CN104232130A - Process of producing needle coke - Google Patents
Process of producing needle coke Download PDFInfo
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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) mixing the clear solution obtained after the insoluble substances are removed with a petroleum series needle coke raw material, separating, and separating the solvent to obtain a needle coke raw material; (4) subjecting the needle coke raw material to delayed coking to obtain green needle coke; and (5) calcinating the green needle coke to prepare the needle coke. The prepared needle coke has advantages of a low coefficient of thermal expansion.
Description
Technical field
The present invention relates to a kind of production technique of needle coke, a kind of technique utilizing coal measures and petroleum raw material to prepare needle coke, belongs to needle coke preparing technical field specifically.
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 petroleum needle coke needle coke.Wherein, the product liquid etc. that coal-based needle coke raw material is had coal tar, coal-tar pitch and obtained by direct hydrogenation cracking coal, its constructional feature is (aromaticity is higher) based on condensed-nuclei aromatics, and total carbon element content is greater than 90%, contained aliphatic lateral chain is short and few, and chemically reactive is poor; And petroleum needle-shape coke raw material has Catalytic Cracking Residual Oil, fluid catalytic cracking decant oil, lubricating oil to extract oil, ethylene bottom oil etc. out, its constructional feature is that the aromaticity of condensed-nuclei aromatics is lower, total carbon element content is 83-87%, and contained aliphatic lateral chain is longer and many, and chemically reactive is high.
The report adopting above-mentioned two class raw materials to prepare separately needle coke has a lot.Prepare separately in the process of needle coke at employing two class raw material, the coking yield of coal-based needle coke raw material is high, but because its constructional feature is based on condensed-nuclei aromatics, in coking, reaction required activation energy is not reached when coking temperature is lower, and coking temperature higher time, multiple reactive center can be formed in system, polycondensation is made to be difficult to control, in addition it contains the alicyclic structure of hydrogenation hardly, make reaction stability poor, system viscosity is higher, and little aliphatic chain cannot discharge more amount gas thus make mesophase spherule can not co-axial orientation, so not easily obtain performance preferably needle coke, and the coking yield of petroleum needle-shape coke raw material is lower, and aromaticity is lower in its constructional feature, containing a large amount of aliphatic side chainses and alicyclic structure, easily too much reactive center is formed like this in reaction process, have little time fully to grow up after making the generation of mesophase spherule spherocrystal and namely mutually melt and and form thin pattern structure, so also not easily obtain the needle coke of excellent performance.
In order to solve the problems of the technologies described above, how people prepares needle coke, the problems referred to above existed during to overcome its independent coking by coal-based needle coke raw material and petroleum needle-shape coke raw material co-carbonization if beginning one's study.But because the molecular structure of coal-based needle coke raw material and petroleum needle-shape coke raw material differs greatly, when coking, consistency is poor, speed of response is different, causes being separated between phase and phase, is still difficult to the needle coke preparing excellent performance.The compatibility problem how solving coal-based needle coke raw material and petroleum needle-shape coke raw material is the key of the needle coke of the two co-carbonization processability excellence.
Chinese patent literature CN1418930A discloses and a kind ofly first to heat-treat coal-based needle coke raw material and petroleum needle-shape coke raw material under lower than the condition of coking temperature, with the consistency of both raisings, and then carry out the method that co-carbonization prepares needle coke, specifically comprise the steps: first petroleum to be mixed with the weight ratio of 1:0.1-10 mutually with coal measures raw material, under 400-440 DEG C and 0.2-2Mpa in inert gas atmosphere thermal treatment 0.5-8h; Then within 2-30 time second, 490-550 DEG C is warmed up to, then at 0.2-2Mpa Using Coke-oven 3-8h.
Above-mentioned technology when preparing needle coke, first by petroleum needle-shape coke raw material and the mixing of coal-based needle coke raw material, 400-440 DEG C, heat-treat 0.5-8h under 0.2-2Mpa condition, and then carry out coking process.Owing to first having carried out thermal treatment to two kinds of raw materials, consistency between the two can be improved like this, thus can prepare that coking yield is higher, the good needle coke of optical texture.But, because above-mentioned technology is at 400-440 DEG C, under 0.2-2Mpa, coal-based needle coke raw material and petroleum needle-shape coke raw material are heat-treated, because thermal treatment temp is high, lower-molecular substance generation polycondensation in coal-based needle coke raw material is caused to generate β resin on the one hand, and generate β resin or coal-based needle coke raw material in original β resin at high temperature further occur polycondensation generate quinoline insolubles, on the other hand, also can polycondensation be there is in oil system needle-shape coke raw material in high-temperature heat treatment process, generate quinoline insolubles, two aspect comprehensive actions cause the content of quinoline insolubles in needle-shape coke raw material greatly to increase, and the existence of quinoline insolubles, make the coefficient of expansion of the needle coke prepared large, have a strong impact on performance when needle coke uses as electrode.
Summary of the invention
Technical problem to be solved by this invention adopts the consistency heat-treating to improve coal-based needle coke raw material and petroleum needle-shape coke raw material under high-temperature condition in prior art in needle coke preparation process, and heat treated temperature is high that part β resin generation polycondensation in raw material can be caused to generate new quinoline insolubles, thus when causing using the coal-based needle coke raw material after Overheating Treatment and petroleum needle-shape coke raw material to prepare needle coke, the problem that the thermal expansivity of needle coke is large, and then a kind of production technique of needle coke is provided, the needle coke using technique of the present invention to prepare has the low advantage of thermal expansivity.
For solving the problems of the technologies described above, the invention provides a kind of production technique of 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 condition, obtain modified pitch after reacting by heating;
(2) by above-mentioned modified pitch and solvent evenly after obtain mixed solution, adopt the method for physical sepn to remove insolubles in described mixed solution;
(3) clear liquor obtained after removing insolubles is mixed with petroleum needle-shape coke raw material, be then separated, after isolating solvent, obtain needle-shape coke raw material;
(4) above-mentioned needle-shape coke raw material is carried out delayed coking process, obtain needle-like green coke;
(5) above-mentioned needle-like green coke 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 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 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 adopt the method for physical sepn to remove insolubles in described mixed solution, this insolubles is the component containing uncombined carbon;
Wherein said solvent is washing oil, to absorb in oil, carbolineum or quinoline any one or a few, and 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, the mass ratio of described solvent and coal-tar pitch or the component that contains uncombined carbon is 8-10.
In described step (1), described heat-up 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; Described coal measures aromatic oil is washing oil, absorb in oil, oily, the carbolineum of cresols one or more.
In described step (4), after first needle-shape coke raw material being carried out hydrotreatment in the presence of a hydrogenation catalyst, carry out delayed coking process again; Wherein, the hydrogenation catalyst of described hydrotreatment 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.
Described petroleum needle-shape coke raw material is through any one of the black petroleum products of furfural extraction, ethylene bottom oil, Catalytic Cracking Residual Oil and thermal cracking residue.
The present invention has following beneficial effect compared with prior art:
(1) production technique of needle coke of the present invention, first by adding uncombined carbon or the component containing uncombined carbon in coal-tar pitch, heat-treat under the comparatively cold condition of 320-360 DEG C again, owing to adding uncombined carbon or the component containing uncombined carbon, make coal-tar pitch can upgrading at a lower temperature, and at low temperatures upgrading time, can ensure that in coal-tar pitch, only xylene solubles generation polycondensation generates β resin, and polycondensation generation quinoline insolubles can not be there is further in β resin, so just be equivalent to the content that increase only β resin in the modified pitch obtained, then after transformation of the way pitch and solvent being removed the uncombined carbon changed a social system and contain in pitch or the impurity such as the component containing uncombined carbon and a small amount of quinoline insolubles, again it is mixed mutually with the petroleum needle-shape coke raw material through furfural extraction, owing to also containing solvent in modified pitch, the existence of this solvent improves the consistency of modified pitch and petroleum needle-shape coke raw material, therefore without the need to heat-treating, modified pitch can be made to mix with petroleum needle-shape coke raw material, then the mixture of the modified pitch after mixing and petroleum needle-shape coke raw material is carried out separated from solvent, isolate solvent, consistency can be obtained good, β resin content is high, the needle-shape coke raw material that quinoline insolubles content is low, the needle coke adopting this needle-shape coke raw material to prepare has extremely low thermal expansivity.After tested, its thermal expansivity can be low to moderate 0.8 × 10
-6-1.2 × 10
-6/ DEG C.
(2) production technique of needle coke of the present invention, preferably in the quality of uncombined carbon, described uncombined carbon or the ratio 5:100-12:100 containing the component of uncombined carbon and the addition of described coal-tar pitch, modified pitch is prepared under this addition, then the modified pitch of removing impurity is mixed mutually with the petroleum needle-shape coke raw material through furfural extraction, then the solvent isolated in mixture obtains needle-shape coke raw material, β resin content in this needle-shape coke raw material is up to 34.44-35.95%, QI is low to moderate 0.01-0.03%, after delayed for this raw material coking process, calcine again, prepare needle coke finished product, this needle coke has the low advantage of thermal expansivity, its thermal expansivity can be low to moderate 0.8 × 10
-6-1.0 × 10
-6/ DEG C.
(3) production technique of needle coke of the present invention, preferably obtain needle-shape coke raw material through hydrotreatment by step (3), β resin content in needle-shape coke raw material after hydrotreatment is up to 34.31-35.47%, QI is low to moderate 0.01-0.02%, after delayed for this raw material coking process, then calcine, prepare needle coke finished product, this needle coke has the low advantage of thermal expansivity, and its thermal expansivity can be low to moderate 0.8 × 10
-6-1.0 × 10
-6/ DEG C.
Embodiment
Embodiment 1
(1) coal-tar pitch of 1000g is mixed with the uncombined carbon of 30g, under 360 DEG C of conditions, obtain modified pitch after reacting by heating 5h;
(2) above-mentioned modified pitch and solvent are evenly obtained mixed solution, under the centrifugal force of 2000g, 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 mixed with black petroleum products, be then separated, after isolating solvent, obtain needle-shape coke raw material; The mass ratio 3:1 of described clear liquor and black petroleum products;
(4) above-mentioned needle-shape coke raw material is carried out delayed coking process, obtain needle-like green coke;
(5) above-mentioned needle-like green coke calcining is prepared needle coke A.
The preparation method of uncombined carbon described in the present embodiment is as follows:
Under 70 DEG C of conditions, coal-tar pitch is fully mixed with quinoline, 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; The mass ratio 8 of described quinoline and described coal-tar pitch.
Embodiment 2
(1) coal-tar pitch of 1000g is mixed with the uncombined carbon of 40g, under 350 DEG C of conditions, obtain modified pitch after reacting by heating 6h;
(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 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 mixed with ethylene bottom oil, be then separated, after isolating solvent, obtain needle-shape coke raw material; The mass ratio 4:1 of described clear liquor and ethylene bottom oil;
(4) above-mentioned needle-shape coke raw material is carried out delayed coking process, obtain needle-like green coke;
(5) above-mentioned needle-like green coke calcining is prepared needle coke B.
The preparation method of uncombined carbon described in the present embodiment is as follows:
Under 60 DEG C of conditions, coal-tar pitch is fully mixed with washing oil, obtains mixed solution, under the centrifugal force of 2500G, 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 43mpas; The mass ratio 9 of described quinoline and described coal-tar pitch.
Embodiment 3
(1) coal-tar pitch of 1000g is mixed with the uncombined carbon of 50g, under 340 DEG C of conditions, obtain modified pitch after reacting by heating 7h;
(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 tar light oil, petroleum naphtha light oil and cresols oil, described tar light oil can be any with the mixing quality ratio of petroleum naphtha light oil, the mass ratio 5:5 of the preferred tar light oil of the present embodiment and petroleum naphtha light oil, in addition, the gross weight of mixture and the mass ratio of cresols oil that control tar light oil and petroleum naphtha light oil are further 10; The mass ratio of described solvent and described modified pitch is 5;
(3) clear liquor obtained after removing insolubles is mixed with Catalytic Cracking Residual Oil, be then separated, after isolating solvent, obtain needle-shape coke raw material; The mass ratio 5:1 of described clear liquor and Catalytic Cracking Residual Oil;
(4) above-mentioned needle-shape coke raw material is carried out delayed coking process, obtain needle-like green coke;
(5) above-mentioned needle-like green coke calcining is prepared needle coke C.
The preparation method of uncombined carbon described in the present embodiment 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 3000G, carry out centrifugation remove insolubles in described mixed solution, the insolubles obtained is uncombined carbon, and the viscosity of carrying out the described mixture of centrifugation is 40mpas;
The carbolineum that described solvent can obtain for any proportioning and the mixture absorbing oil, select carbolineum and absorb oily mass ratio 3:7 in the present embodiment, described carbolineum and the mass ratio 8 absorbing oily mixture and the described component containing uncombined carbon; The component of uncombined carbon described in the present embodiment prepares for there being the preparation method containing uncombined carbon described in embodiment 7 in the present invention.
Embodiment 4
(1) mixed with the component containing uncombined carbon of 500g by the coal-tar pitch of 1000g, the content of the wherein said component Free Carbon containing uncombined carbon is 15wt%, under 330 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 petroleum naphtha light oil and carbolineum, and the mass ratio of described petroleum naphtha light oil and carbolineum is 8; The mass ratio of described solvent and described modified pitch is 8;
(3) clear liquor obtained after removing insolubles is mixed with thermal cracking residue, be then separated, after isolating solvent, obtain needle-shape coke raw material; The mass ratio 4:1 of described clear liquor and thermal cracking residue;
(4) above-mentioned needle-shape coke raw material is carried out delayed coking process, obtain needle-like green coke;
(5) above-mentioned needle-like green coke calcining is prepared needle coke D.
The preparation method of the component containing uncombined carbon described in the present embodiment is as follows:
Fully mixed with washing oil by coal-tar pitch, obtain mixed solution, under the centrifugal force of 1500G, carry out centrifugation remove insolubles in described mixed solution, the viscosity of carrying out the described mixed solution of centrifugation is 74mpas; The mass ratio of described washing oil and described coal-tar pitch is 3.
Embodiment 5
(1) mixed with the component containing uncombined carbon of 400g by the coal-tar pitch of 1000g, the content of the wherein said component Free Carbon containing uncombined carbon is 25.1wt%, under 320 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 2000g, 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 mixed with black petroleum products, be then separated, after isolating solvent, obtain needle-shape coke raw material; The mass ratio 5:1 of described clear liquor and black petroleum products;
(4) above-mentioned needle-shape coke raw material is carried out delayed coking process, obtain needle-like green coke;
(5) above-mentioned needle-like green coke calcining is prepared needle coke E.
The preparation method of the component containing uncombined carbon described in the present embodiment is as follows:
Fully mixed with absorption oil by coal-tar pitch, 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; The described mass ratio absorbing oil and described coal-tar pitch is 5.
Embodiment 6
(1) coal-tar pitch of 1000g is mixed with the uncombined carbon of 120g, under 350 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 described mixed solution after filtration, wherein said solvent is the mixture of BTX and washing oil, and the mass ratio of described BTX and washing oil is 8; The mass ratio of described solvent and described modified pitch is 4;
(3) clear liquor obtained after removing insolubles is mixed with ethylene bottom oil, be then separated, after isolating solvent, obtain needle-shape coke raw material; The mass ratio 4:1 of described clear liquor and ethylene bottom oil;
(4) above-mentioned needle-shape coke raw material is carried out delayed coking process, obtain needle-like green coke;
(5) above-mentioned needle-like green coke calcining is prepared needle coke F.
The preparation method of uncombined carbon described in the present embodiment is as follows:
Under 60 DEG C of conditions, coal-tar pitch is fully mixed with carbolineum, 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 83mpas; The mass ratio 10 of described carbolineum and described coal-tar pitch.
Embodiment 7
(1) mixed with the component containing uncombined carbon of 200g by the coal-tar pitch 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 8h;
(2) above-mentioned modified pitch and solvent are evenly obtained mixed solution, remove the insolubles in described mixed solution in 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 mixed with Catalytic Cracking Residual Oil, be then separated, after isolating solvent, obtain needle-shape coke raw material; The mass ratio 4:1 of described clear liquor and black petroleum products;
(4) above-mentioned needle-shape coke raw material is carried out delayed coking process, obtain needle-like green coke;
(5) above-mentioned needle-like green coke calcining is prepared needle coke G.
The preparation method of the component containing uncombined carbon described in the present embodiment is as follows:
Fully mixed with quinoline by coal-tar pitch, obtain mixed solution, remove the insolubles in described mixed solution under the centrifugal force of 1500G, the viscosity of carrying out the described mixed solution of centrifugation is 83mpas; The mass ratio of described quinoline and described coal-tar pitch is 6.
Embodiment 8
(1) mixed with the component containing uncombined carbon of 200g by the coal-tar pitch 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 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 stone BTX is 4 with the mass ratio of absorption oil; The mass ratio of described solvent and described modified pitch is 2;
(3) clear liquor obtained after removing insolubles is mixed with thermal cracking residue, be then separated, after isolating solvent, obtain needle-shape coke raw material; The mass ratio 3:1 of described clear liquor and thermal cracking residue;
(4) above-mentioned needle-shape coke raw material is carried out delayed coking process, obtain needle-like green coke;
(5) above-mentioned needle-like green coke calcining is prepared needle coke H.
The preparation method of the component containing uncombined carbon described in the present embodiment is as follows:
Fully mixed with carbolineum by coal-tar pitch, obtain mixed solution, under the centrifugal force of 1500G, carry out centrifugation remove insolubles in described mixed solution, the viscosity of carrying out the described mixed solution of centrifugation is 89mpas; The mass ratio of described carbolineum and described coal-tar pitch is 5.
Embodiment 9
(1) mixed with the component containing uncombined carbon of 400g by the coal-tar pitch 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 0.5 of described solvent and described modified pitch;
(3) clear liquor obtained after removing insolubles is mixed with thermal cracking residue, be then separated, after isolating solvent, obtain needle-shape coke raw material; The mass ratio 5:1 of described clear liquor and thermal cracking residue;
(4) above-mentioned needle-shape coke raw material is carried out delayed coking process, obtain needle-like green coke;
(5) above-mentioned needle-like green coke calcining is prepared needle coke I.
The preparation method of the component containing uncombined carbon described in the present embodiment is as follows:
Fully mixed with solvent by coal-tar pitch, obtain mixed solution, by crossing the insolubles filtered in described mixed solution, the viscosity of carrying out the described mixed solution of filtering separation is 93mpas; Described solvent can be the mixture with the absorption oil of arbitrary proportion mixing 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 pitch is 6.
Embodiment 10
(1) coal-tar pitch of 1000g is mixed with the uncombined carbon of 60g, under 340 DEG C of conditions, obtain modified pitch after reacting by heating 7h;
(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 petroleum naphtha light oil and washing oil, and the mass ratio of described petroleum naphtha light oil and washing oil is 10; The mass ratio of described solvent and described modified pitch is 6;
(3) clear liquor obtained after removing insolubles is mixed with Catalytic Cracking Residual Oil, be then separated, after isolating solvent, obtain needle-shape coke raw material; The mass ratio 5:1 of described clear liquor and Catalytic Cracking Residual Oil;
(4) under the condition of hydrogenation catalyst, hydrotreatment is carried out to above-mentioned needle-shape coke raw material, then carry out delayed coking process, obtain needle-like green coke; The temperature condition of described hydrotreatment is 300 DEG C, pressure is 20Mpa, and described hydrogenation catalyst is Ni-Mo series catalysts;
(5) above-mentioned needle-like green coke calcining is prepared needle coke J.
The preparation method of uncombined carbon described in the present embodiment is as follows:
Under 60 DEG C of conditions, coal-tar pitch is fully mixed with washing oil, obtains mixed solution, under the centrifugal force of 2500G, 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 43mpas; The mass ratio 9 of described quinoline and described coal-tar pitch.
Embodiment 11
(1) mixed with the component containing uncombined carbon of 400g by the coal-tar pitch of 1000g, the content of the wherein said component Free Carbon containing uncombined carbon is 25.1wt%, under 360 DEG C of conditions, obtain modified pitch after reacting by heating 6h;
(2) above-mentioned modified pitch and solvent are evenly obtained mixed solution, under the centrifugal force of 2000g, 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 12; The mass ratio of described solvent and described modified pitch is 5;
(3) clear liquor obtained after removing insolubles is mixed with black petroleum products, be then separated, after isolating solvent, obtain needle-shape coke raw material; The mass ratio 4:1 of described clear liquor and black petroleum products;
(4) under the condition of hydrogenation catalyst, hydrotreatment is carried out to above-mentioned needle-shape coke raw material, then carry out delayed coking process, obtain needle-like green coke; The temperature condition of described hydrotreatment is 380 DEG C, pressure is 12Mpa, and described hydrogenation catalyst is Ni-Mo series catalysts;
(5) above-mentioned needle-like green coke calcining is prepared needle coke K.
The preparation method of the component containing uncombined carbon described in the present embodiment is as follows:
Fully mixed with absorption oil by coal-tar pitch, 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; The described mass ratio absorbing oil and described coal-tar pitch is 5.
Embodiment 12
(1) coal-tar pitch of 1000g is mixed with the uncombined carbon of 120g, under 330 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 described mixed solution after filtration, wherein said solvent is the mixture of BTX and washing oil, and the mass ratio of described BTX and washing oil is 8; The mass ratio of described solvent and described modified pitch is 4;
(3) clear liquor obtained after removing insolubles is mixed with ethylene bottom oil, be then separated, after isolating solvent, obtain needle-shape coke raw material; The mass ratio 3:1 of described clear liquor and ethylene bottom oil;
(4) under the condition of hydrogenation catalyst, hydrotreatment is carried out to above-mentioned needle-shape coke raw material, then carry out delayed coking process, obtain needle-like green coke; The temperature condition of described hydrotreatment is 450 DEG C, pressure is 5Mpa, and described hydrogenation catalyst is Ni-W series catalysts;
(5) above-mentioned needle-like green coke calcining is prepared needle coke L.
The preparation method of uncombined carbon described in the present embodiment is as follows:
Under 60 DEG C of conditions, coal-tar pitch is fully mixed with carbolineum, 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 83mpas; The mass ratio 10 of described carbolineum and described coal-tar pitch.
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 embodiment 10-12 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.In addition, described Ni-Mo series catalysts and described Ni-W series catalysts can be the metallic particles of Ni and Mo or Ni and W, and 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 hydrogenation catalyst 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, the black petroleum products in the embodiment of the present invention, ethylene bottom oil, Catalytic Cracking Residual Oil and thermal cracking residue are black petroleum products, ethylene bottom oil, Catalytic Cracking Residual Oil and thermal cracking residue through extracting.Wherein, the condition of described extraction: temperature is 50 DEG C, agent-oil ratio is 2:1, and extraction agent is furfural.
In embodiment of the present invention step (3), the principle of work of the separator that described separation method uses is: to needing the product be separated to carry out flash separation, be separated into solvent oil and needle-shape coke raw material.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.Needle-shape coke raw material described in the present invention refers to the cut of more than 350 DEG C.
In the embodiment of the present invention, 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, under pressure is 0.8MPa, carry out pyrogenic reaction, 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 the embodiment of the present invention 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:
The content of SP, QI, TI, β resin of the described raw material for the preparation of needle coke through obtaining after the process of described step (1)-(3) in above-mentioned all embodiments being measured, obtaining measurement result as shown in table 1.
Table 1
| Embodiment | SP/℃ | QI/% | TI/% | β/% |
| 1 | 99.9 | 0.06 | 33.84 | 33.78 |
| 2 | 101.5 | 0.05 | 34.91 | 34.86 |
| 3 | 102.7 | 0.03 | 35.36 | 35.33 |
| 4 | 104.0 | 0.02 | 35.74 | 35.72 |
| 5 | 103.8 | 0.02 | 35.42 | 35.4 |
| 6 | 106.3 | 0.01 | 35.93 | 35.92 |
| 7 | 101.9 | 0.04 | 34.07 | 34.03 |
| 8 | 101.3 | 0.04 | 33.46 | 33.42 |
| 9 | 100.7 | 0.05 | 33.01 | 32.96 |
| 10 | 102.3 | 0.02 | 32.41 | 32.39 |
| 11 | 105.3 | 0.02 | 32.24 | 32.22 |
| 12 | 101.0 | 0.01 | 32.27 |
The needle coke A-L obtained 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 2.
Table 2
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 embodiment and black petroleum products for raw material, first the impurity such as the quinoline insolubles in coal-tar pitch are removed by filtering separation, the coal-tar pitch of removing impurity is mixed with the weight ratio of 5:1 mutually with black petroleum products, obtains mixture; Then said mixture is dropped into reactor, with nitrogen purging, thermal treatment 8h under 440 DEG C and 2Mpa condition; Then within 30 second time, be warmed up to 550 DEG C of Using Coke-ovens obtain needle-like green coke in 8 hours, then carry out calcining graphitization processing at 2800 DEG C, obtain needle coke finished product.
First carry out performance measurement to the mixture of the coal-tar pitch prepared in comparative example and black petroleum products, measurement result is as shown in table 3.
Table 3
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 0.2-0.6 × 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, in comparative example, the QI of needle-shape coke raw material mixture adds 0.11-0.16% compared to embodiment, and β value reduces 6.68-10.38% compared to embodiment, 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 example being described with removing, and the restriction not to embodiment.For the those of ordinary skill send a letter here in described field, other multi-form change or variations can also be made 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 in the protection domain of the invention claim.
Claims (11)
1. a production technique for needle coke, comprises the steps:
(1) coal-tar pitch is mixed with uncombined carbon or containing the component of uncombined carbon, under 320-360 DEG C of condition, obtain modified pitch after reacting by heating;
(2) by above-mentioned modified pitch and solvent evenly after obtain mixed solution, adopt the method for physical sepn to remove insolubles in described mixed solution;
(3) clear liquor obtained after removing insolubles is mixed with petroleum needle-shape coke raw material, be then separated, after isolating solvent, obtain needle-shape coke raw material;
(4) above-mentioned needle-shape coke raw material is carried out delayed coking process, obtain needle-like green coke;
(5) above-mentioned needle-like green coke is prepared needle coke through calcining.
2. the production technique of needle coke according to claim 1, is characterized in that, in described step (1), in the quality of uncombined carbon, described uncombined carbon or containing the component of uncombined carbon and the addition of described coal-tar pitch than being 3:100-20:100.
3. the production technique of needle coke according to claim 1 or 2, is characterized in that, in described step (1), in the quality of uncombined carbon, described uncombined carbon or containing the component of uncombined carbon and the addition of described coal-tar pitch than being 5:100-12:100.
4. according to the production technique of the arbitrary described needle coke of claim 1-3, 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 production technique of the arbitrary described needle coke of claim 1-4, 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 adopt the method for physical sepn to remove insolubles in described mixed solution, this insolubles is the component containing uncombined carbon;
Wherein said solvent is washing oil, to absorb in oil, carbolineum or quinoline any one or a few, and the mass ratio of described solvent and coal-tar pitch is 3-6.
6. according to the production technique of the arbitrary described needle coke of claim 1-4, 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, the mass ratio of described solvent and coal-tar pitch or the component that contains uncombined carbon is 8-10.
7. according to the production technique of the arbitrary described needle coke of claim 1-6, it is characterized in that, in described step (1), described heat-up time is 5-8h.
8. according to the production technique of the arbitrary described 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. the production technique of needle coke according to claim 8, is characterized in that, described coal measures lightweight oil is one or more in gas light oil, tar light oil, petroleum naphtha light oil; Described coal measures aromatic oil is washing oil, absorb in oil, oily, the carbolineum of cresols one or more.
10. according to the production technique of the arbitrary described needle coke of claim 1-9, it is characterized in that, in described step (4), after first needle-shape coke raw material being carried out hydrotreatment in the presence of a hydrogenation catalyst, carry out delayed coking process again; Wherein, the hydrogenation catalyst of described hydrotreatment 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.
11., according to the production technique of the arbitrary described needle coke of claim 1-10, is characterized in that, described petroleum needle-shape coke raw material is through any one of the black petroleum products of furfural extraction, ethylene bottom oil, Catalytic Cracking Residual Oil and thermal cracking residue.
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| CN107532086A (en) * | 2015-05-12 | 2018-01-02 | 株式会社神户制钢所 | Carbon fiber production of raw material for use pitch |
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| CN112105707A (en) * | 2017-12-22 | 2020-12-18 | 卡本控股知识产权有限责任公司 | Method for producing carbon fibers, resins, graphene and other higher carbon materials from coal |
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| CN110408418A (en) * | 2019-08-08 | 2019-11-05 | 平顶山东晟高科实业有限公司 | A kind of preparation method of high regular carbon crystallite pitch coke |
| CN110408418B (en) * | 2019-08-08 | 2021-09-03 | 山西永鑫煤焦化有限责任公司 | Preparation method of high-regular-carbon microcrystalline pitch coke |
| EP3950887A1 (en) * | 2020-08-05 | 2022-02-09 | Indian Oil Corporation Limited | Process for production of graphite coke from an admixture of coal and petroleum based hydrocarbons |
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