CN103113908A - Coal-based needle coke preparation process - Google Patents
Coal-based needle coke preparation process Download PDFInfo
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- CN103113908A CN103113908A CN201310034986XA CN201310034986A CN103113908A CN 103113908 A CN103113908 A CN 103113908A CN 201310034986X A CN201310034986X A CN 201310034986XA CN 201310034986 A CN201310034986 A CN 201310034986A CN 103113908 A CN103113908 A CN 103113908A
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Abstract
The invention discloses a coal-based needle coke preparation process which comprises the following steps: 1) feeding raw materials into a No.1 tube heating furnace, heating, and then producing a polycondensation material through a polycondensation reaction kettle 3 in a circulation manner; 2) feeding the polycondensation material into a pressurization filtration kettle, filtering, injecting inert gas to perform pressurization, and performing hot filtration; 3) performing centrifugal filtration on the filtrate to obtain a refined and purified polycondensation material, and feeding into a purified polycondensation material tank; 4) feeding the purified polycondensation material into the No.1 tube heating furnace, heating, then respectively feeding into a No.1 flash distillation tower and a No.2 flash distillation tower 9, and performing flash distillation to produce refined and purified asphalt; 5) feeding the produced refined and purified asphalt into a No.2 tube heating furnace, heating, coking, fractionating coking oil gas, and returning heavy oil to the pressurization hot filtration kettle; and 6) calcining green coke in a calcining furnace to obtain the needle coke product. For the refined and purified asphalt prepared by the method, the quinoline insoluble matter content is less than 0.1%, and the thermal expansion coefficient is low, thereby ensuring that the asphalt can be used for large steel-making electric furnaces.
Description
Technical field
The present invention relates to a kind of preparation technology of needle coke, relate in particular to a kind of preparation technology with coal measures raw material needle coke.
Background technology
Needle coke is a fine quality in carbon material, and its outward appearance is silver gray, metalluster is arranged, and because there is significantly texture fibrous or needle-like on surface, gains the name.The hole of needle coke inside is ovalize greatly and less and slightly, and particle has larger long-width ratio.Needle coke is the main raw material that production superpower and smelting steel in ultrahigh-power electric furnace are used Graphite Electrodes, and its greying goods are widely used in Electric furnace steel making electrode, nuclear reactor deceleration material and rocketry.Can improve significantly steel-making efficiency, environmental contamination reduction with the use of the ultra-high power graphite electrode of needle coke manufacture.
According to the difference of raw materials for production, it is two kinds of needle coke and coal-based needle cokes that needle coke can be divided into oil.In short supply due to crude resources, causing oil is the minimizing of needle-shape coke raw material, coal measures raw material production needle coke has price advantage, and the fast development along with China's Coal Chemical Industry industry, the output of the by product coal tar in the Coal dressing process constantly increases, and has promoted the development of coal-based needle coke technology of preparing.
The production technique more complicated of needle coke, typical technique has thermally splitting-coking process integration, general Jiao-needle coke process integration, delay coking process etc., wherein delay coking process is the technique mainly adopted both at home and abroad, it take coal coking byproduct coal tar is raw material, through raw materials pretreatment, delayed coking and 3 workshop sections of calcining, makes coal-based needle coke.The technique of delayed coking and calcining workshop section is similar, and raw materials pretreatment just becomes the key problem in technology that determines the needle coke quality good or not.Owing to containing a certain amount of quinoline insolubles (QI) in coal tar, they be attached to mesophasespherule around, hinder and spherularly grow up, melt also, can not obtain the needle coke tissue that fibrous texture is good after coking, therefore, need carry out pre-treatment to the coal measures raw material.The raw materials pretreatment main method has: hydrogenation method, two sections hot polymerizations are legal, flash method, centrifuging, solvent method, upgrading method etc.At present both at home and abroad industrialized operational path flash distillation-delayed coking-calcining process and solvent method-delayed coking-two kinds of calcining procesies are arranged.
The patent of invention 2003-183669 of Mitsubishi chemical company has announced a kind of method that solvent method is produced needle coke, and the quality product of gained is high, but complex process, cost is higher.
Chinese patent CN1793287A has announced a kind of production method of tar needle-shape coke raw material, by softening temperature be 35 ℃ of 30 ℃ of straight-run viscid bitumens or softening temperatures return join viscid bitumen be heated to after 60 ℃ and aliphatic hydrocarbon/aromatic hydrocarbon solvent of being pre-mixed respectively by being pumped into stirring tank, through stirring, standing, precipitate 2～20hr after, upper strata in stirring tank is light phase straight-run viscid bitumen or returns the mixture of joining viscid bitumen and solvent and extracted out and sent into solvent recovery tower by pump again, reclaim solvent and produce refined asphaltic bitumen through solvent recovery tower, obtaining being applicable to producing the raw material of needle coke.
Chinese patent CN102051191 has announced a kind of production method of carbobitumen, obtains the purifying pitch removed after quinoline insolubles (QI) by solvent processing method, carries out carbonization with this purifying pitch and obtains coal-based needle coke.
Although above-mentioned technique is simple to operate, the good purification of raw material, main drawback is that solvent load is large, needs a plurality of stirring tank switchings to use and could realize serialization production, the recovery of solvent strengthens cost of investment.
Summary of the invention
The preparation technology who the purpose of this invention is to provide a kind of coal-based needle coke.This technique take coal tar, coal-tar pitch, return and join viscid bitumen or coal tar fraction is raw material, raw material removes the quinoline insolubles in raw material with the mode polycondensation of circulation by heat filtering and centrifuging, flash distillation obtains the refined asphaltic bitumen coking raw material again, finally by coking tower coking and calcining furnace high-temperature calcination, makes needle coke.
The present invention is achieved through the following technical solutions above-mentioned purpose:
A kind of preparation technology of coal-based needle coke, is characterized in that, this technique comprises the steps:
1) raw material is sent in the 1# tubular oven, after heating, adopted batch condensation polymerization reactor by Recycle design output polycondensation material;
2) after the polycondensation material of step 1) output is cooling, enter the pressure filtration still, send into pressurized heat with the heat filtering fresh feed pump and filter the filtration material layer filtration of laying in still, filter the still injecting inert gas via air intake valve to heating and pressurizing, pressurization is carried out heat filtering to the polycondensation material under protection of inert gas;
3) through step 2) filtrate of heat filtering, enter in whizzer, centrifuging, the refining purification polycondensation material obtained is sent to and purifies in the polycondensate hopper;
4) obtaining the refining polycondensation material that purifies through step 3) is pumped in the 1# tubular oven with flash evaporation feed, heat laggard 1# flashing tower, hard pitch containing quinoline insolubles is discharged from 1# flashing tower bottom, the flash oil that tower top is overflowed enters the 2# flashing tower and carries out flash distillation, the refining purifying pitch of 2# flashing tower bottom output, tower top effusion light oil;
5) send into again the heating of 2# tubular oven through purifying pitch injected water steam after the furnace charge pump is extracted out of step 4) output, then enter coking tower coking coking, make green coke; The coking oil gas of overflowing from the coking tower top obtains oil gas, light oil and heavy oil through the separation column fractionation, and the heavy constituent oil of separation column bottom is through pipeline and again enter pressurized heat filtration still from the polycondensation mixing of materials of batch condensation polymerization reactor output;
6) green coke made through step 5) is sent in calcining furnace, heats up, and calcining, obtain the product needle coke.
Further, described raw material is coal tar, coal-tar pitch, returns and join viscid bitumen or coal tar fraction.
Further, described polycondensation recycle ratio is 20～50, and the polycondensation process temperature is 380～500 ℃, and pressure is 0.5～2MPa, and the reaction times is 6～24 hours.
Further, filtration material layer in described heating and pressurizing filtration still is combined by mixture and the stainless steel filtering net of diatomite, pearlstone or diatomite and pearlstone, the granularity of diatomite and expanded perlite granule is 50～150 orders, stainless steel filtering net order number is 400～700 orders, and filtering layer thickness is 5～15 centimetres.
Further, described step 2) filter stills hocket filling and the filtration of polycondensation material by two pressurized heats in, it is 150～240 ℃ that pressurized heat filters still opening for feed temperature, is forced into 0.5～2MPa.
Further, described is N to heating and pressurizing filtration still injecting inert gas
2or Ar.
Further, the order number of described centrifuge filtering cloth is 1000～1600 orders, and centrifuge speed is 1000～2000 rev/mins.
Further, in described step 5), 1# flashing tower opening for feed temperature is 420～490 ℃, and the top vacuum degree is 0～80KPa, and the void tower flow velocity is 0.5～2.0m/s; Described 2# flashing tower opening for feed temperature is 340～420 ℃, and the top vacuum degree is 0～120KPa.
Further, in described step 6), coking tower opening for feed temperature is 450～550 ℃, and in coking, tower top pressure is 0.2～2MPa, and scorch time is 12～36 hours.
Further, in described step 7), calcining furnace is raised to 1350～1450 ℃ with the heat-up rate of 50～100 ℃/h, calcines 6～18 hours.
The present invention has compared following advantage with the technology of existing production needle coke:
(1) raw material adopts the pretreatment process of polycondensation, pressurized heat filtration, centrifuging and flash distillation combination, makes quinoline insolubles (QI) content in refining purifying pitch and is less than 0.1%.
(2) the needle coke thermal expansivity prepared is low.
(3) needle coke prepared can meet the requirement of manufacturing ultra-high power graphite electrode, can be used for large-scale steel-smelting electric furnace.
The accompanying drawing explanation
Fig. 1 is the apparatus structure schematic diagram that the preparation technology of coal-based needle coke of the present invention takes.
In figure, 1-feedstock pump 2-1# tubular oven 3-batch condensation polymerization reactor 4-pressurized heat filters still 5-whizzer 6-and purifies polycondensate hopper 7-flash evaporation feed pump 8-1# flashing tower 9-2# flashing tower 10-furnace charge pump 11-2# tubular oven 12-coking tower 13-separation column 14-calcining furnace.
Embodiment
Below by drawings and Examples, the present invention is described in further details.
The preparation technology of coal-based needle coke of the present invention takes device as shown in Figure 1 to realize, the preparation facilities of described coal-based needle coke comprises batch condensation polymerization reactor 3, and batch condensation polymerization reactor 3 is connected with respectively 1# process furnace 2 and pressurized heat filters still 4; 1# process furnace 2 is communicated with respectively and purifies polycondensate hopper 6 and two 1# flashing towers 8 that are connected in series and 2# flashing tower 9 by pipeline; It is two identical kettlies that pressurized heat filters still 4, and two autoclave body bottoms are communicated with whizzer 5, and whizzer 5 is connected with purification polycondensate hopper 6 again; Two 1# flashing towers 8 that are connected in series and 2# flashing tower 9 are communicated with 2# process furnace 11 by furnace charge pump 10,2# process furnace 11 is communicated with two coking towers that are connected in parallel 12, two coking tower 12 top exits are communicated with separation column 13, and separation column 13 is communicated with pressurized heat and filters still 4 formation heavy constituent oil reuse loops; Coking tower 12 bottoms are communicated with calcining furnace 14.
Wherein, the top of batch condensation polymerization reactor 3 is provided with the light oil outlet, bottom is provided with the outlet of polycondensation recycle stock, the outlet of polycondensation recycle stock is connected with the opening for feed pipeline of 1# process furnace 2 bottom heating coils by pipeline, be provided with polycondensation material extraction mouth on the inlet duct of batch condensation polymerization reactor 3, polycondensation material extraction mouth is connected with the entrance of interchanger by pipeline, the feed(raw material)inlet that the outlet of the interchanger pressurized heat identical with two by the pipeline with tee ball valve filters still 4 tops is connected, control two pressurized heats by tee ball valve and filter still 4 alternate operations to realize continuous production.
It is vertical empty still that pressurized heat filters still 4, and bottom is taper, and inside is provided with filtration material layer, and filtration material layer is located at heating and pressurizing and filters at the bottom of the interior tower of still 4 cavitys to 1/6 place of tower top, and filtration material layer is layered on stainless steel filtering net uniformly by solid particulate matter.The top that pressurized heat filters still 4 also is provided with rare gas element inlet mouth and rare gas element venting port.The middle part that pressurized heat filters still 4 is provided with the residue outlet with tightness system, for the replacing of filter material and the removing of filter residue.The bottom that pressurized heat filters still 4 is provided with filtrate outlet, and the filtrate outlet of two pressurized heat filtration still 4 bottoms is connected with the opening for feed of whizzer 5 by three-way pipeline.
Whizzer 5 is link-suspended basket centrifuge, bottom is provided with sludge discharge tube, the discharge port of whizzer 5 is connected by pipeline with the opening for feed that purifies polycondensate hopper 6, being positioned at the discharge port that purifies polycondensate hopper 6 bottoms is connected with the opening for feed of flash evaporation feed pump 7 by pipeline, the discharge port of flash evaporation feed pump 7 is connected by pipeline with the opening for feed of 1# process furnace 2 top heating coils, and the discharge port of 1# process furnace 2 top heating coils is connected with the opening for feed of 1# flashing tower 8 by pipeline.
Coking tower 12 tops are provided with the coking oil gas escape orifice, the coking oil gas escape orifice is connected with the opening for feed pipeline of separation column 13 by three-way pipeline, the discharge port of coking tower 12 bottoms is connected by pipeline with the opening for feed of calcining furnace 14, and the bottom of calcining furnace 14 is provided with the needle coke outlet.Separation column 13 tops are provided with pneumatic outlet, and middle part is provided with the light oil outlet, and bottom is provided with the heavy oil outlet, and bottom is provided with the heavy constituent oil export, and the heavy constituent oil export is connected with the inlet duct that pressurized heat filters still 4 by pipeline.
The present invention realizes by the said apparatus structure comprising the steps: the preparation technology of coal-based needle coke
1) by feed coal tar, coal-tar pitch, return and join viscid bitumen or coal tar fraction is sent in 1# tubular oven 2 with feedstock pump 1, enter batch condensation polymerization reactor 3 after heating, polycondensation adopts Recycle design, the raw material of first polycondensation mixes with the raw material of not polycondensation out from batch condensation polymerization reactor 3 bottoms to advance 1# tubular oven 2 again and heat, from 1# tubular oven 2, a material part out is as product output, and rest part advances batch condensation polymerization reactor 3 circulations again; Recycle ratio is 20～50, and the polycondensation process temperature is 380～500 ℃, and pressure is 0.5～2MPa, and the reaction times is 6～24 hours;
2) enter pressure filtration still 4 after the polycondensation material of step 1) output is cooling, the opening for feed temperature is 150～240 ℃, when the injection rate of polycondensation material reach pressurized heat filter still 4 volumes 2/3 the time, stop charging, injecting inert gas N
2or Ar, be forced into 0.5～2MPa, under protection of inert gas, the polycondensation material is carried out to heat filtering, remove quinoline insolubles (QI).Two pressurized heats filter still 4 hocket the polycondensation material filling and filter to realize continuous production;
Filtration material layer in pressurized heat filtration still 4 is combined by mixture and the stainless steel filtering net of diatomite or pearlstone or diatomite and pearlstone, the mixture of diatomite or pearlstone or diatomite and pearlstone is layered on stainless steel filtering net uniformly, the granularity of diatomite and expanded perlite granule is 50～150 orders, stainless steel filtering net order number is 400～700 orders, and filtering layer thickness is 5～15 centimetres.
3) through step 2) filtrate after heat filtering, enter in link-suspended basket centrifuge 5, the filter cloth order number of whizzer is 1000～1600 orders, rotating speed centrifuging with 1000～2000 rev/mins, further remove quinoline insolubles, in polycondensation material after centrifuging, the content of quinoline insolubles is less than 0.5%, and the purification polycondensation material obtained enters into and purifies polycondensate hopper 6;
4) the purification polycondensation material obtained through step 3) is sent in 1# tubular oven 2 with flash evaporation feed pump 7, heat laggard 1# flashing tower 8, the opening for feed temperature is 420～490 ℃, the top vacuum degree is 0～80KPa, the void tower flow velocity is 0.5～2.0m/s, hard pitch containing quinoline insolubles is discharged from 1# flashing tower 8 bottoms, the flash oil that tower top is overflowed enters 2# flashing tower 9 and carries out flash distillation, the opening for feed temperature is 340～420 ℃, the top vacuum degree is 0～120KPa, 2# flashing tower 9 bottom outputs are made with extra care purifying pitch, tower top effusion light oil, in refining purifying pitch, the content of quinoline insolubles is less than 0.1%,
5) send into again 11 heating of 2# tubular oven through refining purifying pitch injected water steam after pump 10 is extracted out of step 4) output, then enter coking tower 12 coking cokings, the opening for feed temperature is 450～550 ℃, in coking, tower top pressure is 0.2～2MPa, scorch time is 12～36 hours, makes green coke.Two coking tower 12 alternate operations are to realize continuous production.The coking oil gas of overflowing from coking tower 12 tops obtains oil gas, light oil and heavy oil through separation column 13 fractionation, and the heavy constituent oil of separation column 13 bottoms is through pipeline and again enter pressurized heat filtration still 6 from the polycondensation mixing of materials of batch condensation polymerization reactor 3 outputs;
6) green coke made through step 5) is sent in calcining furnace 14, with the heat-up rate of 50～100 ℃/h, is raised to 1350～1450 ℃, calcines 6～18 hours, obtains the product needle coke, and its density is greater than 2.1g/cm
3(adopting standard SH/T0313-92), thermal expansivity (CTE) is less than 1.0 * 10
-6/ ℃ (with reference to GB GB/T3074.4-2003).
Following embodiment is for further illustrating different instances of the present invention.
Embodiment 1:
After being heated by 1# tubular oven 2, feed coal tar enters batch condensation polymerization reactor 3, the polycondensation process temperature is 500 ℃, and pressure is 2MPa, and the reaction times is 6 hours, recycle ratio is 50, enter pressure filtration still 4 after the polycondensation material of output is cooling, the temperature of opening for feed is 240 ℃, and filtration material layer is combined by pearlstone and stainless steel filtering net, the granularity of expanded perlite granule is 50 orders, stainless steel filtering net order number is 700 orders, and filtering layer thickness is 15 centimetres, injects N
2, be forced into 2MPa, filtrate after heat filtering enters in link-suspended basket centrifuge 5, the filter cloth order number of whizzer is 1600 orders, rotating speed centrifuging with 2000 rev/mins, in the purification polycondensation material obtained, the content of quinoline insolubles is 0.46%, purify the laggard 1# flashing tower 8 of polycondensation heating material, the opening for feed temperature is 490 ℃, the top vacuum degree is 80KPa, the void tower flow velocity is 0.5m/s, the flash oil that tower top is overflowed enters 2# flashing tower 9, the opening for feed temperature is 420 ℃, the top vacuum degree is 120KPa, the refining purifying pitch of output at the bottom of tower, the content of quinoline insolubles is 0.091%, the refining purifying pitch of output enters coking tower 12 coking cokings, the opening for feed temperature is 550 ℃, tower top pressure is 2MPa, scorch time is 36 hours, the green coke obtained heat-up rate with 50 ℃/h in calcining furnace 14 is raised to 1450 ℃, calcine 18 hours, the needle coke density of preparation is 2.16g/cm
3, thermal expansivity (CTE) is 0.89 * 10
-6/ ℃.
Embodiment 2:
After being heated by 1# tubular oven 2, feed coal pitch enters batch condensation polymerization reactor 3, the polycondensation process temperature is 380 ℃, pressure is 1MPa, reaction times is 24 hours, recycle ratio is 30, enter pressure filtration still 4 after the polycondensation material of output is cooling, the temperature of opening for feed is 150 ℃, filtration material layer is combined by diatomite and stainless steel filtering net, the granularity of diatomite particle is 150 orders, stainless steel filtering net order number is 600 orders, filtering layer thickness is 5 centimetres, inject Ar, be forced into 0.5MPa, filtrate after heat filtering enters in link-suspended basket centrifuge 5, the filter cloth order number of whizzer is 1000 orders, rotating speed centrifuging with 1000 rev/mins, in the purification polycondensation material obtained, the content of quinoline insolubles is 0.49%, purify the laggard 1# flashing tower 8 of polycondensation heating material, the opening for feed temperature is 420 ℃, the top vacuum degree is 10KPa, the void tower flow velocity is 1m/s, the flash oil that tower top is overflowed enters 2# flashing tower 9, the opening for feed temperature is 360 ℃, the top vacuum degree is 60KPa, the refining purifying pitch of output at the bottom of tower, the content of quinoline insolubles is 0.098%, the refining purifying pitch of output enters coking tower 12 coking cokings, the opening for feed temperature is 450 ℃, tower top pressure is 0.2MPa, scorch time is 24 hours, the green coke obtained heat-up rate with 100 ℃/h in calcining furnace 14 is raised to 1400 ℃, calcine 6 hours, the needle coke density of preparation is 2.13g/cm
3, thermal expansivity (CTE) is 0.98 * 10
-6/ ℃.
Embodiment 3:
Raw material is returned to join after viscid bitumen is heated by 1# tubular oven 2 and enter batch condensation polymerization reactor 3, the polycondensation process temperature is 450 ℃, pressure is 0.5MPa, reaction times is 12 hours, recycle ratio is 20, enter pressure filtration still 4 after the polycondensation material of output is cooling, the temperature of opening for feed is 200 ℃, filtration material layer is combined by mixture and the stainless steel filtering net of diatomite and pearlstone, be crushed to 100 purpose diatomite be crushed to 100 purpose pearlstones in mass ratio 1:1 mix, stainless steel filtering net order number is 400 orders, and filtering layer thickness is 10 centimetres, injects N
2, be forced into 1MPa, filtrate after heat filtering enters in link-suspended basket centrifuge 5, the filter cloth order number of whizzer is 1300 orders, rotating speed centrifuging with 1500 rev/mins, in the purification polycondensation material obtained, the content of quinoline insolubles is 0.46%, purify the laggard 1# flashing tower 8 of polycondensation heating material, the opening for feed temperature is 460 ℃, the top vacuum degree is 50KPa, the void tower flow velocity is 1.2m/s, the flash oil that tower top is overflowed enters 2# flashing tower 9, the opening for feed temperature is 390 ℃, the top vacuum degree is 100KPa, the refining purifying pitch of output at the bottom of tower, the content of quinoline insolubles is 0.091%, the refining purifying pitch of output enters coking tower 12 coking cokings, the opening for feed temperature is 500 ℃, tower top pressure is 1.5MPa, scorch time is 18 hours, the green coke obtained heat-up rate with 60 ℃/h in calcining furnace 14 is raised to 1350 ℃, calcine 15 hours, the needle coke density of preparation is 2.15g/cm
3, thermal expansivity (CTE) is 0.94 * 10
-6/ ℃.
Embodiment 4:
After being heated by 1# tubular oven 2, the feed coal tarry cut enters batch condensation polymerization reactor 3, the polycondensation process temperature is 420 ℃, pressure is 1.5MPa, reaction times is 18 hours, recycle ratio is 40, enter pressure filtration still 4 after the polycondensation material of output is cooling, the temperature of opening for feed is 220 ℃, filtration material layer is combined by pearlstone and stainless steel filtering net, the granularity of expanded perlite granule is 100 orders, stainless steel filtering net order number is 700 orders, filtering layer thickness is 10 centimetres, inject Ar, be forced into 1.5MPa, filtrate after heat filtering enters in link-suspended basket centrifuge 5, the filter cloth order number of whizzer is 1300 orders, rotating speed centrifuging with 1800 rev/mins, in the purification polycondensation material obtained, the content of quinoline insolubles is 0.45%, purify the laggard 1# flashing tower 8 of polycondensation heating material, the opening for feed temperature is 470 ℃, the top vacuum degree is 60KPa, the void tower flow velocity is 1.6m/s, the flash oil that tower top is overflowed enters 2# flashing tower 9, the opening for feed temperature is 420 ℃, the top vacuum degree is 110KPa, the refining purifying pitch of output at the bottom of tower, the content of quinoline insolubles is 0.094%, the refining purifying pitch of output enters coking tower 12 coking cokings, the opening for feed temperature is 550 ℃, tower top pressure is 1.5MPa, scorch time is 30 hours, the green coke obtained heat-up rate with 50 ℃/h in calcining furnace 14 is raised to 1450 ℃, calcine 10 hours, the needle coke density of preparation is 2.15g/cm
3, thermal expansivity (CTE) is 0.93 * 10
-6/ ℃.
Embodiment 5:
After being heated by 1# tubular oven 2, feed coal tar enters batch condensation polymerization reactor 3, the polycondensation process temperature is 480 ℃, pressure is 1.8MPa, reaction times is 21 hours, recycle ratio is 50, the polycondensation material of output enters pressure filtration still 4 after cooling, the temperature of opening for feed is 230 ℃, filtration material layer is combined by mixture and the stainless steel filtering net of diatomite and pearlstone, be crushed to 70 purpose diatomite be crushed to 70 purpose pearlstones in mass ratio 1:1 mix, stainless steel filtering net order number is 600 orders, and filtering layer thickness is 12 centimetres, injects N
2, be forced into 2MPa, filtrate after heat filtering enters in link-suspended basket centrifuge 5, the filter cloth order number of whizzer is 1600 orders, rotating speed centrifuging with 2000 rev/mins, in the purification polycondensation material obtained, the content of quinoline insolubles is 0.41%, purify the laggard 1# flashing tower 8 of polycondensation heating material, the opening for feed temperature is 490 ℃, the top vacuum degree is 40KPa, the void tower flow velocity is 1.5m/s, the flash oil that tower top is overflowed enters 2# flashing tower 9, the opening for feed temperature is 410 ℃, the top vacuum degree is 80KPa, the refining purifying pitch of output at the bottom of tower, the content of quinoline insolubles is 0.091%, the refining purifying pitch of output enters coking tower 12 coking cokings, the opening for feed temperature is 550 ℃, tower top pressure is 1MPa, scorch time is 15 hours, the green coke obtained heat-up rate with 70 ℃/h in calcining furnace 14 is raised to 1450 ℃, calcine 12 hours, the needle coke density of preparation is 2.16g/cm
3, thermal expansivity (CTE) is 0.94 * 10
-6/ ℃.
Embodiment 6:
After being heated by 1# tubular oven 2, feed coal tar enters batch condensation polymerization reactor 3, the polycondensation process temperature is 480 ℃, pressure is 1.8MPa, reaction times is 21 hours, recycle ratio is 50, the polycondensation material of output enters pressure filtration still 4 after cooling, the temperature of opening for feed is 230 ℃, filtration material layer is combined by mixture and the stainless steel filtering net of diatomite and pearlstone, be crushed to 70 purpose diatomite be crushed to 70 purpose pearlstones in mass ratio 1:1 mix, stainless steel filtering net order number is 600 orders, and filtering layer thickness is 12 centimetres, injects N
2, be forced into 2MPa, filtrate after heat filtering enters in link-suspended basket centrifuge 5, the filter cloth order number of whizzer is 1600 orders, rotating speed centrifuging with 2000 rev/mins, in the purification polycondensation material obtained, the content of quinoline insolubles is 0.44%, purify the laggard 1# flashing tower 8 of polycondensation heating material, the opening for feed temperature is 490 ℃, the top vacuum degree is 0KPa, the void tower flow velocity is 2.0m/s, the flash oil that tower top is overflowed enters 2# flashing tower 9, the opening for feed temperature is 340 ℃, the top vacuum degree is 0KPa, the refining purifying pitch of output at the bottom of tower, the content of quinoline insolubles is 0.093%, the refining purifying pitch of output enters coking tower 12 coking cokings, the opening for feed temperature is 550 ℃, tower top pressure is 1MPa, scorch time is 12 hours, the green coke obtained heat-up rate with 70 ℃/h in calcining furnace 14 is raised to 1450 ℃, calcine 12 hours, the needle coke density of preparation is 2.14g/cm
3, thermal expansivity (CTE) is 0.96 * 10
-6/ ℃.
Above content is in conjunction with concrete preferred implementation further description made for the present invention; can not assert that the specific embodiment of the present invention only limits to this; for the general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; can also make some simple deduction or replace, all should be considered as belonging to the present invention and determine scope of patent protection by submitted to claims.
Claims (10)
1. the preparation technology of a coal-based needle coke, is characterized in that, this technique comprises the steps:
1) raw material is sent in the 1# tubular oven, after heating, adopted batch condensation polymerization reactor by Recycle design output polycondensation material;
2) after the polycondensation material of step 1) output is cooling, enter the pressure filtration still, send into pressurized heat with the heat filtering fresh feed pump and filter the filtration material layer filtration of laying in still, filter the still injecting inert gas via air intake valve to heating and pressurizing, pressurization is carried out heat filtering to the polycondensation material under protection of inert gas;
3) through step 2) filtrate of heat filtering, enter in whizzer, centrifuging, the refining purification polycondensation material obtained is sent to and purifies in the polycondensate hopper;
4) obtaining the refining polycondensation material that purifies through step 3) is pumped in the 1# tubular oven with flash evaporation feed, heat laggard 1# flashing tower, hard pitch containing quinoline insolubles is discharged from 1# flashing tower bottom, the flash oil that tower top is overflowed enters the 2# flashing tower and carries out flash distillation, the refining purifying pitch of 2# flashing tower bottom output, tower top effusion light oil;
5) send into again the heating of 2# tubular oven through purifying pitch injected water steam after the furnace charge pump is extracted out of step 4) output, then enter coking tower coking coking, make green coke; The coking oil gas of overflowing from the coking tower top obtains oil gas, light oil and heavy oil through the separation column fractionation, and the heavy constituent oil of separation column bottom is through pipeline and again enter pressurized heat filtration still from the polycondensation mixing of materials of batch condensation polymerization reactor output;
6) green coke made through step 5) is sent in calcining furnace, heats up, and calcining, obtain the product needle coke.
2. the preparation technology of coal-based needle coke according to claim 1, is characterized in that, described raw material is coal tar, coal-tar pitch, returns and join viscid bitumen or coal tar fraction.
3. the preparation technology of coal-based needle coke according to claim 1, is characterized in that, described polycondensation recycle ratio is 20～50, and the polycondensation process temperature is 380～500 ℃, and pressure is 0.5～2MPa, and the reaction times is 6～24 hours.
4. the preparation technology of coal-based needle coke according to claim 1, it is characterized in that, filtration material layer in described heating and pressurizing filtration still is combined by mixture and the stainless steel filtering net of diatomite, pearlstone or diatomite and pearlstone, the granularity of diatomite and expanded perlite granule is 50～150 orders, stainless steel filtering net order number is 400～700 orders, and filtering layer thickness is 5～15 centimetres.
5. the preparation technology of coal-based needle coke according to claim 1, it is characterized in that, described step 2) filter stills hocket filling and the filtration of polycondensation material by two pressurized heats in, it is 150～240 ℃ that pressurized heat filters still opening for feed temperature, is forced into 0.5～2MPa.
6. the preparation technology of coal-based needle coke according to claim 1, is characterized in that, described is N to heating and pressurizing filtration still injecting inert gas
2or Ar.
7. the preparation technology of coal-based needle coke according to claim 1, is characterized in that, the order number of described centrifuge filtering cloth is 1000～1600 orders, and centrifuge speed is 1000～2000 rev/mins.
8. the preparation technology of coal-based needle coke according to claim 1, is characterized in that, in described step 5), 1# flashing tower opening for feed temperature is 420～490 ℃, and the top vacuum degree is 0～80KPa, and the void tower flow velocity is 0.5～2.0m/s; Described 2# flashing tower opening for feed temperature is 340～420 ℃, and the top vacuum degree is 0～120KPa.
9. the preparation technology of coal-based needle coke according to claim 1, is characterized in that, in described step 6), coking tower opening for feed temperature is 450～550 ℃, and in coking, tower top pressure is 0.2～2MPa, and scorch time is 12～36 hours.
10. the preparation technology of coal-based needle coke according to claim 1, is characterized in that, in described step 7), calcining furnace is raised to 1350～1450 ℃ with the heat-up rate of 50～100 ℃/h, calcines 6～18 hours.
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| CN114695846A (en) * | 2020-12-30 | 2022-07-01 | 宝武碳业科技股份有限公司 | Preparation method of needle coke and silicon-containing negative electrode material thereof |
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