CN104045506B - Device and process for extracting phenanthrene, fluoranthene and pyrene products in anthracene oil - Google Patents
Device and process for extracting phenanthrene, fluoranthene and pyrene products in anthracene oil Download PDFInfo
- Publication number
- CN104045506B CN104045506B CN201410300491.1A CN201410300491A CN104045506B CN 104045506 B CN104045506 B CN 104045506B CN 201410300491 A CN201410300491 A CN 201410300491A CN 104045506 B CN104045506 B CN 104045506B
- Authority
- CN
- China
- Prior art keywords
- tower
- fluoranthene
- pyrene
- cut
- anthracene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Indole Compounds (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention belongs to the technical field of advanced treatment of anthracene oil and in particular relates to a device and process for extracting phenanthrene, fluoranthene and pyrene products in anthracene oil. The extracting device comprises an anthracene phenanthrene fraction extraction system and a carbazole fraction extraction system. The extracting device is characterized in that a fluoranthene/pyrene fraction extraction system, a solvent regeneration system, a phenanthrene fraction extraction system and a tail gas purification system are further arranged behind the carbazole fraction extraction system. The extraction device is added with a phenanthrene tower and a fluoranthene/pyrene tower on the previous distillation basis of refined anthracene and carbazole; the setting conditions of the two towers, and the material and filler of the towers are more convenient for extracting the phenanthrene, fluoranthene and pyrene products. The process flow is of four-furnace and four-tower continuous rectification, and capable of producing the anthracene phenanthrene fraction, the carbazole fraction, the fluoranthene fraction, the pyrene fraction and the phenanthrene fraction simultaneously; the process is convenient and flexible to operate, and capable of extracting the phenanthrene, fluoranthene and pyrene having the content of almost 40% in the anthracene oil without increasing more investment; the yield of the products can be more than 80%, and considerable economic benefits can be gained.
Description
Technical field
The invention belongs to carbolineum deep process technology field, especially relate to a kind of carbolineum China and Philippines, fluoranthene, pyrene product extraction element and technique.
Background technology
Coal tar is the byproduct in process of coking, a kind of complex mixture be almost made up of aromatics completely.Isolate carbolineum in coal tar deep processing process, wherein anthracene, phenanthrene, carbazole, fluoranthene, pyrene are all enriched in carbolineum.Phenanthrene is the isomers of the aromatic hydrocarbon with three benzene ring structures, anthracene.For colorless plate crystal, there is blue-fluorescence, can distil, water insoluble.Luxuriant and rich with fragrance solution has blue-fluorescence, can be used for producing dyestuff, medicine and resin etc. after luxuriant and rich with fragrance conversion processing; The luxuriant and rich with fragrance perhydro obtained through hydrogenation is luxuriant and rich with fragrance, can be used for production jet fuel; The luxuriant and rich with fragrance sulfonic acid of sulfonation gained, can be used as binding agent and tanning material.Fluoranthene is a kind of four Polycyclic aromatic hydrocarbons, is yellow-green colour needle crystal, water insoluble, dissolves in dithiocarbonic anhydride and acetic acid, is soluble in ether.Fluoranthene can be used as the raw material of dyestuff and medicine.-8,9 phthaloyl fluoranthene as amino in purple vat dyes 3-, antispasmodic 10b aminoalkyl group-1,2,3 three hydrogen fluoranthene etc.Fluoranthene also can be used as the agent of non-magnetic metal surface inspection.Pyrene is the aromatic hydrocarbon with four benzene ring structures, is the crystallization of faint yellow monocline sheet, water insoluble, is soluble in the organic solvent such as ether and benzene.Pyrene is organic synthesis raw material, can produce Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic, for dyestuff, synthetic resins, dispersed dyestuff and engineering plastics through oxidation; Can the gorgeous orange GR of vat dyes processed and other multiple dyestuffs after acidylate; Also can sterilant processed, softening agent etc.Current whole world coal tar output is about more than 2,200 ten thousand tons, and so carbolineum has about 5,000,000 tons at least, is no less than 180-200 ten thousand tons as the high value added product phenanthrene in carbolineum, fluoranthene, pyrene.
In carbolineum, anthracene, phenanthrene, carbazole, fluoranthene, pyrene are all high boiling point and dystectic aromatics fused ring compound, wherein anthracene content 4.8%-5.5%, carbazole content 2.5%-3.0%, luxuriant and rich with fragrance content 19%-22%, fluoranthene content 9%-11%, pyrene content 6%-8%.Just in carbolineum, anthracene, carbazole are extracted in the extraction process that the outer enterprise of Present Domestic provides, extract total amount and be no more than 6%.For 100,000 tons of carbolineums, I technique: first crystallization goes out crude anthracene from carbolineum, and then extracts anthracene, carbazole with solvent extration, and output is respectively anthracene 1600 tons, carbazole is 600 tons; II technique: be that raw material carries out underpressure distillation with carbolineum, extracts anthracene 3860 tons respectively, (in II technique that extraction effect is good, anthracene, carbazole sum is 5760 tons to carbazole 1900 tons, and phenanthrene+fluoranthene+pyrene extracted amount is 26500 tons, accounts for 26.5% of carbolineum total amount.); So a large amount of high assignments products is used for making charcoal black, and real genus is the great wasting of resources (price of Vehicles Collected from Market phenanthrene is 2.5-3 ten thousand yuan/ton, and the price of fluoranthene is 5-6 ten thousand yuan/ton, and the price of pyrene is 18.5 ten thousand yuan/ton).
Summary of the invention
The object of this invention is to provide a kind of carbolineum China and Philippines, fluoranthene, pyrene product extraction element and technique, the products such as phenanthrene, fluoranthene, pyrene can be extracted in a large number from carbolineum, reduce cost consumption, realize economic interests and maximize.
The object of the invention is to be realized by following technical proposals:
Carbolineum of the present invention is Sino-Philippines, fluoranthene, pyrene product extraction element, comprise the luxuriant and rich with fragrance cut extraction system of anthracene, carbazole cut extraction system, the luxuriant and rich with fragrance cut extraction system of described anthracene comprises the heat exchanger I connected successively, heat exchanger II and interchanger III, the tube furnace I be connected with described interchanger III, the dehydration tower that is connected of tube furnace I therewith, the anthracene tower that is connected of dehydration tower therewith, be connected to the vapour generator I of this anthracene top of tower, the backflash I that is connected of vapour generator I therewith, be connected to the water-and-oil separator at described dehydration tower top, described backflash I is connected with heat exchanger I, described tube furnace I is connected with described anthracene tower, described anthracene tower side line is connected with described heat exchanger II,
Described carbazole cut extraction system comprises carbazole cut tower, the tube furnace II that is connected of carbazole cut tower therewith, be connected to the vapour generator II in described carbazole fraction overhead portion, the backflash II that is connected of vapour generator II therewith, the interchanger IV that is connected of backflash II therewith, described carbazole cut tower is connected with described anthracene tower
It is characterized in that also being provided with fluoranthene/pyrene cut extraction system, solvent regeneration system, luxuriant and rich with fragrance cut extraction system and exhaust gas purification system after described carbazole cut extraction system,
Described fluoranthene and pyrene cut extraction system comprise fluoranthene/pyrene tower, the tube furnace III that fluoranthene therewith/pyrene tower is connected, be connected to the vapour generator III of described fluoranthene/pyrene top of tower, the backflash III that is connected of vapour generator III therewith, the interchanger V that is connected of backflash III therewith, described fluoranthene/pyrene tower is connected with described carbazole cut tower, and described fluoranthene/pyrene tower side line is connected with described interchanger III
Described solvent regeneration system comprises solvent regeneration tower, is connected to dephlegmator and the interchanger VI of this solvent reclamation top of tower, the solvent Receiving bin be connected with described interchanger VI,
Described luxuriant and rich with fragrance cut extraction system comprises luxuriant and rich with fragrance cut tower, the tube furnace IV that is connected of luxuriant and rich with fragrance cut tower therewith, be located at the interchanger VIII of described luxuriant and rich with fragrance cut tower side line, be connected to the interchanger VII in described luxuriant and rich with fragrance fraction overhead portion, described interchanger VII is connected with described solvent Receiving bin, described luxuriant and rich with fragrance cut tower is connected with described solvent regeneration tower
Described exhaust gas purification system comprises tail gas purification tower and pump.
Described anthracene tower, carbazole cut tower, fluoranthene/pyrene tower and Fei Ta are carbon steel.
Described anthracene tower, carbazole cut tower, fluoranthene/pyrene tower and Fei Ta are packing tower.
Described anthracene tower is provided with three opening for feeds and three side take-off mouths.
An extraction process for carbolineum China and Philippines, fluoranthene, pyrene product, is characterized in that:
(1) leave standstill dehydration carbolineum (water content >=0.5%), through heat exchanger I, heat exchanger II and interchanger III, carbolineum temperature is brought up to 180 DEG C-190 DEG C, enter tube furnace I to be heated to more than 220 DEG C and to send dehydration tower to dewater, anhydrous carbolineum after dehydration enters anthracene tower again after the temperature raising of tube furnace I radiation section, dehydration tower gas phase brings water and lightweight oil into water-and-oil separator, and after being separated, water and lightweight oil flow automatically to storage tank respectively;
(2) the anhydrous carbolineum entering into anthracene tower carries out decompression separation, top gaseous phase extraction washing oil oil gas enters backflash I after vapour generator I is condensed to 180 DEG C, part phegma is returned in anthracene tower, a part enters washing oil storage tank after heat exchanger I is cooled to 105 DEG C, the wash oil fraction of extraction, its main component is naphthalene, acenaphthene, dibenzofuran, fluorenes;
(3) the luxuriant and rich with fragrance cut of anthracene tower side take-off anthracene, temperature controls at 274 DEG C-276 DEG C, after volume pump metering extraction, less than 140 DEG C are cooled to send into storage tank through heat exchanger II, as the raw material producing anthracene, the anthracene content of the luxuriant and rich with fragrance cut of the anthracene herein obtained is 25-30%, luxuriant and rich with fragrance content 55-60%;
(4) anthracene tower bottoms is the luxuriant and rich with fragrance later component of anthracene, and this part cut is through liquid level and flow bunch grade adjustment, and part enters carbazole cut tower, and part gets back to tube furnace I, provides thermal source to anthracene tower;
(5) carbazole cut tower, gas phase extraction carbazole cut, tower top oil gas cools laggard backflash II through vapour generator II, part carbazole cut refluxes into carbazole cut tower, a part is through being cooled to 138 DEG C-142 DEG C, and squeezing into storage tank with pump and participate in next procedure washing, is finished product carbazole after washing;
(6) be carbon black oil from the side take-off of carbazole cut tower, be viscid bitumen at the bottom of tower, be the raw material of fluoranthene and pyrene, viscid bitumen fluoranthene content >=40% of now extraction, pyrene content >=30%, asphalt component accounts for 10-12%, and other is for bending and assorted oil distillate;
(7) fluoranthene/pyrene tower, raw material is carbazole cut tower bottoms viscid bitumen, through liquid level and flow bunch grade adjustment, part viscid bitumen enters fluoranthene/pyrene tower, and part gets back to tube furnace II, provides thermal source to carbazole cut tower, fluoranthene/pyrene tower bottoms is heated by tube furnace III, temperature out controls to enter fluoranthene/pyrene tower at 370 DEG C about-380 DEG C, top gaseous phase extraction fluoranthene cut, and oil gas enters backflash III after vapour generator III cools; Part fluoranthene cut refluxes into fluoranthene/pyrene tower, and a part is cooled to 158 DEG C-162 DEG C and enters cut storage tank, and as the raw material producing fluoranthene, fluoranthene/pyrene tower side take-off pyrene cut, squeezes into cut storage tank with after raw material heat exchange, is the raw material producing pyrene;
(8) solvent regeneration tower, the anthracene of this technique, carbazole, pyrene all wash with solvent, the anthracene primary crystallization Residual oil of oil-containing solvent oil, carbazole primary crystallization Residual oil and pyrene primary crystallization Residual oil, be heated in the middle part of 235 ± 3 DEG C of towers entering solvent regeneration tower with carbazole column overhead oil gas, fluoranthene/pyrene column overhead oil gas through interchanger respectively, the solvent oil that tower top is deviate from is cooled to 35 DEG C enters solvent tank through dephlegmator, interchanger, Reusability, solvent regeneration tower tower bottoms, for containing luxuriant and rich with fragrance component, contains luxuriant and rich with fragrance more than 80%;
(9) luxuriant and rich with fragrance cut tower, raw material is containing luxuriant and rich with fragrance component at the bottom of solvent regeneration tower tower, with pump, component luxuriant and rich with fragrance at the bottom of solvent regeneration tower tower is sent into luxuriant and rich with fragrance cut tower, because during solvent regeneration tower extraction solvent, also retain partial solvent in luxuriant and rich with fragrance cut, therefore, luxuriant and rich with fragrance cut column overhead still extraction solvent oil, back dissolving agent receiver after cooling, the luxuriant and rich with fragrance cut of luxuriant and rich with fragrance cut tower side take-off, after heat exchange cooling, enter luxuriant and rich with fragrance pan tank, then go out qualified phenanthrene with the crystallization of rotary drum crystallizer;
(10), in this technological process, all production equipments, storage tank etc. enter tail gas purification tower and carry out tail gas clean-up recovery.
Described anthracene column overhead pressure-controlling is at 10-15KPa, and temperature controls at 230 ± 2 DEG C; Anthracene tower tower bottom pressure controls at 20-30KPa, and temperature controls at 326 ± 2 DEG C.Tube furnace I exports hot oil temperature and controls at 350-355 DEG C.
Described carbazole cut column overhead pressure-controlling is at 10 ± 2KPa, and temperature controls at 290 DEG C ± 2 DEG C; Tower bottom pressure controls at 20-30KPa, and temperature controls 330 DEG C ± 2.
Described fluoranthene/pyrene column overhead pressure-controlling is at 15 ± 2KPa, and tower top temperature controls at 325 ± 2 DEG C, and tower bottom pressure controls at 20-30KPa, and temperature controls at 360-365 DEG C.
In described anthracene tower, carbazole cut tower, fluoranthene/pyrene tower and luxuriant and rich with fragrance cut tower, negative-pressure vacuum degree is >=-85Kpa.
Advantage of the present invention:
(1) carbolineum China and Philippines of the present invention, fluoranthene, pyrene product extraction element and technique, on the distillation basis of former anthracene, carbazole, add Fei Ta and fluoranthene, pyrene tower, the setting model of these two towers, the material of tower and filler are more convenient for the extraction of phenanthrene, fluoranthene, pyrene product.Four stove four tower continuous rectifications are taked in technical process of the present invention, produce the luxuriant and rich with fragrance oil of anthracene, carbazole fraction, fluoranthene fraction simultaneously, pyrene fraction, easy to operate, flexible, when not increasing more investments, by accounting for the phenanthrene of content in carbolineum nearly 40%, fluoranthene, pyrene extract, and yield can reach more than 80%, can obtain considerable economic benefit;
(2) the present invention extracts from carbolineum phenanthrene, fluoranthene, pyrene adopt short route, and namely luxuriant and rich with fragrance raw material sources, in solvent recuperation tower reactor, directly enter luxuriant and rich with fragrance tower with recycle pump; The raw material sources of fluoranthene and pyrene are in carbazole cut tower tower reactor, and be also directly enter fluoranthene and pyrene tower with pump, top gaseous phase is fluoranthene, side line liquid phase extraction pyrene.Adopt short route, mainly solve the physical property that pyrene can not heat repeatedly, thoroughly solve material coking problem; Abbreviated system also considerably reduces gas consumption, avoids the drawback of raw material normal temperature heating temperature raising, decreases a large amount of support equipments, as storage tank, medial launder, interchanger etc. simultaneously; Because of short route, 3 products adopt 2 towers, save a tower than conventional distil-lation, and the type of heating of pump circulation taked by two king-towers, whole system utilizes product and intermediates to conservation measuress such as raw material preheatings simultaneously, and system energy consumption is low, and energy consumption is just with about 75% of scale systems;
(3) carbolineum China and Philippines of the present invention, fluoranthene, pyrene product extraction element and technique adopt underpressure distillation, this underpressure distillation condition requires high than common underpressure distillation, for boiling point and the fusing point of phenanthrene, fluoranthene, pyrene, negative-pressure vacuum degree must ensure more than-85KPa, tower reactor and tower top temperature must control in specified temperature ± 2 DEG C, adopt sub-pressure high-efficient rectifying, reduce rectification temperature, prevent high-temperature coking;
(4) in carbolineum China and Philippines of the present invention, fluoranthene, pyrene product extraction element and technique, the requirement of vacuum tightness is very high, in order to avoid sublimate sucks vacuum pipe, adopts double-condenser, and increases nitrogen purging, efficiently solve the blockage problem of vacuum pipe;
(5) quality index of carbolineum China and Philippines of the present invention, fluoranthene, pyrene product extraction element and technique China and Philippines, fluoranthene, pyrene all can reach more than 98%, and particularly luxuriant and rich with fragrance, fluoranthene does not need with solvent wash, direct crystallization;
(6) in carbolineum China and Philippines of the present invention, fluoranthene, pyrene product extraction element and technique, anthracene tower, carbazole cut tower, fluoranthene/pyrene tower and Fei Ta are packing tower, ensure separating effect, have saved investment.
Accompanying drawing explanation
Fig. 1 is distil process schema of the present invention.
Fig. 2 is washing process schema of the present invention.
Embodiment
The specific embodiment of the present invention is further illustrated below in conjunction with accompanying drawing.
As shown in Figure 1, carbolineum of the present invention is Sino-Philippines, fluoranthene, pyrene product extraction element, comprise the luxuriant and rich with fragrance cut extraction system of anthracene, carbazole cut extraction system, the luxuriant and rich with fragrance cut extraction system of described anthracene comprises the heat exchanger I 1 connected successively, heat exchanger II 2 and interchanger III 3, the tube furnace I 6 be connected with described interchanger III 3, the dehydration tower 5 that is connected of tube furnace I 6 therewith, the anthracene tower 7 that is connected of dehydration tower 5 therewith, be connected to the vapour generator I 8 at this anthracene tower 7 top, the backflash I 9 that is connected of vapour generator I 8 therewith, be connected to the water-and-oil separator 4 at described dehydration tower 5 top, described backflash I 9 is connected with heat exchanger I 1, described tube furnace I 6 is connected with described anthracene tower 7, described anthracene tower 7 side line is connected with described heat exchanger II 2,
Described carbazole cut extraction system comprises carbazole cut tower 11, the tube furnace II 10 that is connected of carbazole cut tower 11 therewith, be connected to the vapour generator II 12 at described carbazole cut tower 11 top, the backflash II 14 that is connected of vapour generator II 12 therewith, the interchanger IV 13 that is connected of backflash II 14 therewith, described carbazole cut tower 11 is connected with described anthracene tower 7
It is characterized in that also being provided with fluoranthene/pyrene cut extraction system, solvent regeneration system, luxuriant and rich with fragrance cut extraction system and exhaust gas purification system after described carbazole cut extraction system,
Described fluoranthene and pyrene cut extraction system comprise fluoranthene/pyrene tower 16, the tube furnace III 15 that fluoranthene therewith/pyrene tower 16 is connected, be connected to the vapour generator III 17 at described fluoranthene/pyrene tower 16 top, the backflash III 19 that is connected of vapour generator III 17 therewith, the interchanger V 18 that is connected of backflash III 19 therewith, described fluoranthene/pyrene tower 16 is connected with described carbazole cut tower 11, and described fluoranthene/pyrene tower 16 side line is connected with described interchanger III 3
Described solvent regeneration system comprises solvent regeneration tower 20, is connected to dephlegmator and the interchanger VI 21 at this solvent regeneration tower 20 top, the solvent Receiving bin 22 be connected with described interchanger VI 21,
Described luxuriant and rich with fragrance cut extraction system comprises luxuriant and rich with fragrance cut tower 24, the tube furnace IV 23 that is connected of luxuriant and rich with fragrance cut tower 24 therewith, be located at the interchanger VIII 25 of described luxuriant and rich with fragrance cut tower 24 side line, be connected to the interchanger VII 26 at described luxuriant and rich with fragrance cut tower 24 top, described interchanger VII 26 is connected with described solvent Receiving bin 22, described luxuriant and rich with fragrance cut tower 24 is connected with described solvent regeneration tower 20
Described exhaust gas purification system comprises tail gas purification tower 27 and pump 28.
Described anthracene tower 7, carbazole cut tower 11, fluoranthene/pyrene tower 16 and Fei Ta 24 are carbon steel.
Described anthracene tower 7, carbazole cut tower 34, fluoranthene/pyrene tower 16 and Fei Ta 24 are packing tower.
Described anthracene tower 7 is provided with three opening for feeds and three side take-off mouths.
An extraction process for carbolineum China and Philippines, fluoranthene, pyrene product, is characterized in that employing four stove four tower negative pressure rectification process, is separated through four towers, obtains the luxuriant and rich with fragrance oil of anthracene, carbazole fraction, fluoranthene and pyrene cut.
One, carbolineum distillation system
(1) carbolineum and the crude anthracene mixing oil (water content ≯ 0.5%) that leave standstill dehydration are got with Beng Congcao district, through heat exchanger I 1, heat exchanger II 2, interchanger III 3(heat exchanger I 1 is raw material/washing oil interchanger, heat exchanger II 2 is the luxuriant and rich with fragrance cut interchanger of raw material/anthracene, interchanger III 3 is raw material/viscid bitumen interchanger) heat exchange is to after 180 ~ 190 DEG C, dehydration tower 5 is sent again after tube furnace I 6 convection zone is heated to 210 ~ 220 DEG C, moisture is wherein deviate to slow down the corrosion of follow-up equipment by High efficiency baffle plate flash distillation, dehydration tower 5 head temperature controls to 170 ~ 180 DEG C, bottom temperature controls to 200 ~ 210 DEG C, anhydrous heavy oil fraction after dehydration is moisture is less than 0.08%, anthracene tower 7 is sent to by after dehydration tower 5 tower reactor liquid level and flow bunch grade adjustment.After dehydration tower 5 tower top oil gas enters water-and-oil separator 4 separation after being condensed to 50 DEG C, waste water is to wastewater trough, and light oil is to washing oil groove;
(2) the anthracene cut after dehydration is in anthracene tower 7 decompression separation, top of tower washing oil oil gas out enters backflash I 9 after vapour generator I 8 is condensed to 180 DEG C, part liquid returns circulation in anthracene tower 7 by backflash I 9 through reflux pump, and a part enters washing oil fraction medial launder to 105 DEG C after being cooled by the adjustment of backflash I 9 liquid level and heat exchanger I 1.The washing oil fraction major ingredient of extraction is naphthalene, acenaphthene, dibenzofuran, fluorenes;
(3) the luxuriant and rich with fragrance cut of anthracene tower 7 side take-off anthracene, temperature controls at 274 DEG C-276 DEG C, after volume pump metering extraction, less than 140 DEG C are cooled to send into storage tank through heat exchanger II 2, as the raw material producing anthracene, the anthracene content of the luxuriant and rich with fragrance cut of the anthracene herein obtained is 25-30%, luxuriant and rich with fragrance content 55-60%; This technique considers diversity and the unstable of raw material, and anthracene tower 7 is provided with three opening for feeds and three side take-off mouths;
(4) anthracene tower 7 bottoms is the luxuriant and rich with fragrance later component of anthracene, and this part cut is through liquid level and flow bunch grade adjustment, and part enters carbazole cut tower 11, and part gets back to tube furnace I 6, provides thermal source to anthracene tower 7; For slowing down coking and the polymerization of heavy constituent in rectifying, anthracene tower 7 adopts rectification under vacuum.The gas phase of the washing oil fraction of tower top effusion is after vapour generator I 8, and liquid phase enters return-flow system, and the non-condensable gas of condensate cooler connects vacuum system.Anthracene tower 7 tower top pressure controls at 10-15KPa, and temperature controls at 230 ± 2 DEG C; Anthracene tower 7 tower bottom pressure controls at 20-30KPa, and temperature controls at 326 ± 2 DEG C.Tower reactor heat is provided by tube furnace I heated by gas, and tube furnace I 6 thermal load is 4,500,000 kcal/h, and tube furnace I 6 exports hot oil temperature 350-355 DEG C;
(5) carbazole cut tower 11, gas phase extraction carbazole cut, tower top oil gas cools laggard backflash II 14 through vapour generator II 12, part carbazole cut refluxes into carbazole cut tower 11, a part is through being cooled to 138 DEG C-142 DEG C, squeezing into storage tank with pump and participate in next procedure washing, is finished product carbazole after washing;
Be condensed to 234 ± 3 DEG C and non-condensable gases condensation at carbazole cut tower 11 tower top oil gas through vapour generator II 12 to be cooled to about 50 DEG C and to enter vacuum system.The pressure-controlling of tower top is at 10 ± 2KPa, and temperature controls at 290 ± 2 DEG C; Tower bottom pressure controls at 20 ~ 30KPa, and temperature controls at 330 DEG C ± 2 DEG C;
In order to reduce system energy consumption further, still reserve carbazole cut tower 11 tower top oil gas and solvent regeneration system regenerates Residual oil heat exchange, after the oil gas and anthracene/carbazole/pyrene primary crystallization Residual oil heat exchange of the temperature 290 ± 2 DEG C of overhead extraction, then enter vapour generator II 12;
(6) carbazole cut tower 11 stripping section is reserved with extraction major ingredient is carbon black oil cut side line, this fraction is got by pump, part through with raw material heat exchange after, carbon black oil cut storage tank is flowed into through cooling, be used for preparing carbon black oil or the raw material as carbolineum hydrogenation, tower reactor part enters after tube furnace II 10 heats and returns carbazole cut tower 11, provides thermal source to carbazole cut tower 11.Tower reactor fluxed bitumen (mainly containing fluoranthene, pyrene) got by recycle pump, and part enters fluoranthene/pyrene tower 16 through liquid level and flow bunch grade adjustment, and part enters tube furnace II 10 and heats, and provides thermal source to carbazole cut tower 11;
(7) fluoranthene/pyrene tower 16 tower top fluoranthene oil gas is condensed to about 170 ± 3 DEG C through vapour generator III 17 and enters backflash III 19, and part returns stream, and part enters fluoranthene storage tank after heat exchange cooling.Non-condensable gases condensate cooler is cooled to about 50 DEG C and enters vacuum system.The pressure-controlling of fluoranthene/pyrene tower 16 tower top is at 15 ± 2KPa, and temperature controls at about 325 ± 2 DEG C; Tower bottom pressure controls at 20 ~ 30KPa, and temperature controls at about 360 ~ 365 DEG C, and tower reactor heat is provided by tube furnace III 15 heated by gas, and tube furnace III 15 thermal load is 2,400,000 kcal/h, and tube furnace III 15 exports hot oil temperature about 375 ~ 385 DEG C;
It is pyrene side line that fluoranthene/pyrene tower 16 stripping section is reserved with extraction major ingredient, this fraction is got by pump, part through with raw material heat exchange after, pyrene cut storage tank is flowed into through cooling, be used as the raw material producing pyrene, tower reactor part enters after tube furnace III 15 heats and returns fluoranthene/pyrene tower 16, provides thermal source to fluoranthene/pyrene tower 16.Part enters carbon black oil groove through liquid level and flow bunch grade adjustment, with the heavy wash oil cut mixture carbon black oil of anthracene tower 7 tower top;
Two, solvent regeneration system
(8) the anthracene primary crystallization Residual oil of oil-containing solvent oil, carbazole primary crystallization Residual oil and pyrene primary crystallization Residual oil are heated in the middle part of 235 ± 3 DEG C of towers entering solvent regeneration tower 20 with carbazole tower 11 tower top oil gas, fluoranthene/pyrene tower 16 tower top oil gas, fluoranthene/pyrene tower 16 tower reactor viscid bitumen through interchanger respectively, tower top deviates from the solvent oil oil gas of 75% through dephlegmator partial reflux, after gas phase and regeneration Residual oil heat exchange, water at low temperature is cooled to 35 ± 3 DEG C to enter regenerated solvent Receiving bin 22.(Residual oil of anthracene primary crystallization) in the middle part of luxuriant and rich with fragrance cut tower 24 is sent into, as producing the luxuriant and rich with fragrance raw material of essence after solvent regeneration tower 20 tower reactor medium liquid level and flow bunch grade adjustment; In order to ensure regeneration efficiency, regeneration adopts negative pressure, and solvent regeneration tower 20 tower top pressure controls at 20 ± 3KPa, and tower bottom pressure controls at 35 ~ 50Kpa; Solvent regeneration tower tower bottoms, for containing luxuriant and rich with fragrance component, contains luxuriant and rich with fragrance more than 80%;
(9) luxuriant and rich with fragrance cut tower 24, raw material is containing luxuriant and rich with fragrance component at the bottom of solvent regeneration tower 20 tower, with pump, component luxuriant and rich with fragrance at the bottom of solvent regeneration tower 20 tower is sent into luxuriant and rich with fragrance cut tower 24, because during solvent regeneration tower 20 extraction solvent, also retain partial solvent in luxuriant and rich with fragrance cut, therefore, luxuriant and rich with fragrance cut tower 24 tower top still extraction solvent oil, back dissolving agent Receiving bin 22 after cooling, the luxuriant and rich with fragrance cut of luxuriant and rich with fragrance cut tower 24 side take-off, after heat exchange cooling, enter luxuriant and rich with fragrance pan tank, then go out qualified phenanthrene with the crystallization of rotary drum crystallizer; The pressure-controlling of luxuriant and rich with fragrance cut tower 24 tower top is at 20 ± 3KPa, and temperature controls at about 280 ± 3 DEG C; Tower bottom pressure controls at 30 ~ 50KPa, and temperature controls at about 310 ~ 315 DEG C; Tower reactor part enters after tube furnace IV 23 heats and returns luxuriant and rich with fragrance cut tower 24, provides thermal source to luxuriant and rich with fragrance cut tower 24.Part enters carbon black oil groove through liquid level and flow bunch grade adjustment, with the heavy wash oil cut mixture carbon black oil of anthracene tower 7 tower top;
(10), in this technological process, the tail gas that all production equipments, storage tank etc. produce enters tail gas purification tower 27 and carries out tail gas clean-up recovery.
In the process engineering of the present invention four stove four column distillation, in anthracene tower 7, carbazole cut tower 11, fluoranthene/pyrene tower 16 and luxuriant and rich with fragrance cut tower 24, negative-pressure vacuum degree is >=-85Kpa.
Three, dehumidification system is washed
As shown in Figure 2, the carbazole/anthracene extracted in carbolineum China and Philippines of the present invention, fluoranthene, pyrene product extraction process/pyrene cut needs through washing, dehumidification system purifies out carbazole, anthracene and pyrene finished product.Carbazole/anthracene/pyrene cut is pumped into carbazole/anthracene/pyrene cut washing filter 30 by transferpump and washs together with solvent after carbazole/anthracene/pyrene cut mixture groove 29 mixing, carbazole/anthracene after washing/pyrene cut drying machine 31 vacuum-drying, obtain carbazole, anthracene and pyrene finished product, enter Residual oil Receiving bin 32 through carbazole/anthracene/pyrene cut washing filter 30 crystallization Residual oil out.Fluoranthene/luxuriant and rich with fragrance cut, without the need to washing dehumidification system washing, can obtain fluoranthene, luxuriant and rich with fragrance finished product through high the putting after groove 33 enters rotary drum crystallizer 34 crystallization of fluoranthene/luxuriant and rich with fragrance cut.
Each shell and tube cooler backwater of the present invention returns water cooling tower after concentrating and entering recirculated water backwater water-main, the circulating hot water of whereabouts is uniformly distributed by the air cooling of rising in water cooling tower, flow automatically in pond after dropping to pond and complete circulation, cooled water is again recycled water pump extraction and is sent to each water cooler, thus completes whole closed cycle.Technique vacuum requirement of the present invention is higher, drawback is that sublimate sucks vacuum pipe, in order to head it off, double-condenser measure can be adopted in the gas phase of anthracene tower 7, carbazole cut tower 11, fluoranthene/pyrene tower 16 and Fei Ta 24 and liquid phase production end, and increasing nitrogen purging, namely the problem of the stifled vacuum pipe occurred in technique can solve completely.
Instrument and supplies flow process of the present invention takes four stove four tower continuous rectifications, produce the luxuriant and rich with fragrance oil of anthracene, carbazole fraction, fluoranthene fraction simultaneously, pyrene fraction, easy to operate, flexible, when not increasing more investments, by accounting for the phenanthrene of content in carbolineum nearly 40%, fluoranthene, pyrene extract, and yield can reach more than 80%, can obtain considerable economic benefit.Adopt short route in technique, mainly solve the physical property that pyrene can not heat repeatedly, thoroughly solve material coking problem.Abbreviated system also considerably reduces gas consumption, avoids the drawback of raw material normal temperature heating temperature raising, decreases a large amount of support equipments, as storage tank, medial launder, interchanger etc. simultaneously.Because of short route, 3 products adopt 2 towers, save a tower than conventional distil-lation, and meanwhile, whole system utilizes product and intermediates to conservation measuress such as raw material preheatings, and system energy consumption is low, and energy consumption is just with about 75% of scale systems.
Through the extraction of present invention process to carbolineum China and Philippines, fluoranthene, pyrene product, the quality index of phenanthrene, fluoranthene, pyrene all can reach more than 98%, and particularly luxuriant and rich with fragrance, fluoranthene does not need with solvent wash, direct crystallization.
Carbolineum China and Philippines of the present invention, fluoranthene, pyrene product extraction element and technology investment are little, and output is high, and improve the purification precision to phenanthrene, fluoranthene, pyrene product, are applicable to extensively promoting and using.
Claims (9)
1. carbolineum China and Philippines, fluoranthene, pyrene product extraction element, comprise the luxuriant and rich with fragrance cut extraction system of anthracene, carbazole cut extraction system, the luxuriant and rich with fragrance cut extraction system of described anthracene comprises the heat exchanger I connected successively, heat exchanger II and interchanger III, the tube furnace I be connected with described interchanger III, the dehydration tower that is connected of tube furnace I therewith, the anthracene tower that is connected of dehydration tower therewith, be connected to the vapour generator I of this anthracene top of tower, the backflash I that is connected of vapour generator I therewith, be connected to the water-and-oil separator at described dehydration tower top, described backflash I is connected with heat exchanger I, described tube furnace I is connected with described anthracene tower, described anthracene tower side line is connected with described heat exchanger II,
Described carbazole cut extraction system comprises carbazole cut tower, the tube furnace II that is connected of carbazole cut tower therewith, be connected to the vapour generator II in described carbazole fraction overhead portion, the backflash II that is connected of vapour generator II therewith, the interchanger IV that is connected of backflash II therewith, described carbazole cut tower is connected with described anthracene tower
It is characterized in that also being provided with fluoranthene/pyrene cut extraction system, solvent regeneration system, luxuriant and rich with fragrance cut extraction system and exhaust gas purification system after described carbazole cut extraction system,
Described fluoranthene and pyrene cut extraction system comprise fluoranthene/pyrene tower, the tube furnace III that fluoranthene therewith/pyrene tower is connected, be connected to the vapour generator III of described fluoranthene/pyrene top of tower, the backflash III that is connected of vapour generator III therewith, the interchanger V that is connected of backflash III therewith, described fluoranthene/pyrene tower is connected with described carbazole cut tower, and described fluoranthene/pyrene tower side line is connected with described interchanger III
Described solvent regeneration system comprises solvent regeneration tower, is connected to dephlegmator and the interchanger VI of this solvent reclamation top of tower, the solvent Receiving bin be connected with described interchanger VI,
Described luxuriant and rich with fragrance cut extraction system comprises luxuriant and rich with fragrance cut tower, the tube furnace IV that is connected of luxuriant and rich with fragrance cut tower therewith, be located at the interchanger VIII of described luxuriant and rich with fragrance cut tower side line, be connected to the interchanger VII in described luxuriant and rich with fragrance fraction overhead portion, described interchanger VII is connected with described solvent Receiving bin, described luxuriant and rich with fragrance cut tower is connected with described solvent regeneration tower
Described exhaust gas purification system comprises tail gas purification tower and pump.
2. carbolineum China and Philippines according to claim 1, fluoranthene, pyrene product extraction element, is characterized in that described anthracene tower, carbazole cut tower, fluoranthene/pyrene tower and Fei Ta are carbon steel.
3. carbolineum China and Philippines according to claim 1, fluoranthene, pyrene product extraction element, is characterized in that described anthracene tower, carbazole cut tower, fluoranthene/pyrene tower and Fei Ta are packing tower.
4. the carbolineum China and Philippines according to claim 1,2 or 3, fluoranthene, pyrene product extraction element, is characterized in that described anthracene tower is provided with three opening for feeds and three side take-off mouths.
5. an extraction process for carbolineum China and Philippines, fluoranthene, pyrene product, is characterized in that:
(1) dehydration carbolineum is left standstill, carbolineum water content >=0.5%, through heat exchanger I, heat exchanger II and interchanger III, carbolineum temperature is brought up to 180 DEG C-190 DEG C, enter tube furnace I to be heated to more than 220 DEG C and to send dehydration tower to dewater, anhydrous carbolineum after dehydration enters anthracene tower again after the temperature raising of tube furnace I radiation section, dehydration tower gas phase brings water and lightweight oil into water-and-oil separator, and after being separated, water and lightweight oil flow automatically to storage tank respectively;
(2) the anhydrous carbolineum entering into anthracene tower carries out decompression separation, top gaseous phase extraction washing oil oil gas enters backflash I after vapour generator I is condensed to 180 DEG C, part phegma is returned in anthracene tower, a part enters washing oil storage tank after heat exchanger I is cooled to 105 DEG C, the wash oil fraction of extraction, its main component is naphthalene, acenaphthene, dibenzofuran, fluorenes;
(3) the luxuriant and rich with fragrance cut of anthracene tower side take-off anthracene, temperature controls at 274 DEG C-276 DEG C, after volume pump metering extraction, less than 140 DEG C are cooled to send into storage tank through heat exchanger II, as the raw material producing anthracene, the anthracene content of the luxuriant and rich with fragrance cut of the anthracene herein obtained is 25-30%, luxuriant and rich with fragrance content 55-60%;
(4) anthracene tower bottoms is the luxuriant and rich with fragrance later component of anthracene, and this part cut is through liquid level and flow bunch grade adjustment, and part enters carbazole cut tower, and part gets back to tube furnace I, provides thermal source to anthracene tower;
(5) carbazole cut tower, gas phase extraction carbazole cut, tower top oil gas cools laggard backflash II through vapour generator II, part carbazole cut refluxes into carbazole cut tower, a part is through being cooled to 138 DEG C-142 DEG C, and squeezing into storage tank with pump and participate in next procedure washing, is finished product carbazole after washing;
(6) be carbon black oil from the side take-off of carbazole cut tower, be viscid bitumen at the bottom of tower, be the raw material of fluoranthene and pyrene, viscid bitumen fluoranthene content >=40% of now extraction, pyrene content >=30%, asphalt component accounts for 10-12%, and other is for bending and assorted oil distillate;
(7) fluoranthene/pyrene tower, raw material is carbazole cut tower bottoms viscid bitumen, through liquid level and flow bunch grade adjustment, part viscid bitumen enters fluoranthene/pyrene tower, and part gets back to tube furnace II, provides thermal source to carbazole cut tower, fluoranthene/pyrene tower bottoms is heated by tube furnace III, temperature out controls to enter fluoranthene/pyrene tower at 370 DEG C-380 DEG C, top gaseous phase extraction fluoranthene cut, and oil gas enters backflash III after vapour generator III cools; Part fluoranthene cut refluxes into fluoranthene/pyrene tower, and a part is cooled to 158 DEG C-162 DEG C and enters cut storage tank, and as the raw material producing fluoranthene, fluoranthene/pyrene tower side take-off pyrene cut, squeezes into cut storage tank with after raw material heat exchange, is the raw material producing pyrene;
(8) solvent regeneration tower, the anthracene of this technique, carbazole, pyrene all wash with solvent, the anthracene primary crystallization Residual oil of oil-containing solvent oil, carbazole primary crystallization Residual oil and pyrene primary crystallization Residual oil, be heated in the middle part of 235 ± 3 DEG C of towers entering solvent regeneration tower with carbazole column overhead oil gas, fluoranthene/pyrene column overhead oil gas through interchanger respectively, the solvent oil that tower top is deviate from is cooled to 35 DEG C enters solvent tank through dephlegmator, interchanger, Reusability, solvent regeneration tower tower bottoms, for containing luxuriant and rich with fragrance component, contains luxuriant and rich with fragrance more than 80%;
(9) luxuriant and rich with fragrance cut tower, raw material is containing luxuriant and rich with fragrance component at the bottom of solvent regeneration tower tower, with pump, component luxuriant and rich with fragrance at the bottom of solvent regeneration tower tower is sent into luxuriant and rich with fragrance cut tower, because during solvent regeneration tower extraction solvent, also retain partial solvent in luxuriant and rich with fragrance cut, therefore, luxuriant and rich with fragrance cut column overhead still extraction solvent oil, back dissolving agent receiver after cooling, the luxuriant and rich with fragrance cut of luxuriant and rich with fragrance cut tower side take-off, after heat exchange cooling, enter luxuriant and rich with fragrance pan tank, then go out qualified phenanthrene with the crystallization of rotary drum crystallizer;
(10), in this technological process, all production equipments, storage tank enter tail gas purification tower and carry out tail gas clean-up recovery.
6. the extraction process of a kind of carbolineum China and Philippines according to claim 5, fluoranthene, pyrene product, it is characterized in that described anthracene column overhead pressure-controlling is at 10-15KPa, temperature controls at 230 ± 2 DEG C; Anthracene tower tower bottom pressure controls at 20-30KPa, and temperature controls at 326 ± 2 DEG C,
Tube furnace I exports hot oil temperature and controls at 350-355 DEG C.
7. the extraction process of a kind of carbolineum China and Philippines according to claim 5, fluoranthene, pyrene product, it is characterized in that described carbazole cut column overhead pressure-controlling is at 10 ± 2KPa, temperature controls at 290 DEG C ± 2 DEG C; Tower bottom pressure controls at 20-30KPa, and temperature controls 330 DEG C ± 2.
8. the extraction process of a kind of carbolineum China and Philippines according to claim 5, fluoranthene, pyrene product, it is characterized in that described fluoranthene/pyrene column overhead pressure-controlling is at 15 ± 2KPa, tower top temperature controls at 325 ± 2 DEG C, and tower bottom pressure controls at 20-30KPa, and temperature controls at 360-365 DEG C.
9. the extraction process of a kind of carbolineum China and Philippines according to claim 5, fluoranthene, pyrene product, is characterized in that in described anthracene tower, carbazole cut tower, fluoranthene/pyrene tower and luxuriant and rich with fragrance cut tower, negative-pressure vacuum degree is >=-85Kpa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410300491.1A CN104045506B (en) | 2014-06-30 | 2014-06-30 | Device and process for extracting phenanthrene, fluoranthene and pyrene products in anthracene oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410300491.1A CN104045506B (en) | 2014-06-30 | 2014-06-30 | Device and process for extracting phenanthrene, fluoranthene and pyrene products in anthracene oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104045506A CN104045506A (en) | 2014-09-17 |
| CN104045506B true CN104045506B (en) | 2015-07-08 |
Family
ID=51498955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410300491.1A Active CN104045506B (en) | 2014-06-30 | 2014-06-30 | Device and process for extracting phenanthrene, fluoranthene and pyrene products in anthracene oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104045506B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111470935B (en) * | 2020-03-13 | 2021-06-04 | 太原理工大学 | Method for separating phenanthrene and fluorene |
| CN112250539B (en) * | 2020-11-13 | 2023-01-24 | 新奥科技发展有限公司 | Oil product separation and refining method |
| CN114307215B (en) * | 2021-12-17 | 2023-09-08 | 新奥科技发展有限公司 | Pyrene rectifying device and pyrene rectifying method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786935B (en) * | 2010-02-26 | 2012-12-12 | 曲靖众一精细化工股份有限公司 | Method for extracting fluorene, anthracene and carbazole from mixed anthracene oil |
| CN103232318B (en) * | 2013-04-16 | 2016-04-06 | 中冶焦耐工程技术有限公司 | With a carbolineum be raw material production anthracene, the method for smart carbazole and luxuriant and rich with fragrance product and device |
| CN103739439B (en) * | 2014-01-22 | 2015-06-17 | 鞍山兴德工程技术有限公司 | Device for preparing refined anthracene and refined carbazole by taking anthracene oil as raw material |
-
2014
- 2014-06-30 CN CN201410300491.1A patent/CN104045506B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104045506A (en) | 2014-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106588579B (en) | A method of extracting phenolic compound from carbolic oil | |
| CN103466874B (en) | High-concentration phenol-ammonia sewage treatment method | |
| CN104045506B (en) | Device and process for extracting phenanthrene, fluoranthene and pyrene products in anthracene oil | |
| CN103242902A (en) | Processing method of coal tar | |
| CN102634363A (en) | Three-tower type atmospheric-vacuum tar distillation process | |
| CN208166891U (en) | A kind of DMAC, DMF or DMSO waste liquid dehydration purification recovery system | |
| CN103333080A (en) | Quadruple-effect method for rectifying and recycling waste water containing DMF (dimethyl formamide) | |
| CN101475435A (en) | Method for preparing industrial naphthalin by single-furnace double-tower vacuum distillation | |
| CN110804486B (en) | Method and system for regenerating waste lubricating oil | |
| CN110015949B (en) | Method for extracting phenolic substances from raw oil containing phenol | |
| CN107446606A (en) | The technique and device of a kind of coal tar production modified coal tar pitch, aliphatic hydrocarbon and aromatic hydrocarbon | |
| CN102634381B (en) | System and method for treating benzene-contained separating water of coking benzol | |
| CN109423318B (en) | Coal tar deep processing technology for directly extracting industrial naphthalene by adding alkali after atmospheric and vacuum distillation | |
| CN206570285U (en) | A kind of coal oven dithio-gas crude benzene recovery device | |
| CN209759339U (en) | Recovery unit of dichloromethane in cefuroxime acid production | |
| CN202849288U (en) | DMF (dimethyl formamide) rectifying, recovering and recycling system | |
| CN106367110A (en) | Energy-saving tar processing technology | |
| CN207143178U (en) | A kind of device of coal tar production modified coal tar pitch, aliphatic hydrocarbon and aromatic hydrocarbon | |
| CN202576341U (en) | Three-tower atmospheric and vacuum tar distillation unit | |
| CN102504852B (en) | Improved Litwin coal tar processing technic | |
| CN110003939A (en) | A kind of efficient carbolic oil dephenolization method | |
| CN103242131A (en) | Industrial naphthalene distillation process | |
| CN212152190U (en) | Coal tar three-tower continuous deep processing system | |
| CN103664616A (en) | Method and device for producing benzyl benzoate | |
| CN109852413A (en) | A kind of method of coal tar production modified coal tar pitch |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |