CN103760053B - A kind of raw material evaluation method instructing needle coke coking production - Google Patents
A kind of raw material evaluation method instructing needle coke coking production Download PDFInfo
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- CN103760053B CN103760053B CN201410018476.8A CN201410018476A CN103760053B CN 103760053 B CN103760053 B CN 103760053B CN 201410018476 A CN201410018476 A CN 201410018476A CN 103760053 B CN103760053 B CN 103760053B
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Abstract
The present invention relates to needle coke production field, particularly relate to a kind of raw material evaluation method instructing needle coke coking production, it is characterized in that, make needle-shape coke raw material interval at the charing sensitive temperature of thermal conversion processes, the relation curve of its β component content, mesophase spherule growing amount and temperature, instruct the temperature schedule formulating and adjust pyrogenetic reaction in needle coke production, make the existing good liquid phase environment of the production of coking mesophase spherule obtain again enough heats and continue reaction, ensure to produce continous-stable direct motion, produce high-quality needle coke.Described raw material is the one in coal measures raw material, coal measures and the oily mixed material being.Compared with prior art, advantage of the present invention is: reaction sensitive temperature interval and the reaction characteristics that can provide needle-shape coke raw material coking more exactly, formulate rational heat-treat condition for coking production and reliable basis is provided, coking is reached more accurately control, this method is simple, time saving and energy saving, without the need to expensive analytical instrument and numerous and diverse analytic process.
Description
Technical field
The present invention relates to needle coke production field, particularly relate to a kind of raw material evaluation method instructing needle coke coking production.
Background technology
Needle coke is a kind of high-quality carbon material greatly developed nineteen seventies, it has low thermal coefficient of expansion, low-porosity, low-sulfur, low ash, low-metal content, some row advantages such as high conductivity and easily graphitization, it is the primary raw material producing electric furnace steel making ultra high power graphite electrode, ultra-high power graphite electrode can make steel-making time shorten 1/3rd, and electric power consumption per ton steel reduces half.The heavy distillate of the processing of needle coke commodity petroleum and coal tar processing is produced, as petroleum residual oil, ethylene bottom oil, Catalytic Cracking Residual Oil and thermal cracking residue, dead oil, coal-tar asphalt etc.According to raw material difference, needle coke is divided into coal-based needle coke and petroleum needle coke.
Coal-tar asphalt is formed with toluene and quinoline process is usually divided into three major types: QI(quinoline insolubles), TI-QS component (toluene insoluble, quinoline solvend component), TS component (xylene solubles), also α component, β component and γ component can be called, corresponding expression high molecular component, Middle molecule component and low-molecular-weight component.The chemical composition of β component (also known as β resin) is close with mesophase spherule, and therefore we can regard β component as the presoma of mesophase spherule.β component has cohesiveness, and therefore the content of conventional β component represents the mobility of system.In general, β component concentration is more than or equal to the good fluidity of 10% system.The content of β component varies with temperature the mobility variations that rule reflects pitch system in thermal conversion processes, and QI content reflects the change of pitch mesophase spherule growing amount in thermal conversion processes.
According to the formation mechenism of needle coke, the generation of the anisotropy tissue of good fluidity, suitable gas escaped quantity, the low viscosity of system long period are the key factors determining needle coke quality.How determining suitable heat-treat condition aborning, make the amount that the system β component concentration long period keeps suitable, mesophase spherule is generated and reaches suitable speed, is the key ensureing technique direct motion, production high-quality needle coke product.In coking, if temperature is too low, heating rate is too slow, not easily reacts, and then enough reaction heat can not be provided for subsequent reactions, finally cause coke immature and soft Jiao of output or oil coke; On the contrary, temperature is too high, the too fast then system viscosity of programming rate rises too fast, causes mesophase spherule to have little time reach full growth with regard to solidification and can not generate good anisotropy needle coke.
The formation mechenism of needle coke is theoretical based on mesophase spherule, although the theory of Carbonaceous mesophase comparative maturity, the developmental process of mesophase spherule obtains extensive approval, but people are still not clear in the effect of mesophase spherule generation and mechanism of coke formation to the fraction in raw material, how much relatively suitable also more indefinite each ends content is, get these problems clear and need expensive large-scale precision analytical instrument, the a series of analyses needing to take time and effort in a large number various raw material, test, this is unfavorable for Instructing manufacture.The raw material type preparing needle coke is many, source is wide, and the change of raw material can bring many difficulties to the adjustment of production technology, and the adjustment that process units carries out technological parameter can at substantial manpower and materials, increase production cost.
Summary of the invention
The object of this invention is to provide a kind of raw material evaluation method instructing needle coke coking production, need not do numerous and diverse fastidious one by one to cut various in raw material, the feature of raw material coking can be obtained within a short period of time, and can determine to provide reliable foundation for coking production technical arrangement plan; Liquid phase environment and the sensitive temperature of taking into account the generation of different material mesophase spherule are interval, rational and its pyrogenetic reaction temperature schedule of adjustment, make the existing good liquid phase environment of the production of coking mesophase spherule obtain again enough heats and continue reaction, make the direct motion of production continous-stable, produce high-quality needle coke.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of raw material evaluation method instructing needle coke coking production, by test needle coke material sample in thermal conversion processes, the relation curve of its β component content, mesophase spherule growing amount and temperature, instruct the temperature schedule formulating and adjust pyrogenetic reaction in needle coke production, ensure to produce continous-stable direct motion, produce high-quality needle coke, its concrete operation step is as follows:
1) material sample is loaded 8 ~ 20 test tubes and be placed in heating furnace;
2) control the programming rate of heating furnace, be warming up to 400 ~ 420 DEG C with the heating rate of 1 ~ 5 DEG C/min, then be warming up to 490 ~ 520 DEG C with the heating rate of 1 ~ 10 DEG C/h;
3), in temperature-rise period, from 420 DEG C of beginnings, get a test tube every 2 ~ 10 DEG C, be cooled to room temperature;
4) take out the sample in test tube and weigh, toluene insolubles and quinoline insolubles content in test sample, the mesophase spherule content obtaining material sample varies with temperature curve and β component content varies with temperature curve, interval according to the responsive to temperature that curve determination mesophase spherule changes greatly, control in order to instruct the temperature of actual coking production.
Described raw material is a kind of in coal measures raw material, oil system raw material or their potpourri.
Quinoline insolubles content in described coal measures raw material is 0 ~ 2%, comprises a kind of in 200 ~ 360 DEG C of cuts of coal-tar asphalt, coal tar or their potpourri.
Quinoline insolubles content in described oil system raw material is 0 ~ 2%, comprises the one in petroleum residual oil, ethylene bottom oil, Catalytic Cracking Residual Oil and thermal cracking residue.
Compared with prior art, the invention has the beneficial effects as follows: reaction sensitive temperature interval and reaction characteristics that needle-shape coke raw material coking can be provided more exactly, formulate rational heat-treat condition for coking production and reliable basis is provided, coking is reached more accurately control, this method is simple, time saving and energy saving, without the need to expensive analytical instrument and numerous and diverse analytic process.
Accompanying drawing explanation
Fig. 1 is the contents temperature curve of the embodiment of the present invention 1;
Fig. 2 is the contents temperature curve of the embodiment of the present invention 2;
Fig. 3 is the contents temperature curve of the embodiment of the present invention 3;
Fig. 4 is the contents temperature curve of the embodiment of the present invention 4;
Fig. 5 is the contents temperature curve of the embodiment of the present invention 5.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described:
A kind of raw material evaluation method instructing needle coke coking production of the present invention, be exactly interval at the charing sensitive temperature of thermal conversion processes by making needle-shape coke raw material, the relation curve of its β component content, mesophase spherule growing amount and temperature, instruct the temperature schedule formulating and adjust pyrogenetic reaction in needle coke production, make the existing good liquid phase environment of the production of coking mesophase spherule obtain again enough heats and continue reaction, ensure to produce continous-stable direct motion, produce high-quality needle coke, its concrete operation step is as follows:
1) material sample is loaded 8 ~ 20 test tubes and be placed in box type furnace, be provided with soaking block in box test tube stove, soaking block is that cast aluminium block or copper billet are made, and can provide uniform temperature field, and with inserting a series of circular holes of test tube, test tube material is pyroceram or stainless steel;
2) control the programming rate of heating furnace, be warming up to 400 ~ 420 DEG C with the heating rate of 1 ~ 5 DEG C/min, then be warming up to 490 ~ 520 DEG C with the heating rate of 1 ~ 10 DEG C/h;
3), in temperature-rise period, from 420 DEG C of beginnings, get a test tube every 2 ~ 10 DEG C, be cooled to room temperature;
4) take out the sample in test tube and weigh, toluene insolubles (TI) and quinoline insolubles content (QI) in test sample, each mesophase spherule content at this temperature spot sample is weighed with quinoline insolubles content (QI), β component content is weighed by the difference of toluene insolubles (TI) and quinoline insolubles (QI) content, the mesophase spherule content obtaining material sample varies with temperature curve and β component content varies with temperature curve, can obtain according to curve the responsive to temperature that mesophase spherule changes greatly interval, control in order to instruct the temperature of actual coking production.
The raw material that the present invention is suitable for is a kind of in coal measures raw material, oil system raw material or their potpourri.Quinoline insolubles content in described coal measures raw material is 0 ~ 2%, comprises a kind of in 200 ~ 360 DEG C of cuts of coal-tar asphalt, coal tar or their potpourri.Quinoline insolubles content in described oil system raw material is 0 ~ 2%, comprises the one in petroleum residual oil, ethylene bottom oil, Catalytic Cracking Residual Oil and thermal cracking residue.
Choose the material sample of heterogeneity in the following example respectively, carry out mesophase spherule content and vary with temperature the drafting that curve and β component content vary with temperature curve.
Embodiment 1
Get about 160g coal-tar asphalt, QI is 0.08%, softening point 22 DEG C, and every root test tube loads 20 grams, loads in 8 test tubes, and loads in box test tube stove.Test tube stove, under temperature programmed control device controls, is warming up to 420 DEG C by room temperature with the heating rate of 2 DEG C/min, then is warming up to 490 DEG C through program with the heating rate of 5 DEG C/h.Start to get first test tube from 420 DEG C, then get a test tube every 2h.After test tube cooling, take out sample, detect QI and TI of every root cuvette sample.Obtain sample mesophase spherule content and β component content varies with temperature curve (see figure 1), can find out that the sensitive temperature interval that its middle phase change is larger is 440 ~ 470 DEG C by curve.
Embodiment 2
Get about 160g coal tar mid-temperature pitch, QI is 0.8%, softening point 80 DEG C, and every root test tube loads about 20 grams, loads in 8 test tubes, and loads in box test tube stove.Test tube stove, under temperature programmed control device controls, is warming up to 420 DEG C by room temperature with the heating rate of 2 DEG C/min, then is warming up to 490 DEG C through program with the heating rate of 5 DEG C/h.Start to get first test tube from 420 DEG C, then get a test tube every 2h.After test tube cooling, take out sample, detect QI and TI of every root cuvette sample.Obtain sample mesophase spherule content and β component content varies with temperature curve (see figure 2), can find out that the sensitive temperature interval that its middle phase change is larger is 460 ~ 480 DEG C by curve.
Embodiment 3
Get the mixture pitch that about 160g carbolineum and softening point are the mid-temperature pitch (mass ratio is 2:5) of 85 DEG C, QI is 0.75%, softening point 30 DEG C, and every root test tube loads about 20 grams, loads in 8 test tubes, and loads in box test tube stove.Test tube stove, under temperature programmed control device controls, is warming up to 420 DEG C by room temperature with the heating rate of 2 DEG C/min, then is warming up to 490 DEG C through program with the heating rate of 5 DEG C/h.Start to get first test tube from 420 DEG C, then get a test tube every 2h.After test tube cooling, take out sample, detect QI and TI of every root cuvette sample.Obtain sample mesophase spherule content and β component content varies with temperature curve (see figure 3), can find out that the sensitive temperature interval that its middle phase change is larger is 450 ~ 480 DEG C by curve.
Embodiment 4
Get the mixture pitch (mass ratio 1:9) of about 200g by petroleum residual oil and softening point 35 DEG C of coal-tar pitch, QI is 0.12%, softening point 25 DEG C, and every root test tube loads about 20 grams, loads in 10 test tubes, and loads in box test tube stove.Test tube stove, under temperature programmed control device controls, is warming up to 420 DEG C by room temperature with the heating rate of 3 DEG C/min, then is warming up to 510 DEG C through program with the heating rate of 5 DEG C/h.Start to get first test tube from 420 DEG C, then get a test tube every 2h.After test tube cooling, take out sample, detect QI and TI of every root cuvette sample.Obtain sample mesophase spherule content and β component content varies with temperature curve (see figure 4), can find out that the sensitive temperature interval that its middle phase change is larger is 440 ~ 480 DEG C by curve.
Embodiment 5
Get about 180g Catalytic Cracking Residual Oil, QI is 0.06%, softening point 25 DEG C, and every root test tube loads about 20 grams, loads in 10 test tubes, and loads in box test tube stove.Test tube stove, under temperature programmed control device controls, is warming up to 420 DEG C by room temperature with the heating rate of 3.5 DEG C/min, then is warming up to 500 DEG C through program with the heating rate of 5 DEG C/h.Start to get first test tube from 420 DEG C, then get a test tube every 2h.After test tube cooling, take out sample, detect QI and TI of every root cuvette sample.Obtain sample mesophase spherule content and β component content varies with temperature curve (see figure 5), can find out that the sensitive temperature interval that its middle phase change is larger is 440 ~ 460 DEG C by curve.
The present invention can obtain sensitive temperature interval and β component, the mesophase spherule content rule of often kind of raw material more exactly, can formulate rational heat-treat condition accordingly in coking production.As in the sensitive temperature interval of raw material, for β component content and the fast raw material of mesophase spherule content, a relatively mild temperature increasing schedule can be formulated in coking production, the contrary comparatively faster temperature increasing schedule of then formulation.Make coking reach so more accurately to control, for production system provides stable heat balance and mass balance, ensure the production of high-quality needle coke product.
Claims (4)
1. one kind is instructed the raw material evaluation method of needle coke coking production, it is characterized in that, by test needle coke material sample in thermal conversion processes, the relation curve of its β component content, mesophase spherule growing amount and temperature, instruct the temperature schedule formulating and adjust pyrogenetic reaction in needle coke production, ensure to produce continous-stable direct motion, produce high-quality needle coke, its concrete operation step is as follows:
1) material sample is loaded 8 ~ 20 test tubes and be placed in heating furnace;
2) control the programming rate of heating furnace, be warming up to 400 ~ 420 DEG C with the heating rate of 1 ~ 5 DEG C/min, then be warming up to 490 ~ 520 DEG C with the heating rate of 1 ~ 10 DEG C/h;
3), in temperature-rise period, from 420 DEG C of beginnings, get a test tube every 2 ~ 10 DEG C, be cooled to room temperature;
4) take out the sample in test tube and weigh, toluene insolubles and quinoline insolubles content in test sample, the mesophase spherule content obtaining material sample varies with temperature curve and β component content varies with temperature curve, interval according to the responsive to temperature that curve determination mesophase spherule changes greatly, control in order to instruct the temperature of actual coking production.
2. a kind of raw material evaluation method instructing needle coke coking production according to claim 1, is characterized in that, described raw material is a kind of in coal measures raw material, oil system raw material or their potpourri.
3. a kind of raw material evaluation method instructing needle coke coking production according to claim 2, it is characterized in that, quinoline insolubles content in described coal measures raw material is 0 ~ 2%, comprises a kind of in 200 ~ 360 DEG C of cuts of coal-tar asphalt, coal tar or their potpourri.
4. a kind of raw material evaluation method instructing needle coke coking production according to claim 2, it is characterized in that, quinoline insolubles content in described oil system raw material is 0 ~ 2%, comprises the one in petroleum residual oil, ethylene bottom oil, Catalytic Cracking Residual Oil and thermal cracking residue.
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| CN106290448A (en) * | 2016-07-13 | 2017-01-04 | 中国石油大学(华东) | A kind of method of quickly evaluating needle coke heat stability |
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| CN109030485B (en) * | 2018-06-20 | 2021-02-12 | 山东益大新材料股份有限公司 | Evaluation method of needle coke raw material |
| CN109253943B (en) * | 2018-08-23 | 2020-10-02 | 辽宁科技大学 | Method for monitoring properties of mixed oil in production process of coal-based needle coke |
| CN110018194A (en) * | 2019-04-12 | 2019-07-16 | 山东益大新材料有限公司 | A kind of reactive apparatus system of evaluation coking raw material and evaluation method |
| CN112779038B (en) * | 2021-01-19 | 2022-02-18 | 山西沁新能源集团股份有限公司 | Preparation method of special coke for ceramic fiber vertical melting furnace, special coke for ceramic fiber vertical melting furnace and application of special coke |
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Application publication date: 20140430 Assignee: Zaozhuang Zhenxing Carbon Material Technology Co., Ltd. Assignor: Sinosteel Anshan Research Institute of Thermo-energy Co., Ltd. Contract record no.: 2019210000014 Denomination of invention: Raw material evaluation method for guiding coking production of needle coke Granted publication date: 20160427 License type: Common License Record date: 20190516 |
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