined carbon described in the present invention is as follows:
Fully mixed with solvent by coal tar, obtain mixed solution, under the centrifugal force of 900g, carry out centrifugation remove insolubles in described mixed solution, the viscosity of carrying out the described mixed solution of centrifugation is 87mpas;
Described solvent is quinoline; The mass ratio of described solvent and described coal tar is 4.5.
embodiment 8
(1) mixed with the component containing uncombined carbon of 200g by the coal tar of 1000g, the content of the wherein said component Free Carbon containing uncombined carbon is 82.7wt%, under 320 DEG C of conditions, obtain modified pitch after reacting by heating 16h;
(2) above-mentioned modified pitch and solvent are evenly obtained mixed solution, under the centrifugal force of 1500g, carry out centrifugation remove insolubles in described mixed solution, wherein said solvent is the mixture of BTX and washing oil, and the mass ratio of described BTX and washing oil is 4; The mass ratio of described solvent and described modified pitch is 2;
(3) clear liquor obtained after removing insolubles is sent into separator, isolate the light solvent in clear liquor, obtain the heavy ends of low QI;
(4) under hydrogenation catalyst existent condition, hydrotreatment is carried out to described heavy ends, obtain needle-shape coke raw material pitch, wherein the temperature condition of hydrotreatment is 320 DEG C, pressure is 18MPa, and the hydrogenation catalyst described in the present embodiment is Ni-W series catalysts;
(5) by delayed for above-mentioned needle-shape coke raw material pitch coking process, needle-like green coke is obtained;
(6) the needle-like green coke in step (5) is carried out calcination processing, prepare needle coke H.
The preparation method of the component containing uncombined carbon described in the present invention is as follows:
Fully mixed with solvent by coal tar, obtain mixed solution, under the centrifugal force of 800g, carry out centrifugation remove insolubles in described mixed solution, the viscosity of carrying out the described mixed solution of centrifugation is 89mpas;
Described solvent is quinoline; The mass ratio of described solvent and described coal tar is 5.
embodiment 9
(1) mixed with the component containing uncombined carbon of 200g by the coal tar of 1000g, the content of the wherein said component Free Carbon containing uncombined carbon is 95wt%, under 360 DEG C of conditions, obtain modified pitch after reacting by heating 8h;
(2) above-mentioned modified pitch and solvent are evenly obtained mixed solution, under the centrifugal force of 1500g, carry out centrifugation remove insolubles in described mixed solution, wherein said solvent is BTX and the mixture absorbing oil, and described BTX is 2 with the mass ratio of absorption oil; The mass ratio of described solvent and described modified pitch is 1;
(3) clear liquor obtained after removing insolubles is sent into separator, isolate the light solvent in clear liquor, obtain the heavy ends of low QI;
(4) under hydrogenation catalyst existent condition, hydrotreatment is carried out to described heavy ends, obtain needle-shape coke raw material pitch, wherein the temperature condition of hydrotreatment is 300 DEG C, pressure is 20MPa, and the hydrogenation catalyst described in the present embodiment is Ni-W series catalysts;
(5) by delayed for above-mentioned needle-shape coke raw material pitch coking process, needle-like green coke is obtained;
(6) the needle-like green coke in step (5) is carried out calcination processing, prepare needle coke I.
The preparation method of the component containing uncombined carbon described in the present invention is as follows:
Fully mixed with solvent by coal tar, obtain mixed solution, under the centrifugal force of 700g, carry out centrifugation remove insolubles in described mixed solution, the viscosity of carrying out the described mixed solution of centrifugation is 91mpas;
Described solvent can be the mixture with the quinoline of arbitrary proportion mixture and washing oil, and in the present embodiment preferred solvent, quinoline mixes with mass ratio 6:4 with washing oil; The mass ratio of described solvent and described coal tar is 5.5.
embodiment 10
(1) mixed with the component containing uncombined carbon of 400g by the coal tar of 1000g, the content of the wherein said component Free Carbon containing uncombined carbon is 50wt%, under 360 DEG C of conditions, obtain modified pitch after reacting by heating 8h;
(2) above-mentioned modified pitch and solvent are evenly obtained mixed solution, under the centrifugal force of 1500g, carry out centrifugation remove insolubles in described mixed solution, wherein said solvent is the mixture of BTX and cresols oil, and the mass ratio of described BTX and cresols oil is 0.25; The mass ratio of described solvent and described modified pitch is 0.5;
(3) clear liquor obtained after removing insolubles is sent into separator, isolate the light solvent in clear liquor, obtain the heavy ends of low QI;
(4) under hydrogenation catalyst existent condition, hydrotreatment is carried out to described heavy ends, obtain needle-shape coke raw material pitch, wherein the temperature condition of hydrotreatment is 300 DEG C, pressure is 20MPa, and the hydrogenation catalyst described in the present embodiment is Ni-W series catalysts;
(5) by delayed for above-mentioned needle-shape coke raw material pitch coking process, needle-like green coke is obtained;
(6) the needle-like green coke in step (5) is carried out calcination processing, prepare needle coke J.
The preparation method of the component containing uncombined carbon described in the present invention is as follows:
Fully mixed with solvent by coal tar, obtain mixed solution, by crossing the insolubles filtered in described mixed solution, the viscosity of carrying out the described mixed solution of centrifugation is 93mpas;
Described solvent can be the mixture with the absorption of arbitrary proportion mixture oil and carbolineum, absorbs oil and mix with mass ratio 4:6 with carbolineum in the present embodiment preferred solvent; The mass ratio of described solvent and described coal tar is 6.
embodiment 11
(1) coal tar of 1000g is mixed with the uncombined carbon of 25g, under 360 DEG C of conditions, obtain modified pitch after reacting by heating 8h;
(2) above-mentioned modified pitch and solvent are evenly obtained mixed solution, under the centrifugal force of 1000g, carry out centrifugation remove insolubles in described mixed solution, wherein said solvent is gas light oil and the mixture absorbing oil, and described gas light oil is 19 with the mass ratio of absorption oil; The mass ratio of described solvent and described modified pitch is 10;
(3) clear liquor obtained after removing insolubles is sent into separator, isolate the light solvent in clear liquor, obtain the heavy ends of low QI;
(4) under hydrogenation catalyst existent condition, carry out hydrotreatment to described heavy ends, obtain needle-shape coke raw material pitch, the temperature condition of wherein hydrotreatment is 450 DEG C, pressure is 5MPa, the hydrogenation catalyst described in the present embodiment is Ni-W series catalysts;
(5) by delayed for above-mentioned needle-shape coke raw material pitch coking process, needle-like green coke is obtained;
(6) the needle-like green coke in step (5) is carried out calcination processing, prepare needle coke K.
The preparation method of uncombined carbon described in the present invention is as follows:
Under 70 DEG C of conditions, coal tar is fully mixed with solvent, obtains mixed solution, under the centrifugal force of 2000g, then carry out centrifugation remove insolubles in described mixed solution, the insolubles obtained is uncombined carbon, and the viscosity of carrying out the described mixed solution of centrifugation is 40mpas;
Described solvent is quinoline, and the mass ratio of described quinoline and described coal tar is 8.
embodiment 12
(1) coal tar of 1000g is mixed with the uncombined carbon of 220g, under 360 DEG C of conditions, obtain modified pitch after reacting by heating 8h;
(2) above-mentioned modified pitch and solvent are evenly obtained mixed solution, under the centrifugal force of 1000g, carry out centrifugation remove insolubles in described mixed solution, wherein said solvent is washing oil; The mass ratio of described solvent and described modified pitch is 15;
(3) clear liquor obtained after removing insolubles is sent into separator, isolate the light solvent in clear liquor, obtain the heavy ends of low QI;
(4) under hydrogenation catalyst existent condition, carry out hydrotreatment to described heavy ends, obtain needle-shape coke raw material pitch, the temperature condition of wherein hydrotreatment is 480 DEG C, pressure is 5MPa, the hydrogenation catalyst described in the present embodiment is Ni-W series catalysts;
(5) by delayed for above-mentioned needle-shape coke raw material pitch coking process, needle-like green coke is obtained;
(6) the needle-like green coke in step (5) is carried out calcination processing, prepare needle coke L.
The preparation method of uncombined carbon described in the present invention is as follows:
Under 70 DEG C of conditions, coal tar is fully mixed with solvent, obtains mixed solution, under the centrifugal force of 2000g, then carry out centrifugation remove insolubles in described mixed solution, the insolubles obtained is uncombined carbon, and the viscosity of carrying out the described mixed solution of centrifugation is 40mpas;
Described solvent is quinoline, and the mass ratio of described quinoline and described coal tar is 8.
It should be noted that, carry out in the device of the carried out hydrogenation reaction of the arbitrary form that the hydrogenation reaction in above-mentioned all embodiments can use in the prior art, as flow type bubbling reactor etc., as preferred embodiment, described hydrogenator can be fixed bed hydrogenation reactor, thus avoids the phenomenon that there is preparing in the raw material of needle coke of obtaining catalyzer precipitation.
The principle of work of the separator in above-described embodiment is: carry out flash separation to the clear liquor obtained after described removing insolubles, be separated into the heavy of solvent oil and low QI.Described separator is being heated to 350 DEG C, and material enters in separator, and the composition that boiling point is less than 350 DEG C becomes vaporised gas on separator top, and the composition that boiling point is more than 350 DEG C forms liquid or slurry is placed in separator bottom.The heavy ends of the low QI described in the present invention is the composition of more than 350 DEG C.
In above-described embodiment, described Ni-Mo series catalysts and described Ni-W series catalysts can be the metal particles of Ni and Mo or Ni and W, also can be described active ingredient Ni and Mo or Ni and W load are prepared from a catalyst support, described carrier can be Al
2o
3carrier, the selection of catalyzer described in the present invention is the conventional prior art in this area, therefore repeats no more in the present invention.In addition, the Ni-Mo series catalysts described in the present invention and described Ni-W series catalysts are commercially available any products.
In addition, in above-described embodiment, delayed coking process carries out in the delayed coking treatment unit commonly used in the prior art, such as adopt tubular oven, coking tower and separation column as delayed coking treatment unit, delayed coking treatment condition adopt delayed coking treatment condition conventional in prior art, such as, adopt following delayed coking treatment condition: heating raw materials heater outlet temperature 450 ~ 550 DEG C; Reaction pressure 0.05 ~ 1.5MPa; Coking cycle 18 ~ 48h.The delayed coking unit adopted in the above embodiment of the present invention is tubular oven, coking tower and separation column, material asphalt is heated to 495 ~ 505 DEG C through tubular oven and enters coking tower, hot charge oil is in coking tower, temperature be 500 DEG C, pressure carries out pyrogenic reaction under being 1.2MPa, coking cycle is 36h, the lighter products generated out enters separation column from top, the needle-like green coke generated is placed at the bottom of coking tower tower, after needle-like green coke fills coking tower successively, draw off through hydraulic decoking, enter calcination stage.
The calcination processing of the needle-like green coke in above-described embodiment adopts calciner conventional in prior art, and calcination condition also adopts calcining temperature conventional in prior art, and the above embodiment of the present invention adopts carries out calcining graphitization processing at 2800 DEG C.
experimental example
In order to illustrate that technical scheme described in the present invention has Substantial technical effect compared to prior art, the present invention is provided with following experimental example:
When testing, the character of the coal-tar pitch used in above-described embodiment is as shown in table 1:
The character of table 1 coal-tar pitch
| Raw material | SP/℃ | CV/% | QI/% | TI/% | β/% | Sulphur content/% |
| Mid-temperature pitch | 70.0 | 47.25 | 5.37 | 10.53 | 5.16 | 0.24 |
Wherein in table 1, SP: the softening temperature of pitch; CV: the coking value of coal-tar pitch; QI: the mass percentage of quinoline insolubles in pitch; TI: the mass percentage of toluene insolubles in pitch; β: the mass percentage of toluene insoluble quinoline solvend in pitch.
To yield, SP, QI of the described material asphalt for the preparation of needle coke obtained after the process of step (1) ~ (4) in above-mentioned all embodiments, content and the CV performance of TI, β resin measure, and obtain result as shown in table 2:
Table 2 for the preparation of the yield of the material asphalt of needle coke, SP, QI, the content performance of TI, β resin
| Embodiment | Needle-shape coke raw material asphalt yield/% | SP/℃ | QI/% | TI/% | β/% | CV/% |
| 1 | 65.32 | 99.2 | 0.04 | 33.84 | 33.8 | 62.71 |
| 2 | 66.27 | 100.8 | 0.04 | 34.91 | 34.87 | 63.24 |
| 3 | 66.84 | 102.1 | 0.02 | 35.36 | 35.34 | 64.32 |
| 4 | 67.92 | 104.4 | 0.01 | 35.74 | 35.73 | 65.78 |
| 5 | 66.58 | 103.2 | 0.02 | 35.42 | 35.4 | 64.27 |
| 6 | 67.93 | 105.6 | 0.01 | 35.93 | 35.92 | 66.41 |
| 7 | 64.15 | 101.2 | 0.03 | 34.07 | 34.04 | 63.51 |
| 8 | 64.23 | 100.7 | 0.03 | 33.46 | 33.43 | 62.34 |
| 9 | 63.97 | 100.1 | 0.04 | 33.01 | 32.97 | 61.88 |
| 10 | 63.21 | 99.6 | 0.04 | 32.41 | 32.37 | 61.92 |
| 11 | 62.97 | 97.6 | 0.05 | 32.24 | 32.19 | 61.37 |
| 12 | 62.83 | 97.3 | 0.06 | 32.27 | 32.21 | 61.22 |
Needle coke A ~ the L prepared in above-mentioned all embodiments is carried out MEASURING THE THERMAL EXPANSION COEFFICIENT, and the thermal expansivity of needle coke is as shown in table 3:
The thermal expansivity of the needle coke A ~ L prepared in table 3 embodiment
comparative example
Have Substantial technical effect in order to further illustrate technical scheme described in the present invention compared to prior art, the present invention is provided with following comparative example:
The preparation method of the coal-based needle coke in this comparative example, comprise: with the coal-tar pitch used in experimental example for raw material, be added in the mixed solvent groove filling quinoline and washing oil mixed solvent by described asphalt stock and modulate, the mass ratio of asphalt stock and mixed solvent is 1:8; After raw material after modulation is heated to 400 DEG C by tubular oven, through sedimentation, centrifugal and removed by filtration quinoline insolubles, be purified raw material; Above-mentioned purification raw material is heated to 500 DEG C in tubular oven, under 2.0MPa, carries out polycondensation 12h, polycondensation product, after separation column fractionation, obtains polycondensation fine fodder; Polycondensation fine fodder is as needle-shape coke raw material pitch, enter coking tower being heated to 495 ~ 505 DEG C through tubular oven, hot charge oil carries out pyrogenic reaction in coking tower, the lighter products generated out enters separation column from top, the needle-like green coke generated is placed at the bottom of coking tower tower, after needle-like green coke fills coking tower successively, draw off through hydraulic decoking; At 2800 DEG C, carry out calcining graphitization processing again, obtain needle coke finished product.
First carry out performance measurement to the character and yield that prepare needle-shape coke raw material pitch in comparative example, measurement result is as shown in table 4:
Character and the yield of needle-shape coke raw material pitch is prepared in table 4 comparative example
| Title | Needle-shape coke raw material asphalt yield | SP/℃ | QI/% | TI/% | β/% | CV/% | Sulphur content/% |
| Material asphalt | 62.32 | 96.3 | 0.17 | 25.71 | 25.54 | 56.78 | 0.20 |
Further, also carry out thermal expansivity test to the needle coke prepared in comparative example, from test result, the thermal expansivity of the needle coke that this comparative example prepares is 1.4 × 10
-6/ DEG C.
By above-mentioned more known, in comparative example, the thermal expansivity of needle coke adds 0.1-0.6 × 10 compared to embodiment
-6/ DEG C, when reality uses, this quality being enough to Graphite Electrodes prepared by needle coke is a greater impact; In addition, the QI of comparative example Raw pitch adds 0.11 ~ 0.16% compared to embodiment, and coking rate rate reduces 5-10% compared to embodiment, and in visible the present invention, the preparation technology of needle coke is compared to prior art, has obvious Substantial technical effect.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments, and thus the apparent change of extending out or variation be still among the protection domain of the invention claim.
Claims (10)
1. produce a technique for needle coke, comprise the steps:
(1) coal-tar pitch is mixed with uncombined carbon or containing the component of uncombined carbon, under 320 ~ 360 DEG C of conditions, obtain modified pitch after reacting by heating;
(2) above-mentioned modified pitch and solvent are evenly obtained mixed solution, the method for employing physical sepn removes the insolubles in described mixed solution;
(3) clear liquor obtained after removing insolubles is separated, isolates the solvent in clear liquor, obtain the heavy ends of low QI;
(4) under hydrogenation catalyst existent condition, hydrotreatment is carried out to described heavy ends, obtain needle-shape coke raw material pitch;
(5) by delayed for above-mentioned needle-shape coke raw material pitch coking process, needle-like green coke is obtained;
(6) the needle-like green coke in step (5) is prepared needle coke through calcining.
2. produce the technique of needle coke according to claim 1, it is characterized in that, in described step (1), in the quality of uncombined carbon, described uncombined carbon or containing the addition of the component of uncombined carbon and described coal-tar pitch than being 3:100 ~ 20:100.
3. produce the technique of needle coke according to claim 2, it is characterized in that, in the quality of uncombined carbon, described uncombined carbon or containing the addition of the component of uncombined carbon and described coal-tar pitch than being 5:100 ~ 12:100.
4. according to the technique of the arbitrary described production needle coke of claims 1 to 3, it is characterized in that, in described step (1), the content of the described component Free Carbon containing uncombined carbon is 15 ~ 95wt%, and surplus is impurity.
5. according to the technique of the arbitrary described production needle coke of Claims 1 to 4, it is characterized in that, in described step (1), the described component containing uncombined carbon obtains mixed solution after fully being mixed with solvent by coal-tar pitch, then employing physical separation method removes the insolubles in described mixed solution, and this insolubles is the component containing uncombined carbon;
Wherein, described solvent is washing oil, absorb in oil, carbolineum or quinoline any one or a few, the mass ratio of described solvent and coal-tar pitch is 3 ~ 6.
6. according to the technique of the arbitrary described production needle coke of Claims 1 to 4, it is characterized in that, in described step (1), described uncombined carbon is at 50 ~ 70 DEG C, mixed solution is obtained by coal-tar pitch or after fully mixing with solvent containing the component of uncombined carbon, then under 2000 ~ 3000G centrifugal force, be separated the insolubles in the described mixed solution of removing, this insolubles is uncombined carbon;
Wherein, described solvent is washing oil, absorb in oil, carbolineum or quinoline one or more, described solvent and described coal-tar pitch or the mass ratio containing free carbon component are 8 ~ 10.
7. according to the technique of the arbitrary described production needle coke of claim 1 ~ 6, it is characterized in that, in described step (1), the described reacting by heating time is 5 ~ 8h.
8. according to the technique of the arbitrary described production needle coke of claim 1 ~ 7, it is characterized in that, in described step (2), described solvent is the mixture of coal measures lightweight oil and coal measures aromatic oil, or the mixture of BTX and coal measures aromatic oil, the mass ratio of described coal measures lightweight oil or BTX and coal measures aromatic oil is 0.25-19; The mass ratio of described solvent and described pitch is 0.5-10.
9. produce the technique of needle coke according to claim 8, it is characterized in that, described coal measures lightweight oil is one or more in gas light oil, tar light oil, petroleum naphtha light oil, and described coal measures aromatic oil is washing oil, absorb oil, cresols is oily, one or more in carbolineum.
10. according to the technique of the arbitrary described production needle coke of claim 1 ~ 9, it is characterized in that, hydrogenation catalyst in described step (4) is any one in Ni-Mo series catalysts or Ni-W series catalysts, and the condition of described hydrotreatment is: temperature is 300 ~ 450 DEG C, and pressure is 5 ~ 20Mpa.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104946288A (en) * | 2015-06-10 | 2015-09-30 | 神华集团有限责任公司 | Modified pitch and preparation method thereof |
| CN107694552A (en) * | 2017-11-07 | 2018-02-16 | 西北大学 | A kind of technique that coal-based needle coke is produced as raw material using middle coalite tar pitch |
| CN108102708A (en) * | 2016-11-25 | 2018-06-01 | 中国石油化工股份有限公司 | A kind of combined technical method of coal tar production needle coke |
| CN109735361A (en) * | 2019-01-21 | 2019-05-10 | 辽宁科技大学 | A kind of preparation method of high micro strength mosaic texture pitch coke |
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| CN103013566A (en) * | 2011-09-23 | 2013-04-03 | 北京三聚创洁科技发展有限公司 | Technology for preparing needle coke raw material from coal-tar pitch |
| CN103102891A (en) * | 2013-01-30 | 2013-05-15 | 陕西煤业化工技术研究院有限责任公司 | Preparation method of coal based needle coke |
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| JPS6051783A (en) * | 1983-08-31 | 1985-03-23 | Osaka Gas Co Ltd | Production of binder |
| CN103013566A (en) * | 2011-09-23 | 2013-04-03 | 北京三聚创洁科技发展有限公司 | Technology for preparing needle coke raw material from coal-tar pitch |
| CN103102891A (en) * | 2013-01-30 | 2013-05-15 | 陕西煤业化工技术研究院有限责任公司 | Preparation method of coal based needle coke |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104946288A (en) * | 2015-06-10 | 2015-09-30 | 神华集团有限责任公司 | Modified pitch and preparation method thereof |
| CN104946288B (en) * | 2015-06-10 | 2018-04-06 | 神华集团有限责任公司 | Modified coal tar pitch and preparation method thereof |
| CN108102708A (en) * | 2016-11-25 | 2018-06-01 | 中国石油化工股份有限公司 | A kind of combined technical method of coal tar production needle coke |
| CN108102708B (en) * | 2016-11-25 | 2020-07-07 | 中国石油化工股份有限公司 | Combined process method for producing needle coke from coal tar |
| CN107694552A (en) * | 2017-11-07 | 2018-02-16 | 西北大学 | A kind of technique that coal-based needle coke is produced as raw material using middle coalite tar pitch |
| CN107694552B (en) * | 2017-11-07 | 2019-05-14 | 西北大学 | A kind of technique that coal-based needle coke is produced as raw material using middle coalite tar pitch |
| CN109735361A (en) * | 2019-01-21 | 2019-05-10 | 辽宁科技大学 | A kind of preparation method of high micro strength mosaic texture pitch coke |
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