CN106566570A - Method for preparing high-quality needle coke through heavy oil - Google Patents
Method for preparing high-quality needle coke through heavy oil Download PDFInfo
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- CN106566570A CN106566570A CN201610920010.6A CN201610920010A CN106566570A CN 106566570 A CN106566570 A CN 106566570A CN 201610920010 A CN201610920010 A CN 201610920010A CN 106566570 A CN106566570 A CN 106566570A
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- needle coke
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- quality needle
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
Abstract
The invention relates to a preparation method for preparing high-quality needle coke through heavy oil. The preparation method comprises the steps that firstly, after the raw material is pre-treated, a reaction is conducted for 1-3 hours at the temperature of 480-520 DEG C and the pressure of 1-6 Mpa under the nitrogen condition, and intermediate components 1 are obtained; and secondly, the intermediate components react for 6-12 hours at the temperature of 410-470 DEG C and the pressure of 0-2 Mpa, and the high-quality needle coke is obtained. According to the preparation method, the process is simple, the operation conditions are mild, the cost is low, and the final product is excellent in properties.
Description
Technical field
The present invention relates to one kind is with mink cell focus as raw material, through two-step reaction the preparation method of high-quality needle coke, category are prepared
In the preparing technical field of senior new carbon high-quality needle coke.
Background technology
Needle coke is a kind of new carbon, and needle coke is silver gray, has the porosu solid of metallic luster, and surface is in obvious
Elongated needle-like or fibrous texture trend, that what is touched has lubrication sense, internal holes are big and lack, it is slightly ob-round, be a kind of high-quality
Carbon raw materials.Needle coke is the molecular crystal of macromole condensed aromatics, and aromatic hydrocarbon is with stratiform accumulation, graphite-like microcrystal unit orientation
Degree is high, in the optical texture of polarized light microscopy Microscopic observation coke, one group of parallel needle-like anisotropy unit by slightly radian
Composition.The characteristics of needle coke, is mainly：(1) purity is high, is mainly made up of carbon, hydrogen, sulfur, nitrogen, oxygen and some metallic elements
Content is little, and content of ashes height can hinder the generation of crystal structure, and affect the purity of graphite products；(2) density is big, pore
Rate is low, degree of crystallinity is high；(3) thermal coefficient of expansion is little, and CTE little carbon product is little with the change in volume of temperature, is equally bearing prominent
Shock resistance when so rising to high temperature or the thermal shock from high temperature quick refrigeration is good, will not rupture；(4) heat conductivity and electric conductivity are good
Good, degree of graphitization is high.Needle coke is a kind of typical easily graphitized charcoal, and the microstructure with Fanklin models is heated to
More than 2000 DEG C this microstructures are easy to develop into graphite laminate structure.Needle coke can be used to do high power electrodes (HP)
With ultra-high power graphite electrode (UHP), after coming out from uhp electric arc furnace smelting technique in 1969, as HP and UHP primary raw materials
Needle coke production is developed rapidly.The high power electrodes of needle coke manufacture have that resistivity is little, resistance to sudden heating strong, mechanical strength
High, antioxygenic property is good, consume low outstanding advantages.Needle coke can be divided into coal-based needle coke by the raw material of production needle coke
With petroleum needle coke.To produce based on coal-based needle coke, the U.S. is producing based on petroleum needle coke for wherein Japan.At present,
China is due to raw materials for production and technical reason, and needle coke product quality and yield all extremely unstables are raw greatly all in low-grade level
Produce the big needle-type coke overwhelming majority required for HP and UHP and depend on import.The intensity of domestic needle coke awaits further carrying
Height, the thermal coefficient of expansion of domestic needle coke awaits further reduction.
The general requirement to needle-shape coke raw material is：Density is more than 0.96g/cm3(more preferably greater than 1.0g/cm3), arene content
High (weight is than being about the short-side chain polycyclic aromatic hydrocarbon of 30%～50% 2～4 rings, the ring of average out to 3), gum asphaltic content are low
(general control heptane insolubles<2.0%), sulphur content content low (no more than 0.6%), ash is low, it is desirable to catalyst fines, vanadium,
Nickel total content is less than 100 μ g/g, and quinoline insolubles is 0.H/C atomic ratios are 1.0～1.4.The production technology of needle coke is more multiple
Miscellaneous, at present, preparing the method for needle coke has：Thermal cracking-coking process integration, Pu Jiao-needle coke process integration, delay coke chemical industry
Skill etc..But at present these method technics comparings are complicated, the needle coke total quality index of its production still has much room for improvement.
Mink cell focus aromaticity used in the present invention is high, and hetero atom, tenor are low.Contain in aromatic compound in its raw material
There is more cycloalkane structure and short-side chain alkane structure, be the good raw material for preparing needle coke.
The content of the invention
Present invention mainly solves the existing needle coke method for preparing is complicated, and the second-rate problem of the needle coke that produces.With
The deasphalted oil of the double distilled segmentation, the line fraction that subtracts four of naphthene base crude and/or cycloalkyl decompression residuum of FCC slurry is raw material,
First pretreatment is carried out to raw material, then carry out two-step reaction, produce the needle coke of high-quality.
The present invention takes for achieving the above object technical scheme below：
A kind of method that mink cell focus prepares high-quality needle coke, raw material adopts two-step reaction after pretreatment：(1) pretreatment
At temperature 480-520 DEG C, under a nitrogen atmosphere, pressure 1-6Mpa reacts 1-3h to raw material afterwards, obtains intermediate species 1；(2)
Intermediate species 1 reacts 6-12h at 410-470 DEG C under 0-2Mpa, obtains needle coke.
Wherein described raw material is the double distilled segmentation of FCC slurry, the line fraction that subtracts four of naphthene base crude and/or cycloalkyl subtract
The deasphalted oil of pressure residual oil.
Above-mentioned raw materials carry out carrying out step (1) after pretreatment again, and its preprocessing process is to raw oil with dimethyl sulfoxide
It is stripped, obtains the rich aromatic component that molecular weight is 350-500.
True density >=the 2.1gcm of the needle coke-3, thermal coefficient of expansion≤2.1 × 10-6/ DEG C, ash≤0.03%
(mass percent).
Two-step reaction is adopted in the present invention.In reactions steps 1, reaction temperature is higher, can reduce system viscosity, and
Be conducive to the fracture of alkyl side chain, simultaneously because during there is hydrogen migration and transalkylation reaction, heating process is suppressed significantly
It is middle to produce excessive condensation product, it is to avoid the adverse effect to subsequent process.Certain pressure can be by low molecular weight volatile material
Suppress in condensed phase, improve its mobility, greatly promote mesophase ball abundant growth, melt and and mesophase molecule weight
Arrangement, enables crystallite to align.In step 2, reaction temperature is reduced, and reaction is unlikely to too fierce, can suppress a large amount of
Reactant is acutely polymerized, and prevents system from producing disorderly, and the prolongation of simultaneous reactions time is conducive to the orderly carbonization of reaction molecular, makes crystalline substance
Body can reach full growth and align.Under low pressure, small molecule light hydrocarbon gas can form steady air flow, be conducive to carrying out air-flow
Draw burnt, wide area is streamlined, fibrous green coke structure so as to be formed, and finally solidifies coking, obtains needle coke.
The beneficial effect compared with existing preparation method of the invention is：
(1) present invention is simple to operation, with short production cycle, beneficial to the industrialization promotion and application of the scheme of preparation；
(2) the raw material arene content that adopts is high in the present invention, and for short-side chain polycyclic aromatic hydrocarbon, the orderly carbon in carbonization process
Change reactivity high, be conducive to generating high-quality needle coke.And raw material is to equipment non-corrosiveness；
(3) present invention can be effectively improved purity, yield and the performance of needle coke using two-step reaction：Thermal expansion system
The low, ash of number is few, good conductivity, is a kind of needle coke of high-quality.
Specific embodiment
It is further discussed below with reference to embodiment provided by the present invention with the segmentation of FCC slurry double distilled, naphthene base crude
The line fraction that subtracts four, the deasphalted oil of cycloalkyl decompression residuum are the method that raw material prepares high-quality needle coke.
Embodiment 1：
The double distilled segmentation for taking 200gFCC slurry oils is added in stainless steel autoclave, is passed through nitrogen purging displaced air, flow
2L/min, after purging 3 times, with 2 DEG C/min 100 DEG C is at the uniform velocity warming up to, and starts stirring；Continuation is at the uniform velocity warming up to 490 DEG C, in nitrogen
Under the conditions of, 3Mpa with pressure reacts 1h, obtains intermediate species 1.The 100g of intermediate species 1 is taken, at pressure 1Mpa, 410 DEG C of temperature,
Reaction 6h, discharges pressure, and slow cooling obtains high-quality needle coke, true density 2.13gcm-3, thermal coefficient of expansion 2.1 × 10-6/
DEG C, ash is 0.01%.
Embodiment 2：
The line fraction that subtracts four for taking 200g naphthene base crudes is added in stainless steel autoclave, is passed through nitrogen purging displaced air,
Flow 2L/min, after purging 3 times, with 2 DEG C/min 100 DEG C is at the uniform velocity warming up to, and starts stirring；Continuation is at the uniform velocity warming up to 480 DEG C,
Under condition of nitrogen gas, 2Mpa with pressure reacts 2h, obtains intermediate species 1.The 100g of intermediate species 1 is taken, in pressure 2Mpa, temperature 420
At DEG C, 8h is reacted, discharge pressure, slow cooling obtains needle coke, true density 2.5gcm-3, thermal coefficient of expansion 1.8 × 10-6/
DEG C, ash is 0.02%.
Embodiment 3：
The deasphalted oil for taking 200g cycloalkyl decompression residuum is added in rustless steel autoclave, is passed through nitrogen purging displacement
Air, flow 2L/min after purging 3 times, with 2 DEG C/min 100 DEG C is at the uniform velocity warming up to, and starts stirring, is continuously heating to 500 DEG C,
Under a nitrogen atmosphere, 3Mpa with pressure, reacts 3h, obtains intermediate species 1. and takes the 100g of intermediate species 1, in pressure 1Mpa, temperature
At 450 DEG C, 10h is reacted, discharge pressure, slow cooling obtains needle coke, true density 2.3gcm-3,, thermal coefficient of expansion 1.5 ×
10-6/ DEG C, ash is 0.01%
Embodiment 4：
The double distilled segmentation for taking 200gFCC slurry oils is added in rustless steel autoclave, is passed through nitrogen purging displaced air, stream
Amount 2L/min, after purging 3 times, with 2 DEG C/min 100 DEG C is at the uniform velocity warming up to, and starts stirring, 500 DEG C is continuously heating to, in nitrogen bar
Under part, 3Mpa with pressure reacts 1h, obtains intermediate species 1. and takes the 100g of intermediate species 1, at pressure 2Mpa, 460 DEG C of temperature, instead
9h is answered, pressure is discharged, slow cooling obtains needle coke, true density 2.2gcm-3, thermal coefficient of expansion 1.7 × 10-6/ DEG C, ash
For 0.03%.
Embodiment 5：
The double distilled segmentation for taking 200gFCC slurry oils is added in stainless steel autoclave, is passed through nitrogen purging displaced air, flow
2L/min, after purging 3 times, with 2 DEG C/min 100 DEG C is at the uniform velocity warming up to, and starts stirring；Continuation is at the uniform velocity warming up to 490 DEG C, in nitrogen
Under the conditions of, 6Mpa with pressure reacts 1h, obtains intermediate species 1.The 100g of intermediate species 1 is taken, at pressure 1Mpa, 410 DEG C of temperature,
Reaction 6h, discharges pressure, and slow cooling obtains high-quality needle coke, true density 2.5gcm-3, thermal coefficient of expansion 1.5 × 10-6/
DEG C, ash is 0.01%.
Embodiment 6：
The double distilled segmentation for taking 200gFCC slurry oils is added in stainless steel autoclave, is passed through nitrogen purging displaced air, flow
2L/min, after purging 3 times, with 2 DEG C/min 100 DEG C is at the uniform velocity warming up to, and starts stirring；Continuation is at the uniform velocity warming up to 490 DEG C, in nitrogen
Under the conditions of, 1Mpa with pressure reacts 1h, obtains intermediate species 1.The 100g of intermediate species 1 is taken, at pressure 1Mpa, 410 DEG C of temperature,
Reaction 6h, discharges pressure, and slow cooling obtains high-quality needle coke, true density 2.1gcm-3, thermal coefficient of expansion 2.1 × 10-6/
DEG C, ash is 0.01%.
Embodiment 7：
FCC slurry is stripped using dimethyl sulfoxide, obtains the rich aromatic component that molecular weight is 450, take 200gFCC
Slurry oil double distilled segmentation add stainless steel autoclave in, be passed through nitrogen purging displaced air, flow 2L/min, purging 3 times after, with
2 DEG C/min is at the uniform velocity warming up to 100 DEG C, starts stirring；Continuation is at the uniform velocity warming up to 490 DEG C, under a nitrogen atmosphere, 6Mpa with pressure, and instead
1h is answered, intermediate species 1 is obtained.The 100g of intermediate species 1 is taken, at pressure 1Mpa, 410 DEG C of temperature, 6h is reacted, pressure is discharged, is delayed
Slow cooling, obtains high-quality needle coke, true density 2.53gcm-3, thermal coefficient of expansion 1.4 × 10-6/ DEG C, ash is 0.01%.
Claims (4)
1. a kind of method that mink cell focus prepares high-quality needle coke, raw material adopts two-step reaction after pretreatment：(1) raw material is in temperature
At 480-520 DEG C of degree, under a nitrogen atmosphere, pressure 1-6Mpa reacts 1-3h, obtains intermediate species 1；(2) intermediate species 1 exists
At 410-470 DEG C, 6-12h is reacted under 0-2Mpa, obtain needle coke.
2. the method that a kind of mink cell focus according to claim 1 prepares high-quality needle coke, it is characterised in that：Described raw material
For the deasphalted oil of the double distilled segmentation, the line fraction that subtracts four of naphthene base crude and/or cycloalkyl decompression residuum of FCC slurry.
3. the method that a kind of mink cell focus according to claim 1 prepares high-quality needle coke, it is characterised in that：The needle coke
True density >=2.1gcm-3, thermal coefficient of expansion≤2.1 × 10-6/ DEG C, ash≤0.03% (mass percent).
4. the method that a kind of mink cell focus according to claim 1 prepares high-quality needle coke, it is characterised in that：Above-mentioned raw materials enter
Carry out step (1) after row pretreatment again, its pre-treatment step is that raw oil is stripped using dimethyl sulfoxide, is divided
Son amount is the rich aromatic component of 350-500.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110066676A (en) * | 2019-04-24 | 2019-07-30 | 中国石油大学(华东) | A kind of continuous processing producing high-quality needle coke |
| CN110066675A (en) * | 2019-04-24 | 2019-07-30 | 中国石油大学(华东) | A kind of method of the high-quality needle coke of continuous production |
| CN111575036A (en) * | 2020-05-22 | 2020-08-25 | 中国石油大学(华东) | Method for preparing high-quality needle coke by size exclusion separation-fractional carbonization of heavy oil |
| CN111592902A (en) * | 2020-05-22 | 2020-08-28 | 中国石油大学(华东) | Method for preparing needle coke for ultrahigh-power electrode from heavy oil |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104560104A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Method for producing needle coke |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104560104A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Method for producing needle coke |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110066676A (en) * | 2019-04-24 | 2019-07-30 | 中国石油大学(华东) | A kind of continuous processing producing high-quality needle coke |
| CN110066675A (en) * | 2019-04-24 | 2019-07-30 | 中国石油大学(华东) | A kind of method of the high-quality needle coke of continuous production |
| CN111575036A (en) * | 2020-05-22 | 2020-08-25 | 中国石油大学(华东) | Method for preparing high-quality needle coke by size exclusion separation-fractional carbonization of heavy oil |
| CN111592902A (en) * | 2020-05-22 | 2020-08-28 | 中国石油大学(华东) | Method for preparing needle coke for ultrahigh-power electrode from heavy oil |
| CN111592902B (en) * | 2020-05-22 | 2021-05-28 | 中国石油大学(华东) | Method for preparing needle coke for ultrahigh-power electrode from heavy oil |
| CN111575036B (en) * | 2020-05-22 | 2021-05-28 | 中国石油大学(华东) | Method for preparing high-quality needle coke by size exclusion separation-fractional carbonization of heavy oil |
| WO2021232560A1 (en) * | 2020-05-22 | 2021-11-25 | 中国石油大学(华东) | Method for preparing needle coke for ultra-high power electrode from heavy oil |
| US11286425B2 (en) | 2020-05-22 | 2022-03-29 | China University Of Petroleum | Method for preparing needle coke for ultra-high power (UHP) electrodes from heavy oil |
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