CN101565630B - Method for preparing orderly mesophase needle coke - Google Patents
Method for preparing orderly mesophase needle coke Download PDFInfo
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- CN101565630B CN101565630B CN 200910074451 CN200910074451A CN101565630B CN 101565630 B CN101565630 B CN 101565630B CN 200910074451 CN200910074451 CN 200910074451 CN 200910074451 A CN200910074451 A CN 200910074451A CN 101565630 B CN101565630 B CN 101565630B
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Abstract
A method for preparing orderly mesophase needle coke takes coal tar pitch as the raw material, generates directional action to the molecular orientation of polycyclic aromatic hydrocarbons in thermal polymerization under the joint action of the stretching of an electric field and air flow, and solves the problem that the directional arrangement to the mesophase is difficult to control by only adopting the stretching action of an air flow field. The technical process comprises the steps of: leading the raw material coal tar pitch to conduct purification treatment and then ultrasound treatment, centrifugation, and solvent removing, later placing the coal tar pitch in a reactor with an electric field generating device under the protection of inert gas for programmed temperature, and beginning to impose an electric field with the strength of 8.0x10<4>-1.0x10<6>V/m when the temperature is increased to 100 DEG C-120 DEG C, and then maintaining for 1-2.5h when the temperature is increased to400 DEG C-500 DEG C, and finally cutting off the electric field and stopping heating when the temperature continues to be increased to 500 DEG C-580 DEG C and is maintained for 9-20h, thereby preparing the orderly mesophase needle coke.
Description
Technical field
The present invention relates to a kind of preparation method of orderly mesophase needle coke, especially a kind ofly produce the preparation that directive action realizes orderly mesophase needle coke by the molecular orientation to the polycyclic arene compound of hot polymerization reaction under the electric field booster action.
Technical background
Needle coke be a kind of structure very in order, degree of graphitization is very high, a class Carbon Materials with utmost point low thermal coefficient of expansion, is widely used in computer, space flight, nuclear industry and the field such as metallurgical.Prepare the ultra-high power graphite electrode that Electric furnace steel making is used such as metallurgical industry with needle coke, can improve efficiency and output of steel, reduce power consumption and steel-making cost.It is different with raw material sources to press machining, and needle coke divides oil system and coal measures two large classes.Needle coke take petroleum residual oil as raw material production as oil be needle coke; Needle coke take coal-tar pitch and cut thereof as raw material production is as coal-based needle coke.The storage capacity of nature coal rationally utilizes coal resource that protection of the environment, energy-saving and emission-reduction and economic Sustainable development are had important practical significance more than rich in petroleum resources.Coal tar or coal-tar pitch are the by products of coal tar process, and its composition is very complicated.Research can significantly promote coal deep-processing process middle and lower reaches value-added content of product take coal tar or coal-tar pitch as the high high-quality needle coke of raw material production added value, is conducive to adjust enterprise's industrial structure.
Existing document, publication number is that CN1418931 has reported " a kind of method for preparing needle coke ", proposed heating raw materials to a certain degree rear by having put aside a certain amount of gas in the system, then venting decompression, make the anisotropy zone produce wall pressure and shearing force along air flow line, thereby form strong airflow scouring power, make whole anisotropy zone when air-flow is discharged, force to align, realize that by changing the air-flow size the middle mutually anisotropic order of control is orientated to improve the quality product of needle coke.Yet, this middle mutually orientation of air-flow size control that only depends on is difficult to form stable middle phase structure, because the gas volume that overflows in the different steps of coking is changing, the consistence of phase structure in the middle of this fluctuation directly affects, and the middle different steps that is oriented in mutually will realize that the order arrangement is also different to the traffic requirement of air-flow.Therefore, be difficult to make middle phase structure to obtain constitutionally stable effect by the method.
Existing document, publication number are that CN 1940017A has reported " the phase ordering growth prepares the method for needle coke in the middle of a kind of the impelling ", be by to the raw material separating for several times with realize by the multistage control process in the middle of mutually ordering growth with the preparation needle coke.For this reason, the ordering growth of phase in the middle of minute three phases promotes, the initial stage that forms mutually in the middle of (1), 400～450 ℃ of temperature of reactor, 8～15 hours reaction times, reactor gauge pressure 0.1～0.5MPa; (2) in the middle of mutually growth with melt in order and the initial stage 450～500 ℃ of temperature of reactor, 5～10 hours reaction times, atmospheric operation and the slow gas that produces of rejected heat cracking; (3) the phase ordering growth later stage in the middle of, gas, end reaction device gauge pressure-200Pa that 500～580 ℃ of temperature of reactor, 5～15 hours reaction times, decompression operation and slow rejected heat cracking produce.There is the defective that technical process is long, route is complicated, energy consumption is high, product cost is high in this method.
Summary of the invention
There is the problem that made needle coke quality is unstable or technological process is long in the preparation method who the purpose of this invention is to provide a kind of orderly mesophase needle coke to only depend on airflow function that middle phase order is led in the solution traditional technology process.
The invention provides a kind of preparation method of orderly mesophase needle coke; comprise the method for organic solvent and coal-tar pitch mixture being carried out ultrasonication and centrifugal treating; its concrete grammar is that organic solvent and coal-tar pitch are mixed take mass ratio as 3: 1～1: 3 ratio; after ultrasonic wave and centrifugal treating; get the top mixture; under vacuum 10KPa～85KPa reduced pressure, distill; remove organic solvent; again it is inserted in protection of inert gas and the reactor with the generation electric field arrangement and carry out temperature programming; when temperature rises to 100 ℃～120 ℃; begin to apply electric field, its strength of electric field is 8.0 * 10
4～1.0 * 10
6Volt/rice; When temperature rises to 400～450 ℃, keep 1～2.5h after, when continuing to be warming up to 500～580 ℃, keep 9～20h after, stopped heating, cooled product is the order mesophase needle coke.
Organic solvent described in the technique scheme of the present invention is washing oil, benzene or toluene; Described rare gas element is nitrogen, argon gas or carbonic acid gas; The speed of carrying out temperature programming in the described reactor is 2～15 ℃/min; Described reactor with producing electric field arrangement is to be provided with the pole plate that connects high-voltage power supply in the reactor both sides, when form electric field behind the plugged in reactor.
The orientations of phase structure and molecule plays a crucial role to the needle coke quality in the middle of in the production process of needle coke.The present invention is polycyclic arene compound according to the contained essential substance of raw material, the large π bonding electron of conjugation that has ring-type in the two dimensional structure above and below of these molecules, in the presence of the multiple synergistic effects such as electrical forces, intermolecular forces and air-flow stretching action that electric field, thermal field and airflow field produce to the reaction molecular effect, it is aligned not to be the motion effects random alignment of being heated, but controlled by the reactive force of electric field.For realizing this orientation, need to carry out heating operation by described temperature control program, namely begin to apply electric field from 100～120 ℃ of temperature of initial reaction stage, make the arrangement of a part of molecule in the reaction system have certain order and arrange, and the order of this a part of molecule plays very important guide effect to the formation of orderly crystal of later stage.Along with the rising of temperature, distance increases between reactant molecule, and Intermolecular Forces weakens, and electric field action power is acting on always, and by the synergy of this heating power and electrical forces, the order of reaction molecular further enlarges.Further rising temperature, hot polymerization reaction and scission reaction begin to occur simultaneously, cracking gas molecules out is in overflowing the process of reactant in the reaction process, reaction molecular electrical forces and overflow gas pulling or the bump under, the inevitable direction of travel adjustment of the molecular arrangement that part is not yet consistent with the direction of an electric field reactive force makes the direction of its arrangement and electric field action power consistent, thereby the order of molecule is further improved.When temperature of reaction reaches 400～450 ℃ temperature section, speed of response is accelerated, and for the order that makes molecule that prevents vigorous reaction is damaged, needs keep 1～2.5h in this temperature, and this process too acutely also has a certain effect to the generation of subsequent reactions is unlikely.Thereby, to only have temperature program(me) of the present invention and electric field controls process combined utilization, this middle phase order just can be achieved.Can fine adjustment and control strength of electric field by changing voltage of supply, and temperature can be by the program calling and controlling of setting, thereby whole process can realize automated operation fully, it is short to have a technical process, the characteristics of processing ease.In addition, there is the stability of being overflowed the orientation that how much affects molecule of gas volume and then affecting the needle coke quality in the middle phase oriented growth of airflow field effect control that leans on of bibliographical information, the present invention is converted into favorable factor with this unfavorable factor, namely under the synergistic effect of electric field action power can make those not yet with electric field action direction inconsistent molecular arrangement make its orientation further with electric field action direction consistent to the pulling of reactant molecule with shock action by overflowing gas, solve the problem of the variable effect needle coke quality stability of being overflowed gas volume.Accompanying drawing has provided to have or not to exist affects situation to the needle coke orientation.
Description of drawings
Fig. 1 is the not polarizing microscope photo of mesophase needle coke during added electric field of the present invention.
Among the figure: the middle needle coke weave construction that do not present mutually.
Fig. 2 is the polarizing microscope photo of the present invention's orderly mesophase needle coke when having electric field to exist.
Among the figure: white portion is filamentary structure, and the phase optical texture is obvious acicular structure structure in the middle of the expression.
Embodiment
Further describe the preparation method of a kind of orderly mesophase needle coke of the present invention below by specific embodiment, those skilled in the art is after having read this specific embodiment, can understand and implement technical solutions according to the invention, its described beneficial effect also can obtain embodying by specific embodiment.
Embodiment 1
The ratio that is in mass ratio 1: 2 is mixed coal-tar pitch with benzene; then ultrasonic 5min under ul-trasonic irradiation; change in the centrifuge tube; with the centrifugal 10min of 3000r/min speed; getting the top mixing liquid goes out benzene distillation under～10KPa the reduced pressure in vacuum tightness; place nitrogen protection and carry out temperature programming with the reactor that produces electric field arrangement; nitrogen flow rate is 200ml/min; when with the temperature rise rate of 15 ℃/min reaction being heated to 100 ℃; the beginning plugged applies electric field, and its strength of electric field is 8.0 * 10
4Volt/rice, continue to be heated to 400 ℃ after, keep this temperature 1h, be heated to afterwards 500 ℃, after this temperature continues 10h, stopped heating, cooled product is the order mesophase needle coke.
Embodiment 2
The ratio that is in mass ratio 1: 3 is mixed coal-tar pitch with toluene; then ultrasonic 10min under hyperacoustic effect; change in the centrifuge tube; with the centrifugal 15min of 5000r/min speed; get the top mixing liquid after organic solvent is removed in distillation under vacuum tightness～25KPa reduced pressure; then be placed in argon shield and the reactor with the generation electric field arrangement and carry out temperature programming; the argon gas flow velocity is 250ml/min; after with the temperature rise rate of 3 ℃/min reaction being heated to 100 ℃; the beginning plugged applies electric field, and strength of electric field is 1.6 * 10
5Volt/rice, continue to be heated to 430 ℃ after, keep this temperature 1.5h, be heated to afterwards 500 ℃, after this temperature continues 20h, stopped heating, the cooling after product is the order mesophase needle coke.
Embodiment 3
The ratio that is in mass ratio 3: 1 is mixed coal-tar pitch with washing oil; then ultrasonic 20min under hyperacoustic effect; change in the centrifuge tube; with the centrifugal 10min of 4000r/min speed; get the top mixing liquid after vacuum tightness is removed organic solvent for distillation under the～85KPa reduced pressure; place nitrogen protection and carry out temperature programming with the reactor that produces electric field arrangement; nitrogen flow rate is 300ml/min; when the temperature rise rate take heating rate as 5 ℃/min is heated to 100 ℃ with reaction; the beginning plugged applies electric field, and its strength of electric field is 4.0 * 10
5The volt/rice, continue to be heated to 400 ℃ after, keep this temperature 2.5h, with same heating rate reactor is heated to 580 ℃ afterwards, keep this temperature 9h after, stopped heating, the cooling after product be the order mesophase needle coke.
Embodiment 4
The ratio that is in mass ratio 1: 1 is mixed coal-tar pitch with gasoline, then ultrasonic 15min under hyperacoustic effect, change in the centrifuge tube, with the centrifugal 10min of 4000r/min speed, get the top mixing liquid after vacuum tightness is removed organic solvent for distillation under the～60KPa reduced pressure, place carbon dioxide and carry out temperature programming with the reactor that produces electric field arrangement, flow of carbon dioxide gas speed is 300ml/min, when then with the temperature rise rate of 2 ℃/min reaction being heated to 100 ℃, the beginning plugged applies electric field, its strength of electric field 1.0 * 10
6Volt/rice, continue to be heated to 400 ℃ after, keep this temperature 1h, reactor is heated to 550 ℃ afterwards, after this temperature continues 16h, stopped heating, the cooling after product is the order mesophase needle coke.
The above-mentioned reactor with producing electric field arrangement of the present invention is that both sides are provided with the reactor that connects the high-voltage power supply pole plate in ceramic reactor, when form electric field behind the plugged in reactor.
Claims (4)
1. the preparation method of an orderly mesophase needle coke; comprise the method for organic solvent and coal-tar pitch mixture being carried out ultrasonication and centrifugal treating; it is characterized in that organic solvent and coal-tar pitch are mixed take mass ratio as 3: 1～1: 3 ratio; after ultrasonic wave and centrifugal treating; get the top mixture; under vacuum 10KPa～85KPa reduced pressure, distill; remove organic solvent; again it is inserted nitrogen; carry out temperature programming in argon gas or CO 2 gas-shielded and the reactor with the generation electric field arrangement; when temperature rises to 100 ℃～120 ℃; begin to apply electric field, its strength of electric field is 8.0 * 10
4～1.0 * 10
6Volt/rice; When temperature rises to 400～450 ℃, keep 1～2.5h after, when continuing to be warming up to 500～580 ℃, keep 9～20h after, stopped heating, cooled product is orderly mesophase needle coke.
2. the preparation method of a kind of orderly mesophase needle coke claimed in claim 1 is characterized in that organic solvent is washing oil, benzene or toluene.
3. the preparation method of a kind of orderly mesophase needle coke claimed in claim 1, the speed that it is characterized in that carrying out in the reactor temperature programming is 2～15 ℃/min.
4. the preparation method of a kind of orderly mesophase needle coke claimed in claim 1 is characterized in that with the reactor that produces electric field arrangement it being that both sides are provided with the pole plate that connects high-voltage power supply in ceramic reactor, when form electric field behind the plugged in reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910074451 CN101565630B (en) | 2009-05-23 | 2009-05-23 | Method for preparing orderly mesophase needle coke |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910074451 CN101565630B (en) | 2009-05-23 | 2009-05-23 | Method for preparing orderly mesophase needle coke |
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| CN101565630A CN101565630A (en) | 2009-10-28 |
| CN101565630B true CN101565630B (en) | 2013-04-17 |
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| CN 200910074451 Expired - Fee Related CN101565630B (en) | 2009-05-23 | 2009-05-23 | Method for preparing orderly mesophase needle coke |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059893A (en) * | 2013-01-14 | 2013-04-24 | 太原理工大学 | Method for preparing mesophase pitch by utilizing electrochemical catalysis |
| CN108949212B (en) * | 2018-08-01 | 2020-11-13 | 国家能源投资集团有限责任公司 | Preparation method and preparation device of coal liquefied asphalt and coal liquefied asphalt |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5066384A (en) * | 1985-02-28 | 1991-11-19 | Sumitomo Metal Industries, Ltd. | Process for refining coal-derived heavy carbonaceous materials |
| CN1940017A (en) * | 2006-09-27 | 2007-04-04 | 上海应用技术学院 | Method for improving intermediate growth sequently to produce needle-shaped coke |
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2009
- 2009-05-23 CN CN 200910074451 patent/CN101565630B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5066384A (en) * | 1985-02-28 | 1991-11-19 | Sumitomo Metal Industries, Ltd. | Process for refining coal-derived heavy carbonaceous materials |
| CN1940017A (en) * | 2006-09-27 | 2007-04-04 | 上海应用技术学院 | Method for improving intermediate growth sequently to produce needle-shaped coke |
Non-Patent Citations (1)
| Title |
|---|
| 金鸣林等.有序性中间相焦的制备研究.《高校化学工程学报》.2008,第22卷(第4期),644－649. * |
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