CN103087745B - A kind of coal tar that utilizes prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle - Google Patents

A kind of coal tar that utilizes prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle Download PDF

Info

Publication number
CN103087745B
CN103087745B CN201110339693.3A CN201110339693A CN103087745B CN 103087745 B CN103087745 B CN 103087745B CN 201110339693 A CN201110339693 A CN 201110339693A CN 103087745 B CN103087745 B CN 103087745B
Authority
CN
China
Prior art keywords
solvent
needle
coal tar
technique
conjunction
Prior art date
Application number
CN201110339693.3A
Other languages
Chinese (zh)
Other versions
CN103087745A (en
Inventor
井口宪二
坂脇弘二
韩珏
Original Assignee
北京宝塔三聚能源科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 北京宝塔三聚能源科技有限公司 filed Critical 北京宝塔三聚能源科技有限公司
Priority to CN201110339693.3A priority Critical patent/CN103087745B/en
Publication of CN103087745A publication Critical patent/CN103087745A/en
Application granted granted Critical
Publication of CN103087745B publication Critical patent/CN103087745B/en

Links

Abstract

Utilize coal tar to prepare a technique for needle-shape coke raw material in conjunction with heavy phase recycle, comprising: coal tar fully mixes with the first solvent by (1), the method for employing physical sepn removes the first solvent insolubles in described mixture, obtains the first clear liquor; (2) be separated removing first solvent, hydrogenation carried out to the remaining component after described first solvent of removing, obtains refined asphaltic bitumen; (3) fully mixed with the second solvent by the first solvent insolubles, the method for employing physical sepn removes the second solvent insolubles in described mixture, obtains the second clear liquor; (4) be separated the second solvent in described second clear liquor of removing, obtain refining heavy ingredient; (5) by described refined asphaltic bitumen and described refining heavy ingredient mixing, the raw material for the preparation of needle coke is namely obtained.The needle-shape coke raw material that technique in the present invention prepares has more much higher fragrant fused-ring aromatic content, effectively improves the productive rate of described needle coke product.

Description

A kind of coal tar that utilizes prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle
Technical field
The present invention relates to needle coke preparation field, be specifically related to a kind of coal tar that utilizes and prepare the technique of needle-shape coke raw material in conjunction with heavy phase recycle.
Background technology
Needle coke is the quality matetrial manufacturing superpower and ultra-high power graphite electrode, has the advantages such as thermal shock resistance is strong, physical strength is high, oxidation susceptibility is good, consumption of electrode is low and allow current density is large with the Graphite Electrodes that needle coke is made.The needle coke of current production can be divided into petroleum needle coke and the large class of coal-based needle coke two according to using the difference of raw material; big lake carbon element company of the U.S. first developed the production technique of petroleum needle coke in the fifties; but because refining of petroleum trend is towards the future development of catalytic cracking lighting deep processing; the raw material of petroleum needle coke is caused to reduce gradually; in addition the seventies twice oil crisis; people are more made to feel the instability of raw material supply; so from the later stage seventies, the preparation technology of coal-based needle coke is developed.
Coal-based needle coke is that raw material is prepared from coal tar, coal tar main body of oil is polycyclc aromatic compound, also containing a certain amount of quinoline insolubles (QI), quinoline insolubles is when pitch thermal transition generates mesophasespherule, spherular growth can be hindered, make it form carbonization structure, and then affect the quality of needle coke.Therefore, when preparing high-quality needle-shape coke raw material with coal tar, must remove the purifying treatment of quinoline insolubles to coal tar, in the method for many purifying treatment, solvent method is widely used because of simple to operate, low cost.Solvent method is mixed with pitch by suitable solvent, in stirring tank after stirring, leave standstill, precipitating, pitch is made to be dissolved in solvent, thus the mixture of pitch and solvent is formed on upper strata, this mixture is extracted out feeding solvent recovery tower again by pump, recycling design also produces refined asphaltic bitumen, finally obtains the raw material being applicable to preparing needle coke.In prior art, conventional solvent is the mixed solution that aliphatic hydrocarbon and aromatic hydrocarbon are made by a certain percentage.
As Chinese patent literature CN101531909A discloses a kind of continuous sedimentation process for the production of needle coke, this technique take coal tar soft asphalt as raw material, take organic solvent as extraction agent, through the settlement separate quinoline insolubles removed in raw material, the light of acquisition obtains needle coke produced by refined asphaltic bitumen raw material as cracking units after distillation, and the heavy phase settled down then is made outside binder pitch and sold after distillation.The organic solvent used in this technique is exactly the mixture of aliphatic hydrocarbon and aromatic hydrocarbon, and wherein, the mass ratio of described aliphatic hydrocarbon and aromatic hydrocarbon is 1:0.6-1.4; Described organic solvent initial boiling point >=150 DEG C at ambient pressure, the quantity of distillate >=95%(w/w before 310 DEG C).The qualified refined asphaltic bitumen of quinoline insolubles content can be obtained by above-mentioned technique, and there is equipment advantage few, simple to operate.
In fact, the applicant is found by research, in the heavy phase settled down in above-mentioned technique except the quinoline insolubles of obstruction microsphere growth and impurity, also containing a large amount of how fragrant fused-ring aromatic compositions, and this part composition is the basic substance that greying generates needle coke, but but the heavy phase settled down is removed completely in above-mentioned technique, cause the how fragrant fused-ring aromatic component content in the needle-shape coke raw material obtained lower, if so utilize above-mentioned raw materials to prepare needle coke, and then cause the productive rate of described needle coke product lower; And the conventional techniques means of the prior art exactly that this technique embodies, that is, the technology prejudice that technical development those skilled in the art for many years exist all the time is exactly the heavy phase containing substantial quinoline-insoluble content and impurity will be removed, and so just can make in needle-shape coke raw material containing the least possible quinoline insolubles affecting greying process.So, up to the present, in prior art, not yet there is the technology carrying out processing Posterior circle utilization to described heavy phase.
Summary of the invention
Heavy phase composition is isolated owing to completely removes in solvent method in order to solve to use in prior art to prepare in the technique of needle-shape coke raw material, and cause the how fragrant fused-ring aromatic component content in the needle-shape coke raw material obtained lower, and cause thus utilize above-mentioned raw materials to prepare needle coke time, the problem that the productive rate of described needle coke product is lower.The invention provides a kind of coal tar that utilizes and prepare the technique of needle-shape coke raw material in conjunction with heavy phase recycle, the needle-shape coke raw material that this technique prepares has more much higher fragrant fused-ring aromatic content, effectively improves the productive rate of described needle coke product.
The technical scheme utilizing coal tar to prepare the technique of needle-shape coke raw material in conjunction with heavy phase recycle of the present invention is:
Utilize coal tar to prepare a technique for needle-shape coke raw material, comprising:
(1) fully mixed with the first solvent by coal tar, the method for employing physical sepn removes the first solvent insolubles in described mixture, obtains the first clear liquor;
Described first solvent is lightweight oil, and the mass ratio of described first solvent and described coal tar is 0.05-10;
(2) be separated the first solvent in described first clear liquor of removing, hydrogenation carried out to the remaining component after described first solvent of removing, obtains refined asphaltic bitumen;
(3) fully mixed with the second solvent by the first solvent insolubles obtained in step (1), the method for employing physical sepn removes the second solvent insolubles in described mixture, obtains the second clear liquor;
Described second solvent is matter oil in coal measures, and in described coal measures, matter oil is 1:0.1-1:2 with the mass ratio of described lightweight oil, and the mass ratio of described second solvent and described first solvent insolubles is 0.5-50;
(4) be separated the second solvent in described second clear liquor of removing, obtain refining heavy ingredient;
(5) by described refined asphaltic bitumen and described refining heavy ingredient mixing, the raw material for the preparation of needle coke is namely obtained.
The mass ratio of described first solvent and described coal tar is 0.1-5.
The mass ratio of described first solvent and described coal tar is 0.3-0.7.
In described coal measures, matter oil is 1:0.1-1:1 with the mass ratio of described lightweight oil.
The mass ratio of described second solvent and described first solvent insolubles is 1-10.
Described lightweight oil is coal measures lightweight oil.
Described coal measures lightweight oil is one or more in vapour light oil, BTX, tar light oil, petroleum naphtha.
In described coal measures, matter oil is one or more in washing oil, absorption oil, creosote, carbolineum.
The temperature of described hydrogenation reaction is 300-400 DEG C, and pressure is 5-20MPa.
Hydrogenation catalyst is nickel molybdenum series catalyst.
The temperature of described hydrogenation reaction is 300-350 DEG C, and pressure is 10-15MPa.
Physical sepn in described step (1) and step (3) is centrifugation, and the centrifugal acceleration of described centrifugation is 2000-4000G.
The centrifugal acceleration of described centrifugation is 2200-3500G.
The coal tar that utilizes of the present invention prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle, and coal tar fully mixes with the first solvent by step (1), and the method for employing physical sepn removes the first solvent insolubles in described mixture, obtains the first clear liquor; Wherein, described first solvent is chosen as lightweight oil, and the mass ratio of described first solvent and described coal tar is 0.05-10, is preferably 0.1-5, more preferably 0.3-0.7; This step is to provide to hydrogenation reaction the raw material that quinoline insolubles content is low, because in hydrogenation reaction, quinoline insolubles in raw material can cause hydrogenation catalyst deterioration, reduce speed of reaction, the productive rate of described hydrogenation reaction is reduced, and economy also declines thereupon, therefore, for making hydrotreatment carry out for a long time, stably, need in advance by the quinoline insolubles removing in asphalt stock.
Step (2) is separated the first solvent in described first clear liquor of removing, carries out hydrogenation, obtain refined asphaltic bitumen to the remaining component after described first solvent of removing; The object of removing lightweight oil solvent is the processing efficiency improving described hydrogenator.Hydrotreatment is carried out to described heavy ends, object is the carbohydrate content in order to improve in described pitch, and in the process of hydrotreatment, the impurity in described pitch can be removed, thus substantially increase carbohydrate content, effectively prevent the swelling of needle coke product.
The the first solvent insolubles obtained in step (1) fully mixes with the second solvent by step (3), and the method for employing physical sepn removes the second solvent insolubles in described mixture, obtains the second clear liquor; Described second solvent is matter oil in coal measures, and in described coal measures, matter oil is 1:0.1-1:2 with the mass ratio of described lightweight oil, and is preferably set to 1:0.1-1:1; The mass ratio of described second solvent and described first solvent insolubles is 0.5-50, and be preferably set to 1-10, the object of this step is to refine heavy ends isolated in solvent method further, extract how fragrant fused-ring aromatic composition wherein, thus abandon the technology prejudice that heavy phase that existing technical staff thinks containing substantial quinoline-insoluble content and impurity ought to remove.In coal measures in the present invention, matter oil refers to the oil product of boiling temperature within the scope of 220-350 DEG C.
Step (4) is separated the second solvent in described second clear liquor of removing with (5), obtain refining heavy ingredient; Again by described refined asphaltic bitumen and described refining heavy ingredient mixing, thus obtain the higher needle-shape coke raw material of how fragrant fused-ring aromatic component content, effectively improve the productive rate of needle coke product.
The technological advantage utilizing coal tar to prepare needle-shape coke raw material in conjunction with heavy phase recycle described in the present invention is:
(1) coal tar that utilizes described in the present invention prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle, first coal-tar pitch is fully mixed with the first solvent, the method of employing physical sepn removes the first solvent insolubles in described mixture, obtain the first clear liquor, after hydrogenation is carried out to described first clear liquor, obtain refined asphaltic bitumen; Again described first solvent insolubles is fully mixed with matter oil in coal measures, the method of employing physical sepn removes the insolubles in described mixture, obtain the second clear liquor, remove in the coal measures in described second clear liquor and obtain refining heavy ends after matter oil, finally described refined asphaltic bitumen is mixed with described refining heavy ends, namely obtain the raw material for the preparation of needle coke.The present invention has abandoned the technology prejudice that heavy phase that existing technical staff thinks containing substantial quinoline-insoluble content and impurity ought to remove, by using matter oil in coal measures, described first solvent insolubles is extracted, effectively can extract how fragrant fused-ring aromatic composition wherein, refining heavy ends containing a large amount of how fragrant fused-ring aromatic composition is back to and prepares needle coke, effectively can improve the productive rate of described needle coke product.
(2) coal tar that utilizes described in the present invention prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle, arranging described lightweight oil is coal measures lightweight oil, and the described coal measures lightweight oil of restriction is one or more in vapour light oil, BTX, tar light oil, petroleum naphtha further.Reason is to use this several oil to be suitable for the uncombined carbon in coal tar, solid impurity containing uncombined carbon and heavy ingredient effectively to separate.
(3) coal tar that utilizes described in the present invention prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle, and the method selecting the physical sepn arranged in described step (1) and (3) is centrifugation, and the centrifugal acceleration of described centrifugation is 2000-4000G.Reason with, the method for described centrifugation, compared to other physical separation method, such as filtration method, settling process etc., has higher separation efficiency, by described centrifugal method, effectively can remove the quinoline insolubles in described coal tar raw material.In order to improve centrifugal effect further, it is 2200-3500G that the present invention also limits described centrifugal acceleration further.
Accompanying drawing explanation
More being convenient to make content of the present invention understand, below in conjunction with accompanying drawing embodiment, technical solutions according to the invention being described further;
That the coal tar that utilizes of the present invention prepares the schematic diagram of needle-shape coke raw material technique in conjunction with heavy phase recycle as shown in Figure 1.
Embodiment
embodiment 1
the coal tar that utilizes described in the present embodiment prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle, comprising:
(1) fully mixed with the first solvent by coal tar, the method for employing filtering separation removes the first solvent insolubles in described mixture, obtains the first clear liquor;
First solvent described in the present embodiment is petroleum petroleum naphtha, and the mass ratio of described first solvent and described coal tar is 0.05;
(2) be separated the first solvent in described first clear liquor of removing, carry out hydrogenation to the remaining component after described first solvent of removing, obtain refined asphaltic bitumen, the temperature of described hydrogenation reaction is 410 DEG C, and reaction pressure is 22MPa;
(3) fully mixed with the second solvent by the first solvent insolubles obtained in step (1), the method for employing physical sepn removes the second solvent insolubles in described mixture, obtains the second clear liquor;
The second solvent selected in the present embodiment is used as the petroleum petroleum naphtha of the first solvent and the mixture of washing oil, and the mass ratio of described washing oil and described petroleum petroleum naphtha is 1:2; The mass ratio of described second solvent and described first solvent insolubles is 0.5;
(4) be separated the second solvent in described second clear liquor of removing, obtain refining heavy ingredient;
(5) by described refined asphaltic bitumen and described refining heavy ingredient mixing, the raw material for the preparation of needle coke is namely obtained.
embodiment 2
The coal tar that utilizes described in the present embodiment prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle, comprising:
(1) coal tar is fully mixed with the first solvent, adopt settlement separate method to remove the first solvent insolubles in described mixture, obtain the first clear liquor;
First solvent described in the present embodiment is petroleum petroleum naphtha, and the mass ratio of described first solvent and described coal tar is 10;
(2) be separated the first solvent in described first clear liquor of removing, carry out hydrogenation to the remaining component after described first solvent of removing, obtain refined asphaltic bitumen, the temperature of described hydrogenation reaction is 410 DEG C, and reaction pressure is 22MPa;
(3) fully mixed with the second solvent by the first solvent insolubles obtained in step (1), the method for employing physical sepn removes the second solvent insolubles in described mixture, obtains the second clear liquor;
The second solvent selected in the present embodiment is used as the petroleum petroleum naphtha of the first solvent and the mixture absorbing oil, and absorbing oil with the mass ratio of described petroleum petroleum naphtha is 1:2; The mass ratio of described second solvent and described first solvent insolubles is 50;
(4) be separated the second solvent in described second clear liquor of removing, obtain refining heavy ingredient;
(5) by described refined asphaltic bitumen and described refining heavy ingredient mixing, the raw material for the preparation of needle coke is namely obtained.
embodiment 3
The coal tar that utilizes described in the present embodiment prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle, comprising:
(1) coal tar is fully mixed with the first solvent, adopt settlement separate method to remove the first solvent insolubles in described mixture, obtain the first clear liquor;
First solvent described in the present embodiment is petroleum petroleum naphtha, and the mass ratio of described first solvent and described coal tar is 0.1;
(2) be separated the first solvent in described first clear liquor of removing, carry out hydrogenation to the remaining component after described first solvent of removing, obtain refined asphaltic bitumen, the temperature of described hydrogenation reaction is 400 DEG C, and reaction pressure is 5MPa;
(3) fully mixed with the second solvent by the first solvent insolubles obtained in step (1), the method for employing physical sepn removes the second solvent insolubles in described mixture, obtains the second clear liquor;
The second solvent selected in the present embodiment is used as the petroleum petroleum naphtha of the first solvent and the mixture absorbing oil, and absorbing oil with the mass ratio of described petroleum petroleum naphtha is 1:2; The mass ratio of described second solvent and described first solvent insolubles is 10;
(4) be separated the second solvent in described second clear liquor of removing, obtain refining heavy ingredient;
(5) by described refined asphaltic bitumen and described refining heavy ingredient mixing, the raw material for the preparation of needle coke is namely obtained.
embodiment 4
The coal tar that utilizes described in the present embodiment prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle, comprising:
(1) coal tar is fully mixed with the first solvent, adopt settlement separate method to remove the first solvent insolubles in described mixture, obtain the first clear liquor;
First solvent described in the present embodiment is petroleum petroleum naphtha, and the mass ratio of described first solvent and described coal tar is 5;
(2) be separated the first solvent in described first clear liquor of removing, carry out hydrogenation to the remaining component after described first solvent of removing, obtain refined asphaltic bitumen, the temperature of described hydrogenation reaction is 400 DEG C, and reaction pressure is 20MPa;
(3) fully mixed with the second solvent by the first solvent insolubles obtained in step (1), the method for employing physical sepn removes the second solvent insolubles in described mixture, obtains the second clear liquor;
The second solvent selected in the present embodiment is used as the petroleum petroleum naphtha of the first solvent and the mixture absorbing oil, and described absorption oil is 1:2 with the mass ratio of described petroleum petroleum naphtha; The mass ratio of described second solvent and described first solvent insolubles is 1;
(4) be separated the second solvent in described second clear liquor of removing, obtain refining heavy ingredient;
(5) by described refined asphaltic bitumen and described refining heavy ingredient mixing, the raw material for the preparation of needle coke is namely obtained.
embodiment 5
The coal tar that utilizes described in the present embodiment prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle, comprising:
(1) coal tar is fully mixed with the first solvent, adopt settlement separate method to remove the first solvent insolubles in described mixture, obtain the first clear liquor;
First solvent described in the present embodiment is coal measures lightweight oil, and described coal measures lightweight oil is vapour light oil, and the mass ratio of described first solvent and described coal tar is 0.3;
(2) be separated the first solvent in described first clear liquor of removing, carry out hydrogenation to the remaining component after described first solvent of removing, obtain refined asphaltic bitumen, the temperature of described hydrogenation reaction is 350 DEG C, and reaction pressure is 10MPa;
(3) fully mixed with the second solvent by the first solvent insolubles obtained in step (1), the method for employing physical sepn removes the second solvent insolubles in described mixture, obtains the second clear liquor;
The second solvent selected in the present embodiment is used as the vapour light oil of the first solvent and the mixture absorbing oil, and described absorption oil is 1:1.5 with the mass ratio of described vapour light oil; The mass ratio of described second solvent and described first solvent insolubles is 1;
(4) be separated the second solvent in described second clear liquor of removing, obtain refining heavy ingredient; The mass ratio of described second solvent and described first solvent insolubles is 5;
(5) by described refined asphaltic bitumen and described refining heavy ingredient mixing, the raw material for the preparation of needle coke is namely obtained.
embodiment 6
The coal tar that utilizes described in the present embodiment prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle, comprising:
(1) coal tar is fully mixed with the first solvent, adopt settlement separate method to remove the first solvent insolubles in described mixture, obtain the first clear liquor;
First solvent described in the present embodiment is coal measures lightweight oil, and described coal measures lightweight oil is BTX, and the mass ratio of described first solvent and described coal tar is 0.7;
(2) be separated the first solvent in described first clear liquor of removing, carry out hydrogenation to the remaining component after described first solvent of removing, obtain refined asphaltic bitumen, the temperature of described hydrogenation reaction is 320 DEG C, and reaction pressure is 12MPa;
(3) fully mixed with the second solvent by the first solvent insolubles obtained in step (1), the method for employing physical sepn removes the second solvent insolubles in described mixture, obtains the second clear liquor;
The second solvent selected in the present embodiment is coal measures vapour light oil and the mixture absorbing oil, and described absorption oil is 1:2 with the mass ratio of described vapour light oil; The mass ratio of described second solvent and described first solvent insolubles is 1;
(4) be separated the second solvent in described second clear liquor of removing, obtain refining heavy ingredient;
(5) by described refined asphaltic bitumen and described refining heavy ingredient mixing, the raw material for the preparation of needle coke is namely obtained.
embodiment 7
The coal tar that utilizes described in the present embodiment prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle, comprising:
(1) fully mixed with the first solvent by coal tar, the method for employing centrifugation removes the first solvent insolubles in described mixture, and obtain the first clear liquor, the centrifugal acceleration of described centrifugation is 2000G;
First solvent described in the present embodiment is coal measures lightweight oil, and described coal measures lightweight oil is petroleum naphtha, and the mass ratio of described first solvent and described coal tar is 0.5;
(2) be separated the first solvent in described first clear liquor of removing, carry out hydrogenation to the remaining component after described first solvent of removing, obtain refined asphaltic bitumen, the temperature of described hydrogenation reaction is 300 DEG C, and reaction pressure is 15MPa;
(3) fully mixed with the second solvent by the first solvent insolubles obtained in step (1), the method for employing physical sepn removes the second solvent insolubles in described mixture, obtains the second clear liquor;
The second solvent selected in the present embodiment is the mixture of coal measures tar light oil and carbolineum, and the mass ratio of described carbolineum and described tar light oil is 1:0.1; The mass ratio of described second solvent and described first solvent insolubles is 10;
(4) be separated the second solvent in described second clear liquor of removing, obtain refining heavy ingredient;
(5) by described refined asphaltic bitumen and described refining heavy ingredient mixing, the raw material for the preparation of needle coke is namely obtained.
embodiment 8
The coal tar that utilizes described in the present embodiment prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle, comprising:
(1) fully mixed with the first solvent by coal tar, the method for employing centrifugation removes the first solvent insolubles in described mixture, and obtain the first clear liquor, the centrifugal acceleration of described centrifugation is 4000G;
First solvent described in the present embodiment is coal measures lightweight oil, and described coal measures lightweight oil is vapour light oil, and the mass ratio of described first solvent and described coal tar is 0.3;
(2) be separated the first solvent in described first clear liquor of removing, carry out hydrogenation to the remaining component after described first solvent of removing, obtain refined asphaltic bitumen, the temperature of described hydrogenation reaction is 350 DEG C, and reaction pressure is 15MPa;
(3) fully mixed with the second solvent by the first solvent insolubles obtained in step (1), the method for employing physical sepn removes the second solvent insolubles in described mixture, obtains the second clear liquor;
The second solvent selected in the present embodiment is the mixture of coal measures tar light oil and carbolineum, and the mass ratio of described carbolineum and described tar light oil is 1:1; The mass ratio of described second solvent and described first solvent insolubles is 1;
(4) be separated the second solvent in described second clear liquor of removing, obtain refining heavy ingredient;
(5) by described refined asphaltic bitumen and described refining heavy ingredient mixing, the raw material for the preparation of needle coke is namely obtained.
embodiment 9
The coal tar that utilizes described in the present embodiment prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle, comprising:
(1) fully mixed with the first solvent by coal tar, the method for employing centrifugation removes the first solvent insolubles in described mixture, and obtain the first clear liquor, the centrifugal acceleration of described centrifugation is 2200G;
First solvent described in the present embodiment is coal measures lightweight oil, and described coal measures lightweight oil is vapour light oil, and the mass ratio of described first solvent and described coal tar is 0.7;
(2) be separated the first solvent in described first clear liquor of removing, carry out hydrogenation to the remaining component after described first solvent of removing, obtain refined asphaltic bitumen, the temperature of described hydrogenation reaction is 330 DEG C, and reaction pressure is 15MPa;
(3) fully mixed with the second solvent by the first solvent insolubles obtained in step (1), the method for employing physical sepn removes the second solvent insolubles in described mixture, obtains the second clear liquor;
Described second solvent is the mixture of coal measures tar light oil and creosote, and the mass ratio of described creosote and described tar light oil is 1:1; The mass ratio of described second solvent and described first solvent insolubles is 1;
(4) be separated the second solvent in described second clear liquor of removing, obtain refining heavy ingredient;
(5) by described refined asphaltic bitumen and described refining heavy ingredient mixing, the raw material for the preparation of needle coke is namely obtained.
embodiment 10
The coal tar that utilizes described in the present embodiment prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle, comprising:
(1) fully mixed with the first solvent by coal tar, the method for employing centrifugation removes the first solvent insolubles in described mixture, and obtain the first clear liquor, the centrifugal acceleration of described centrifugation is 3500G;
First solvent described in the present embodiment is coal measures lightweight oil, and described coal measures lightweight oil is vapour light oil, and the mass ratio of described first solvent and described coal tar is 0.3;
(2) be separated the first solvent in described first clear liquor of removing, carry out hydrogenation to the remaining component after described first solvent of removing, obtain refined asphaltic bitumen, the temperature of described hydrogenation reaction is 350 DEG C, and reaction pressure is 10MPa;
(3) fully mixed with the second solvent by the first solvent insolubles obtained in step (1), the method for employing physical sepn removes the second solvent insolubles in described mixture, obtains the second clear liquor;
Described second solvent is the mixture of coal measures tar light oil and carbolineum, and the mass ratio of described carbolineum and described tar light oil is 1:1; The mass ratio of described second solvent and described first solvent insolubles is 1;
(4) be separated the second solvent in described second clear liquor of removing, obtain refining heavy ingredient;
(5) by described refined asphaltic bitumen and described refining heavy ingredient mixing, the raw material for the preparation of needle coke is namely obtained.
In the above-described embodiments, as preferred embodiment, described hydrogenation reaction is carried out under nickel molybdenum series hydrocatalyst existent condition, and described nickel molybdenum series hydrocatalyst is prepared from a catalyst support described active ingredient Ni and Mo load, and described carrier is 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 is commercially available product.Certainly, as selectable embodiment, also such as FeS can be selected 2deng the hydrogenation catalyst of other kind.
experimental example
In order to prove that technical solutions according to the invention have substantial technique effect compared to prior art, below in conjunction with specific experiment example, the technique effect of technical scheme of the present invention is described further.
The mensuration of experiment 1:QI content and hydrocarbon concentration
The QI content of the first clear liquor obtained after removal the first solvent insolubles in above-described embodiment step (1) is measured, result shows that the first clear liquor QI content in embodiment 1-10 is all lower than 0.01wt%, and the initial Q I concentration of the coal tar raw material used in above-described embodiment is 5.2wt%.
Concentration for the preparation of the QI content in the raw material of needle coke and carbon and hydrogen described in obtaining in above-described embodiment measures, result show in embodiment 1-10 obtained for the preparation of the QI content in the raw material of needle coke all lower than 0.01wt%.The described concentration for the preparation of the carbon in the raw material of needle coke and hydrogen is as shown in the table:
Experiment 2: the mensuration of needle coke thermal expansivity and productive rate
When testing, described in obtaining in above-described embodiment, putting into for the preparation of the raw material of needle coke the coker preparing needle coke, 550 DEG C of condition Using Coke-ovens 5 hours, obtaining needle coke.
Described needle coke product is carried out graphitization processing under 1300 DEG C of conditions, and the thermal expansivity of the needle coke after greying is as shown in the table:
Needle coke productive rate when preparing needle coke to described raw material obtained above further measures, and obtains result as shown in the table:
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:
(1) adopt the coal tar raw material identical with embodiment, fully mixed by described coal tar with solvent, the method for employing filtering separation removes the solvent insolubles in described mixture, obtains clear liquor;
Solvent described in this comparative example is the mixture of aliphatic hydrocarbon and aromatic hydrocarbon, and the mass ratio of described aliphatic hydrocarbon and aromatic hydrocarbon is 1:1; Described solvent initial boiling point at ambient pressure about 160 DEG C, the quantity of distillate of described mixture before 310 DEG C is 97%(w/w)
(2) be separated the solvent in the described clear liquor of removing, namely obtain the raw material for the preparation of needle coke.
Described in obtaining in this comparative example, put into for the preparation of the raw material of needle coke the coker preparing needle coke, 550 DEG C of condition Using Coke-ovens 5 hours, obtain needle coke.
Described needle coke product is carried out graphitization processing under 1300 DEG C of conditions, and the thermal expansivity of the needle coke after greying is 1.5 × 10 -6/ DEG C.
Needle coke productive rate when needle coke prepared by the described raw material obtained this comparative example further measures, and the productive rate obtaining needle coke is 35%.
By above-mentioned more known, in comparative example, the thermal expansivity of needle coke adds 0.4-0.8 × 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 productive rate of needle coke reduces 12-18% compared to embodiment, and the technical scheme in visible the present invention can significantly improve the productive rate of needle coke product, therefore, technical scheme in the present invention, compared to prior art, has obvious Substantial technical effect.
Although the present invention is elaborated it by embodiment; but; those skilled in the art should be understood that and made on this basis not exceed any form of claims and the change of details, all belong to invention which is intended to be protected.

Claims (17)

1. utilize coal tar to prepare a technique for needle-shape coke raw material in conjunction with heavy phase recycle, comprising:
(1) fully mixed with the first solvent by coal tar, the method for employing physical sepn removes the first solvent insolubles in described mixture, obtains the first clear liquor;
Described first solvent is coal measures lightweight oil, and the mass ratio of described first solvent and described coal tar is 0.05-10;
(2) be separated the first solvent in described first clear liquor of removing, hydrogenation carried out to the remaining component after described first solvent of removing, obtains refined asphaltic bitumen;
(3) fully mixed with the second solvent by the first solvent insolubles obtained in step (1), the method for employing physical sepn removes the second solvent insolubles in described mixture, obtains the second clear liquor;
Described second solvent is matter oil in coal measures, and in described coal measures, matter oil is 1:0.1-1:2 with the mass ratio of described coal measures lightweight oil, and the mass ratio of described second solvent and described first solvent insolubles is 0.5-50;
(4) be separated the second solvent in described second clear liquor of removing, obtain refining heavy ingredient;
(5) by described refined asphaltic bitumen and described refining heavy ingredient mixing, the raw material for the preparation of needle coke is namely obtained.
2. the coal tar that utilizes according to claim 1 prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle, it is characterized in that, the mass ratio of described first solvent and described coal tar is 0.1-5.
3. the coal tar that utilizes according to claim 2 prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle, it is characterized in that, the mass ratio of described first solvent and described coal tar is 0.3-0.7.
4. the coal tar that utilizes according to claim 1 or 2 or 3 prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle, it is characterized in that, in described coal measures, matter oil is 1:0.1-1:1 with the mass ratio of described coal measures lightweight oil.
5. the coal tar that utilizes according to claim 1 or 2 or 3 prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle, it is characterized in that, the mass ratio of described second solvent and described first solvent insolubles is 1-10.
6. the coal tar that utilizes according to claim 4 prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle, it is characterized in that, the mass ratio of described second solvent and described first solvent insolubles is 1-10.
7. the coal tar that utilizes according to claim 1,2,3 or 6 prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle, it is characterized in that, described coal measures lightweight oil is one or more in vapour light oil, BTX, tar light oil, petroleum naphtha.
8. the coal tar that utilizes according to claim 1,2,3 or 6 prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle, it is characterized in that, in described coal measures, matter oil is one or more in washing oil, absorption oil, creosote, carbolineum.
9. the coal tar that utilizes according to claim 1,2,3 or 6 prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle, it is characterized in that, the temperature of described hydrogenation reaction is 300-400 DEG C, and pressure is 5-20MPa.
10. the coal tar that utilizes according to claim 4 prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle, it is characterized in that, the temperature of described hydrogenation reaction is 300-400 DEG C, and pressure is 5-20MPa.
11. coal tar that utilize according to claim 5 prepare the technique of needle-shape coke raw material in conjunction with heavy phase recycle, it is characterized in that, the temperature of described hydrogenation reaction is 300-400 DEG C, and pressure is 5-20MPa.
12. coal tar that utilize according to claim 7 prepare the technique of needle-shape coke raw material in conjunction with heavy phase recycle, it is characterized in that, the temperature of described hydrogenation reaction is 300-400 DEG C, and pressure is 5-20MPa.
13. coal tar that utilize according to claim 8 prepare the technique of needle-shape coke raw material in conjunction with heavy phase recycle, it is characterized in that, the temperature of described hydrogenation reaction is 300-400 DEG C, and pressure is 5-20MPa.
14. according to claim 1,2,3,6, the coal tar that utilizes described in any one of 10-13 prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle, it is characterized in that, hydrogenation catalyst is nickel molybdenum series catalyst.
15. according to claim 1,2,3,6, the coal tar that utilizes described in any one of 10-13 prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle, it is characterized in that, the temperature of described hydrogenation reaction is 300-350 DEG C, and pressure is 10-15MPa.
16. according to claim 1,2,3,6, the coal tar that utilizes according to any one of 10-13 prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle, it is characterized in that, physical sepn in described step (1) and step (3) is centrifugation, and the centrifugal acceleration of described centrifugation is 2000-4000G.
17. coal tar that utilize according to claim 16 prepare the technique of needle-shape coke raw material in conjunction with heavy phase recycle, it is characterized in that, the centrifugal acceleration of described centrifugation is 2200-3500G.
CN201110339693.3A 2011-11-01 2011-11-01 A kind of coal tar that utilizes prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle CN103087745B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201110339693.3A CN103087745B (en) 2011-11-01 2011-11-01 A kind of coal tar that utilizes prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201110339693.3A CN103087745B (en) 2011-11-01 2011-11-01 A kind of coal tar that utilizes prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle

Publications (2)

Publication Number Publication Date
CN103087745A CN103087745A (en) 2013-05-08
CN103087745B true CN103087745B (en) 2015-09-02

Family

ID=48200891

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201110339693.3A CN103087745B (en) 2011-11-01 2011-11-01 A kind of coal tar that utilizes prepares the technique of needle-shape coke raw material in conjunction with heavy phase recycle

Country Status (1)

Country Link
CN (1) CN103087745B (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103962187B (en) * 2014-05-08 2016-08-31 北京宝塔三聚能源科技有限公司 Hydrogenation upgrading catalyst carrier and preparation method thereof, use the hydrogenation upgrading catalyst of this carrier
CN106520164B (en) * 2016-10-28 2019-08-23 中国矿业大学(北京) A kind of method that overcritical combination extraction mode separates needle-shape coke raw material from high temperature coal-tar
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
CN109943354B (en) * 2019-03-29 2020-09-22 山东益大新材料股份有限公司 Co-carbonization process of mixed raw material of aromatic oil and refined asphalt
CN110396423A (en) * 2019-08-22 2019-11-01 七台河宝泰隆新能源有限公司 A kind of device of hydrogenation of high temperature coal tar coproduction needle coke
CN111834634A (en) * 2020-07-07 2020-10-27 鞍钢化学科技有限公司 High-performance artificial graphite negative electrode material and production process thereof
CN111826188A (en) * 2020-07-07 2020-10-27 鞍钢化学科技有限公司 Raw material asphalt for carbon-based new material and production process thereof
CN111826187A (en) * 2020-07-07 2020-10-27 鞍钢化学科技有限公司 Novel high-performance asphalt special for carbon material and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101787298A (en) * 2009-01-23 2010-07-28 北京石油化工学院 Coal art pitch purification method
CN101962560A (en) * 2010-09-29 2011-02-02 神华集团有限责任公司 Extraction method of direct coal liquefaction residues and application of extracts

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101787298A (en) * 2009-01-23 2010-07-28 北京石油化工学院 Coal art pitch purification method
CN101962560A (en) * 2010-09-29 2011-02-02 神华集团有限责任公司 Extraction method of direct coal liquefaction residues and application of extracts

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
中温沥青的喹啉不溶物脱除;孙振兴等;《炭素技术》;20091231;第28卷(第3期);第10-13页 *
煤焦油脱除喹啉不溶物( QI) 的净化处理研究;罗道成等;《煤化工》;20080430(第2期);第11-13页 *
煤系针状焦原料预处理技术进展;郭少青等;《炭素技术》;20110630;第30卷(第3期);第40-43页 *

Also Published As

Publication number Publication date
CN103087745A (en) 2013-05-08

Similar Documents

Publication Publication Date Title
US6183854B1 (en) Method of making a reinforced carbon foam material and related product
JP4866351B2 (en) Process for direct coal liquefaction
KR101610989B1 (en) Process for producing binder for coke production and process for producing coke
CN102127462B (en) Direct biomass hydroliquefaction process comprising two ebullated bed hydroconversion steps
AU662644B2 (en) Process for producing solvated mesophase pitch and carbon artifacts therefrom
JP4045229B2 (en) Production method of ashless coal
CN101962560B (en) Extraction method of direct coal liquefaction residues and application of extracts
CA1130743A (en) Process for the production of a petroleum pitch or coke of a high purity
CN101885982B (en) Hydrogenation method for coal tar suspension bed of heterogeneous catalyst
JP2013523592A (en) Method for producing a carbonaceous material
CN102225755B (en) Preparation method of mesophase carbon microspheres from coal liquefaction residues
CN101511977A (en) Method for production of ashless coal
CN101580729B (en) Method for preparing mesophase asphalt by coal liquefaction residue
CN102399565B (en) Method for extracting heavy liquefied oil from residue of coal direct liquefaction, extracted heavy liquefied oil, and application thereof
CN103265971B (en) Heterogeneous coal tar suspension bed hydrogenation method
WO2006109497A1 (en) Process for production of mesocarbon microbeads
CN104650938B (en) Needle coke, MCMB, the joint production process method of high-quality asphalt
CN101724421B (en) Production method of needle coke
CN102796559B (en) Method and the device of oil fuel are produced in hydrocracking
CN102492451A (en) Extracting and separating method of high-temperature coal tar
CN1597866A (en) Process for producing chemical industry products and fuel oil from coal tar
KR20120026561A (en) Method for producing carbon materials
AU603223B2 (en) Process for preparing pitches
CN105238430B (en) A kind of method that catalytic cracked oil pulp hydroisomerizing thermal polycondensation prepares mesophase pitch
CN107694552B (en) A kind of technique that coal-based needle coke is produced as raw material using middle coalite tar pitch

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
TA01 Transfer of patent application right

Effective date of registration: 20130802

Address after: 100080 Beijing, Renmin University, North Road, No. 33, building 1429, room 1, room

Applicant after: Beijing Baotasanju Energy Technology Co., Ltd.

Address before: 100080 Beijing City People's Congress of Haidian District No. 33 North Road, building 17 Dahon Foundation

Applicant before: Beijing Sanju Chuangjie Technology Development Co.,Ltd.

Effective date of registration: 20130802

Address after: 100080 Beijing, Renmin University, North Road, No. 33, building 1429, room 1, room

Applicant after: Beijing Baotasanju Energy Technology Co., Ltd.

Address before: 100080 Beijing City People's Congress of Haidian District No. 33 North Road, building 17 Dahon Foundation

Applicant before: Beijing Sanju Chuangjie Technology Development Co.,Ltd.

ASS Succession or assignment of patent right

Owner name: BAODING BAOTA TRIMERIZATION ENERGY TECHNOLOGY CO.,

Free format text: FORMER OWNER: BEIJING SANJU CHUANGJIE TECHNOLOGY DEVELOPMENT CO., LTD.

Effective date: 20130802

C41 Transfer of patent application or patent right or utility model
SE01 Entry into force of request for substantive examination
C10 Entry into substantive examination
GR01 Patent grant
C14 Grant of patent or utility model
CP01 Change in the name or title of a patent holder

Address after: 100080 Beijing, Renmin University, North Road, No. 33, building 1429, room 1, room

Patentee after: Beijing Baoju Energy Technology Co Ltd

Address before: 100080 Beijing, Renmin University, North Road, No. 33, building 1429, room 1, room

Patentee before: Beijing Baotasanju Energy Technology Co., Ltd.

Address after: 100080 Beijing, Renmin University, North Road, No. 33, building 1429, room 1, room

Patentee after: Beijing Baoju Energy Technology Co Ltd

Address before: 100080 Beijing, Renmin University, North Road, No. 33, building 1429, room 1, room

Patentee before: Beijing Baotasanju Energy Technology Co., Ltd.

CP01 Change in the name or title of a patent holder
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20201021

Address after: 100080, Beijing, Haidian District North Road, No. 33, building 1, foundation building, 9 floor

Patentee after: BEIJING SJ ENVIRONMENTAL PROTECTION AND NEW MATERIAL Co.,Ltd.

Address before: 100080, room 1, building 33, 1429 North Road, Renmin University, Beijing, Haidian District

Patentee before: BEIJING BAOJU ENERGY SCIENCE AND TECHNOLOGY Co.,Ltd.