CN104449819B - The method that fuel oil accelerates desulfurization, denitrogenation and ionic liquid recycling - Google Patents

The method that fuel oil accelerates desulfurization, denitrogenation and ionic liquid recycling Download PDF

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Publication number
CN104449819B
CN104449819B CN201310418383.XA CN201310418383A CN104449819B CN 104449819 B CN104449819 B CN 104449819B CN 201310418383 A CN201310418383 A CN 201310418383A CN 104449819 B CN104449819 B CN 104449819B
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ionic liquid
recovery process
oil recovery
process step
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CN104449819A (en
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张伟民
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/28—Recovery of used solvent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
    • C10G27/14—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen with ozone-containing gases
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G7/00—Distillation of hydrocarbon oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

A kind of method that fuel oil accelerates desulfurization, denitrogenation and ionic liquid recycling, include a fuel oil extraction processing step, an oxidation treatment step, a centrifuging treatment step, an Oil recovery process step, ionic liquid recycling step, a public process step, with ozone (Ozone-O wherein in oxidation treatment step3) as oxidant replacing traditional hydrogen peroxide (H2O2), fuel oil is accelerated reaction in desulfurization, the extraction processing step of denitrogenation, but ionic liquid or aromatic hydrocarbon (Aromatic) substance characteristics will not be changed.The fuel oil of low-sulfur, low nitrogen is then reclaimed with short-distance distiller respectively in Oil recovery process step, ionic liquid recycling step, and reclaims ionic liquid；The present invention has can carry out deep desulfuration, denitrogenation under relative low temperature, operating on low voltage environment, have more security with the feature that does not cause secondary pollution and operation and with relative energy-conservation and the features such as can save manufacturing cost.

Description

The method that fuel oil accelerates desulfurization, denitrogenation and ionic liquid recycling
Technical field
The invention relates to a kind of method of desulfurization of fuel oil purification, it is that a kind of fuel oil accelerates to take off to particularly relate to it The method of sulphur, denitrogenation and ionic liquid recycling.
Background technology
Because the fuel oil market demand of below the standard sulfur content 10PPM disclosed in low sulphur fuel oil particularly European Union is carried Rise, therefore the correlative study of fuel oil deep desulfuration and denitrogenation never stops；However, still big in the technology for using on the market at present Mostly it is traditional hydrodesulfurization technology, it is main reasons is that hydrodesulfurization technology relative maturity, and its treatment energy is big, because This, is still used by most oil plant at present；But existing traditional hydrodesulfurization technology processes it in so-called deep desulfuration Made fuel oil afterwards, its sulfur content is still about in 50PPM；And due to require below sulfur content 10PPM deep desulfuration it is low Sulphur fuel oil market demand is ardent, with existing traditional hydrodesulfurization technology for, unless lifting catalyst reaction rate, increased work Make pressure and improve reaction temperature, cannot otherwise reach the index of deep desulfuration with existing hydrodesulfurization technology；So And, improve catalyst reaction rate and be intended to research and develop new catalyst, increase operating pressure and improve operating temperature etc. then anticipate Taste technique and equipment and need to be transformed again, and these measures can not only greatly improve operating cost, and can greatly improve the behaviour of technique Make risk；Moreover, it is also a great problem that how the remaining catalyst after being processed through deep desulfuration carries out treatment；Therefore, current main flow The rare correlation technique improved as source with traditional hydrodesulfurization technology of in the market, is instead then other Different methods.
Technological property used by, the technology during these are developed at present can substantially be summarized as following 5 kinds, hereby sketch such as Under：
1. the technology of solvent extraction desulfurization：It is in brief that, with specific solvent as extractant, and sulphur can be dissolved with the solvent Compound but the characteristic of other hydrocarbons will not be dissolved, and the method that the sulfide in fuel oil is extracted.Used Solvent include DMF, DMSO, MDEA polar solvent, but during operation, therefore class solvent has volatility and toxicity, so The pollution of environment can be caused.
2. oxidative desulfurization techniques：Its method is to use hydrogen peroxide (H2O2), ozone (Ozone-O3), ultraviolet (Ultraviolet), the Strong oxdiative thing such as peroxy acid (Peroxyacid Peracid) is first aoxidized to fuel oil, then with polarity Solvent such as ACN (Acetonitrile), DMSO (dimethylsufoxide), DMF (N, N-dimethyformamide) etc. Separating and extracting is carried out, but because these polar solvents have high volatile and inflammability, holds fire hazardous and blast.
3. desulfurization technology is adsorbed：Main method is that adsorbent is added in sulfur removal technology with the vulcanization in adsorbed fuel Thing, then the purpose of desulfurization is reached by hydrodesulfurization reaction；And the adsorbent containing sulfide is then re-fed into regenerator, utilize Oxidizing process is regenerated；This method is similar to hydrodesulfurization, and one of subject matter is for the DBT (two in sulfide Benzene thiophene) etc sulfide its adsorption capacity it is not good, be the blind spot for technology.
4. Technology for Microbial Desulfurization：Main method be using microbial metabolism produce desulfurase be catalyst to be urged Change desulphurization reaction, to reach the effect of desulfurization；This method can be operated under normal pressure, normal temperature environment, and safe is its advantage； It is its shortcoming but reaction speed is slow, efficiency is low and desulfurization bacterial strain toxigenic capacity is high.Additionally, still there is the culture skill including enzyme How art is commercialized, bacterial strain how volume production problem etc., these problems all urgently overcome, therefore, in practice, such technology is still It is difficult to commercially carry out the application of commerciality.
5. desulfurization and denitrogenation are carried out by extractant of ionic liquid：This method and the foregoing side with solvent as extractant Method is similar, and main difference is that this method uses avirulent room-temperature ion liquid (Room Temperature Ionic Liquid it is) extractant, is lifting reaction rate, oxidant such as hydrogen peroxide H is then added after extraction process2O2And urge Agent such as acetic acid Ethanoic Acid (CH3COOH), formic acid (HCOOH) or trifluoracetic acid (CF3COOH) accelerating desulfurization anti- The carrying out answered；Reacted mixed liquor is then allowed to settle precipitation, and upper liquid is the fuel oil after purification, and subnatant is ion The reactant mixture of liquid, oxidant and catalyst；Afterwards, then with centrifuge by upper and lower layer feed separation, upper strata fuel oil Again by obtaining low sulphur fuel oil after dehydration and distillation, lower floor's material recycles back extraction thing such as n-hexane (C6H14) or N- methyl Pyrrolidones (NMP) is stripped, and the aromatic hydrocarbon compound (Aromatic compound) in mixed liquor is extracted Come, then ionic liquid is separated with n-hexane (or NMP) with centrifuge again, complete the mesh of ionic liquid recycling 's.
In above-mentioned method, it is clear that, above-mentioned the 5th kind of method extracted with ionic liquid and be aided with again oxidation Catalytic processes accelerate extractive reaction, reclaim ionic liquid for recycling to be stripped mode again afterwards, are in the market Operated in the method for research it is most safe, be also a kind of preferred mode that can most reach deep desulfuration effect；But aoxidized in addition Agent to lift reaction rate during the oxidant such as hydrogen peroxide (H that is used2O2) high concentration occasion run into it is water miscible The chemical reaction of fierceness can be produced during ionic liquid, can also produce the hyperpyrexia of moment to cause ionic liquid to produce hydrolysis, can all made Into ionic liquid cannot recycling problem.Therefore, use instead to produce intense reaction and not result in ionic liquid and produce water The oxidant for solving reaction is exactly a kind of necessary improved main points, because this problem can cause that ionic liquid produces the change of quality to make Into can only be partially recycled or with that originally cannot reclaim；Further, since using acetic acid, formic acid or trifluoracetic acid all can be extracted out The aromatic hydrocarbon compound for coming produces chemical reaction and is more combined closely with ionic liquid, and causing finally must be with the side of back extraction Method is such as stripped aromatic hydrocarbon compound with n-hexane, to isolate ionic liquid；These measures can all produce extra operation Cost；Further, since n-hexane has toxicity, can be accumulated in human body, Long Term Contact n-hexane will also result in it is neuropathic in Poison, these are all the reason for causing this kind of technique generation technology bottleneck.
The present invention be directed to the above-mentioned relevant issues that abstraction desulfurization technology is carried out with ionic liquid provide one it is improved Method so that this kind of technology operationally can safer, efficiency can be lifted and running cost can be reduced more, to This kind of technology can be used extensively at last so that the popularization of the clean fuel oil of low-sulfur and low nitrogen and using can more popularization, To the environmental quality that we are lived can be lifted, and acid rain and atmosphere pollution can be reduced to the harm caused by the earth.
Therefore, the present inventor is the actively research and development, via reality in line with being engaged in the practical experience that petroleum technology is designed and developed for many years Border is tested, and cause has generation of the invention.
The content of the invention
The present invention provides one kind using ozone (Ozone-O3) as oxidant to replace traditional hydrogen peroxide (H2O2), with Accelerate reaction in desulfurization, the extraction process of denitrogenation, but fuel oil acceleration desulfurization, denitrogenation and the ion of substance characteristics will not be changed The method of liquid recycling.
The present invention provides a kind of operating system by short-distance distiller, and can be in low temperature, the safe working environment of low pressure Under with reclaim low-sulfur, the fuel oil of low nitrogen and reclaim ionic liquid, the present invention have can enter under relative low temperature, operating on low voltage environment Row deep desulfuration, denitrogenation, security is had more and with relative energy-conservation and can with the feature that does not cause secondary pollution and operation The features such as saving manufacturing cost.
Be that the present invention includes a fuel oil extraction processing step, an oxidation treatment step up to above-mentioned, at a centrifugation Reason step, an Oil recovery process step, ionic liquid recycling step, wherein a public process step, the fuel oil Extraction processing step is used to mix to carry out the extraction procedures of desulfurization and denitrogenation with ionic liquid by the fuel oil；
And the oxidation treatment step includes：A. the oxidation treatment step application has several material-handling pumps and one includes The ozone generator assembly and a venturi of one air compressor machine, the drainage of a gases at high pressure and contaminant filter, an ozone generator Air and liquid mixer and a mixed liquor for including a gas purger buffer mixing channel and an exhaust blower and an activated carbon Adsorption tank and an acceleration reactive tank；B. ozone generator assembly manufacture ozone and ozone storage is standby, and with one of them Material-handling pump will send into this article mound in the fuel oil extraction processing step by the fuel oil and the mixed liquor of ionic liquid that extract In air and liquid mixer, and make the venturi air and liquid mixer suck compression ozone and with by blender and by extraction The mixed liquor of fuel oil and ionic liquid carries out gas-liquid mixed, forms the disturbance of bubble type；C. the venturi air and liquid mixer is passed through Gas and the blended effect of liquid after, mixed liquor is then reacted into mixed liquor buffering mixing channel, effusion mixed liquor Ozone then rises to gas purger accumulation, and is emitted into after gas is drawn through into active carbon adsorption groove by means of exhaust blower In air, and the mixed liquor of mixing channel is buffered then up to reaching predetermined fluid level into the mixed liquor, restart material-handling pump, will Mixed liquor feeding accelerates reactive tank persistently to be reacted；
And centrifuging treatment step, it is used to borrow a high-speed centrifuge by the acceleration reactive tank in oxidation treatment step Mixed liquor after extractive reaction carries out high-speed separation, to form the mixed liquor of an ionic liquid and extract, and a fuel oil and The mixed liquor of a small amount of extract；
And the Oil recovery process step, with short-path distillation as operation core, it includes：A. at the Oil recovery Reason step includes several Oil recovery process step material-handling pumps, an Oil recovery process step preheater, a combustion Material oil recycling step short-distance distiller, an Oil recovery process step heat kerosene expansion slot, Oil recovery treatment Step heat kerosene heating furnace, several Oil recovery process step heat kerosene delivery pumps, a fuel oil receive temporary tank, a fuel Oil recycling step byproduct is received at temporary tank, an Oil recovery process step vacuum buffer groove, an Oil recovery Reason step gas-liquid separator, an Oil recovery process step vavuum pump, a product oil accumulator tank, Oil recovery treatment step Rapid byproduct accumulator tank；B. with Oil recovery process step heat kerosene heating furnace and the heat kerosene of Oil recovery process step Delivery pump processes the cylinder wall interlayer of heat kerosene warp let-off Oil recovery process step short-distance distiller and Oil recovery The heating jacket layer of step preheater, is recycled back into Oil recovery process step heat kerosene heating furnace；And another strand of heating agent It is oily then send into the Oil recovery process step heat kerosene expansion slot, it is recycled back into the Oil recovery process step heat kerosene Heating furnace, until the cylinder wall interlayer and the Oil recovery process step of the Oil recovery process step short-distance distiller The heating jacket layer of preheater reaches predetermined operating temperature, and afterwards, heat kerosene heating furnace carries out intermittent starting again, to maintain System job temperature；C. starting fluid oil recycles step vavuum pump, by the Oil recovery process step vacuum buffer Groove and Oil recovery process step gas-liquid separator are to Oil recovery process step short-distance distiller, the fuel oil Temporary tank is received, the Oil recovery process step byproduct receives temporary tank carries out lasting pumping (vacuumizing), until reaching Untill predetermined operating pressure, afterwards, vavuum pump carries out intermittent pumping again, only to hold system in default operating pressure；d. One of them Oil recovery process step material-handling pump, the fuel oil that centrifuging treatment step is formed and a small amount of extraction The mixed liquor warp let-off Oil recovery process step preheater heating of thing is taken, Oil recovery process step short-path distillation is re-fed into Device, the scraper plate set by Oil recovery process step short-distance distiller inside smears the mixed liquor of fuel oil and a small amount of extract Film is formed in the cylinder wall surface of Oil recovery process step short-distance distiller, the film is walked by Oil recovery treatment Preset temperature produced by the cylinder wall interlayer of rapid short-distance distiller is heated and evaporates fuel oil molecule, and allows fuel oil Son is flown to set by Oil recovery process step short-distance distiller by the auxiliary of molecular free path and the suction function of pumping Built-in condenser, then by the condenser will attach to condenser surface fuel oil molecule cooling condensation and revert back to liquid Condense out, enter back into the fuel oil and receive temporary tank and send into the product oil accumulator tank；E. the fuel oil and a small amount of extract Mixed liquor in a small amount of extract turn into point because default operating temperature and operating pressure fail to reach evaporating temperature Sub- shape, therefore, this part of extract is then still presented liquid and progressively glides and fall into the Oil recovery process step short distance Distiller lower inside, enters back into the Oil recovery process step byproduct and receives temporary tank and send at the Oil recovery Reason step byproduct accumulator tank；
And the ionic liquid recycles step with short-path distillation as operation core, it includes：A. ionic liquid recycling Step contains several ionic liquid recycling step material-handling pumps, ionic liquid recycling step preheater, an ionic liquid Recycling step short-distance distiller, ionic liquid recycling step heat kerosene expansion slot, ionic liquid recycling step Heat kerosene heating furnace, several ionic liquid recycling step heat kerosene delivery pumps, an ionic liquids are received temporary tank, an ionic liquid and are returned Receive process step byproduct and receive temporary tank, ionic liquid recycling step vacuum buffer groove, ionic liquid recycling step Rapid gas-liquid separator, ionic liquid recycling step vavuum pump, an ionic liquid accumulator tank, ionic liquid recycling step pair Product accumulator tank；B. step heat kerosene heating furnace and ionic liquid recycling step heat kerosene are recycled with the ionic liquid Delivery pump reclaims the cylinder wall interlayer and the ionic liquid of heat kerosene warp let-off ionic liquid recycling step short-distance distiller The heating jacket layer of process step preheater, is recycled back into ionic liquid recycling step heat kerosene heating furnace, and another Stock heat kerosene then sends into ionic liquid recycling step heat kerosene expansion slot, is recycled back into ionic liquid recycling step Heat kerosene heating furnace, at the cylinder wall interlayer of ionic liquid recycling step short-distance distiller and the ionic liquid recovery The heating jacket layer for managing step preheater reaches predetermined operating temperature, and afterwards, row batch (-type) is started heat kerosene heating furnace again, with Maintenance system is in default operating temperature；C. ionic liquid recycling step vavuum pump is started, at the ionic liquid recovery Reason step vacuum buffer groove, ionic liquid recycling step gas-liquid separator recycle step short-path distillation to the ionic liquid Device, the ionic liquid are received temporary tank, ionic liquid recycling step byproduct and receive temporary tank and vacuumized, until reaching Predetermined operating pressure, afterwards, row batch (-type) starts pumping to vavuum pump again, to maintain system in default operating pressure；D. its One of ionic liquid recycling step material-handling pump, the ionic liquid that the centrifuging treatment step is formed and extraction The mixed liquor warp let-off of thing ionic liquid recycling step preheater heating, is re-fed into ionic liquid recycling step short distance and steams Device is evaporated, the scraper plate set by ionic liquid recycling step short-distance distiller inside smears the mixed liquor of ionic liquid and extract The film of a predetermined thickness is formed in the cylinder wall surface of ionic liquid recycling step short-distance distiller, makes the film by this Predetermined temperature produced by the cylinder wall interlayer of ionic liquid recycling step short-distance distiller is heated and evaporates ionic liquid Molecule, and the molecule of the ionic liquid flies to ionic liquid recycling step by the air-extraction function of molecular free path and system One of set built-in condenser inside rapid short-distance distiller, then the ionic liquid that condenser surface is will attach to by the condenser Molecule is lowered the temperature and reverts back to liquid condensation and get off, and is entered back into the ionic liquid and is received temporary tank and send into the ionic liquid accumulator tank；e. And the extract in the mixed liquor of the ionic liquid and extract does not reach condition of work because of system operating temperatures and operating pressure, therefore Fail to be evaporated as molecularity, and liquid is still presented and progressively glides and falls into ionic liquid recycling step short distance Distiller lower inside, enters back into ionic liquid recycling step byproduct and receives temporary tank and send at the ionic liquid recovery Reason step byproduct accumulator tank；And the public process step, cooling tower generation cooling water, it is used to provide the cooling water to this The condenser of Oil recovery process step short-distance distiller, the condenser of ionic liquid recycling step short-distance distiller are made Used for condensed water.Reaction can be accelerated in desulfurization, the extraction processing step of denitrogenation accordingly, to carry out deep desulfuration, denitrogenation But do not change the substance characteristics of extract, and low-sulfur, the clean fuel oil of low nitrogen can be reclaimed under low temperature, the working environment of low pressure And ionic liquid is reclaimed for recycling.
Below only by specific embodiment, and assistant be described in detail with accompanying drawing, enable for various functions of the invention, Feature, has a better understanding and awareness.
Brief description of the drawings
Fig. 1 is that the systems such as fuel oil extraction processing step of the invention, oxidation treatment step, centrifuging treatment step are shown It is intended to.
Fig. 2 is Oil recovery process step system schematic of the invention.
Fig. 3 is that ionic liquid of the invention recycles step system schematic diagram.
Fig. 4 is public process step system schematic of the invention.
【Symbol description】
Fuel oil extraction processing step 10 fuel oil mediation heating tank 11
The room-temperature ion liquid storage tank 14 of material-handling pump 121/122/131/132
The mixed liquor dashpot 16 of the fuel oil of centrifugal extracter 15 and extract
The material-handling pump 211/212/221/222 of oxidation treatment step 20
The air compressor machine 231 of ozone generator assembly 23
The drainage and the ozone generator 233 of contaminant filter 232 of gases at high pressure
The mixed liquor of venturi air and liquid mixer 24 buffers mixing channel 25
The exhaust blower 26 of gas purger 251
Active carbon adsorption groove 27 accelerates reactive tank 28
Centrifuging treatment step 30 counts material-handling pump 311/312
High-speed centrifuge 32
The temporary tank 33 of ionic liquid and extract mixed liquor
The temporary tank 34 of fuel oil and a small amount of extract mixed liquor
Oil recovery process step 40
Oil recovery process step material-handling pump 411/412/421/422/431/432
The Oil recovery process step short-distance distiller 45 of Oil recovery process step preheater 44
The cold well 453 of 451 reductor of motor 452
The material storing groove 455 of Oil recovery process step material-handling pump 454
Oil recovery process step heat kerosene expansion slot 46
Oil recovery process step heat kerosene heating furnace 47
Oil recovery process step heat kerosene delivery pump 481/482
Fuel oil receives temporary tank 491
Oil recovery process step byproduct receives temporary tank 492
Oil recovery process step vacuum buffer groove 493
Oil recovery process step gas-liquid separator 494
The product oil accumulator tank 496 of Oil recovery process step vavuum pump 495
Oil recovery process step byproduct accumulator tank 497
Ionic liquid recycles step 50
Ionic liquid recycling step material-handling pump 511/512/521/522/531/532
The ionic liquid recycling step short-distance distiller 55 of ionic liquid recycling step preheater 54
The cold well 553 of 551 reductor of motor 552
Ionic liquid recycling step material-handling pump 554
The ionic liquid of material storing groove 555 recycling step heat kerosene expansion slot 56
Ionic liquid recycling step heat kerosene heating furnace 57
Ionic liquid recycling step heat kerosene delivery pump 581/582
Ionic liquid receives temporary tank 591
Ionic liquid recycling step byproduct receives temporary tank 592
Ionic liquid recycling step vacuum buffer groove 593
Ionic liquid recycling step gas-liquid separator 594
The ionic liquid accumulator tank 596 of ionic liquid recycling step vavuum pump 595
Ionic liquid recycling step byproduct accumulator tank 597
The cooling tower 61 of public process step 60
The frozen water machine cooling water delivery pump 631/632 of frozen water unit 62
The cooling water delivery pump 651/652 of cooling water recovery pump 641/642
Cooling water delivery pump 661/662.
Specific embodiment
Refer to shown in Fig. 1 to Fig. 4, present pre-ferred embodiments include a fuel oil extraction processing step (Fuel Oil Extraction Process) centrifuging treatment of 10, one oxidation treatment step (Oxidation Process) 20, Step (High Speed Centrifuge Separation Process) 30, one Oil recovery process step (Fuel Oil Recovery Process) 40, one ionic liquid recycling step (Ionic Liquid Recovery Process) 50th, a public process step (Utility Facility) 60, is below described in detail.
Refer to shown in Fig. 1, the fuel oil extraction processing step 10, be used to mix to carry out with ionic liquid by the fuel oil Desulfurization and the extraction procedures of denitrogenation.
The fuel oil extraction processing step 10 with have a fuel oil reconcile heating tank 11, several material-handling pumps 121/122/ 131/132nd, room-temperature ion liquid 1- octyl group -3- methyl imidazolium tetrafluoroborates are stored inside one（OMIM BF4）Or 1- butyl -3- The room-temperature ion liquid storage tank 14 of methylimidazole titanium tetrachloride salt (BMIMFeCl4), a centrifugal extracter (Centrifugal Extractor) the mixed liquor dashpot 16 of 15, one fuel oil and extract.
When the fuel oil extraction processing step 10 is operated, fuel oil is first heated to 70 DEG C in fuel oil mediation heating tank 11； Afterwards, synchronous averaging material-handling pump 121/122/131/132, according to default charge proportion, fuel oil and ionic liquid is sent Entering centrifugal extracter 15 carries out the extraction processing step of desulfurization and denitrogenation, and the fuel oil of contact is completed by centrifugal extractor 15 And the mixed liquor of ionic liquid then persistently carries out extractive reaction into mixed liquor dashpot 16.
The property and the number of sulfur content of the default charge proportion foundation fuel oil of above-mentioned fuel oil, ionic liquid, fuel The matching ratio of oil and ionic liquid is different；According to experiment, variety classes fuel oil can be from 3 with the charge proportion of ionic liquid: 1~1:3.5, but this charging matching ratio work when can also be subject to contained DBTs contents and extraction processing step in fuel oil Make temperature and influenceed.
The oxidation treatment step 20, includes：
A. the oxidation treatment step 20 is containing several material-handling pumps 211/212/221/222 and includes an air compressor machine 231st, the drainage of a gases at high pressure and contaminant filter 232, the ozone of an ozone generator (Ozone Generator) 233 are produced The venturi air and liquid mixer of life assembly 23 and (Venturi Ejector) 24 and one includes a gas purger (Ventilator) 251 mixed liquor the buffering exhaust blower 26 of mixing channel 25 and one and an active carbon adsorption groove 27 and Accelerate reactive tank 28；
B. when practical operation, ozone generator 233 starts the oxidation treatment step 20 in advance, starts manufacture ozone and incites somebody to action Ozone is with 2 ~ 3kg/cm2Pressure compression be stored in it is standby in steel cylinder；And fuel oil inside mixed liquor dashpot 16 and from When the mixed liquor of sub- liquid reaches default high level, material-handling pump 211/212 starts, and will previously pass through centrifugal extracter 15 Fuel oil and ionic liquid mixed liquor feeding venturi air and liquid mixer 24, and pass through venturi air and liquid mixer 24 in liquid When sucked compressed ozone and carry out gas-liquid with mixed liquor into venturi air and liquid mixer 24 simultaneously by lateral bypass inlet Mixing, when passing through the throat of venturi air and liquid mixer 24 due to ozone, is reduced but by again unexpected after throat because of passage Amplify, therefore ozone gas can form the fierce disturbance of bubble type in venturi air and liquid mixer 24, this kind of phenomenon can be carried High ozone contacts with each other with the mixed liquor of fuel oil and ionic liquid, with the reaction speed of accelerated oxidation reaction lifting extraction processing step Rate, but its substance characteristics (ionic liquid or aromatic hydrocarbon Aromatic) will not be changed；Mixed liquor after gas-liquid mixed then enters mixing Liquid buffering mixing channel 25 is reacted, and includes that the ozone after decay then rises to gas purger from mixed liquor escaping gas 251 accumulations, now air blower 26 starts, and gas is drawn through in the air discharged after active carbon adsorption groove 27, this mechanism The air emissions that can exist is adsorbed in advance, to avoid causing air pollution；And it is mixed to enter mixed liquor buffering The mixed liquor for closing groove 25 then persistently carries out extractive reaction, until the liquid level in mixed liquor buffering mixing channel 25 reaches default high level When, then row startup material-handling pump 221/222, accelerate reactive tank 28 persistently to be reacted mixed liquor feeding, to be ready for The process step of next stage.
Centrifuging treatment step 30 is used to accelerating in the oxidation treatment step 20 mixed after the extractive reaction of reactive tank 28 Closing liquid carries out high-speed separation, and to form the mixed liquor of an ionic liquid and extract, and a fuel oil and a small amount of extract is mixed Close liquid.
The centrifuging treatment step 30 includes several material-handling pumps 311/312, a high-speed centrifuge (High Speed Disc Separator) temporary tank 33 of 32, one ionic liquid and extract mixed liquor, a fuel oil and a small amount of extract The temporary tank 34 of mixed liquor.
When operation, the mixed liquor of fuel oil and ionic liquid is in accelerating reactive tank 28 with pre- for the centrifuging treatment step 30 If time cycle in complete extractive reaction after, material-handling pump 311/312 start start, by mixed material feeding at a high speed from Centrifugal separator 32, by mixed liquor, liquid is fuel oil from ionic liquid containing the different otherness of proportion between extract at the middle and upper levels, with Two strands of different compositions are carried out high-speed separation by supercentrifuge；Ionic liquid (containing extract) after separation follows pipeline and enters ion The temporary tank 33 of liquid and extract mixed liquor, and fuel oil (containing a small amount of extract) then follows pipeline incoming fuel oil and a small amount of extraction The temporary tank 34 of thing mixed liquor is taken to treat further treatment.
The proportion of above-mentioned ionic liquid (OMIM BF4) is about 1.10kg/liter；Ionic liquid (BMIMFeCl4) proportion be 1.365kg/liter；The proportion of fuel oil then depending on the group composition of fuel oil, gasoline about 0.73 ~ 0.76kg/liter, light bavin Oily (High Speed Diesel) is 0.83 ~ 0.86kg/liter, and marine diesel oil and boiler are with diesel oil (Marine Diesel) About 0.85 ~ 0.87kg/liter, and aviation fuel oil (Jet Fuel) is then about 0.75 ~ 0.8kg/liter；Heavy fuel (Heavy Fuel Oil) oil then depending on species, commonly uses IFO-180 ~ IFO-380 or 1 ~ No. 6 heavy oil, then proportion is distributed in Between 0.86 ~ 0.991kg/liter.But with ionic liquid phase ratio, ionic liquid still has considerable degree of with the proportion of both fuel oil Gap, can be used supercentrifuge by two bursts of feed separations.
Refer to shown in Fig. 2, the Oil recovery process step 40 is operation core with short-path distillation, and it includes：a. The Oil recovery process step 40 contains the several material-handling pumps 411/412/421/422/ of Oil recovery process step 431/432nd, the preheater 44 of an Oil recovery process step, the short-distance distiller (Short of an Oil recovery process step Path Evaporator) 45, one Oil recovery process step heat kerosene expansion slot 46, an Oil recovery process step Heat kerosene heating furnace 47, the heat kerosene delivery pump 481/482 of several Oil recovery process steps, a fuel oil receive it is temporary Groove 491, the byproduct of an Oil recovery process step receive temporary tank 492, the vacuum of an Oil recovery process step is delayed Jet-bedding 493, the gas-liquid separator 494 of an Oil recovery process step, the vavuum pump 495 of an Oil recovery process step, The byproduct accumulator tank 497 of one product oil accumulator tank 496, an Oil recovery process step；
B. when practical operation, first starting fluid oil recycles the heat kerosene of step to the Oil recovery process step 40 The heat kerosene delivery pump 481/482 of heating furnace 47 and Oil recovery process step, starts heat kerosene warp let-off Oil recovery The heat kerosene heating of the cylinder wall interlayer of process step short-distance distiller 45 and the preheater 44 of Oil recovery process step Chuck layer, is recycled back into the heat kerosene heating furnace 47 of Oil recovery process step；The branch pipe and another strand of heat kerosene is then dutiful Line feeding Oil recovery process step heat kerosene expansion slot 46, is recycled back into the conveying of Oil recovery process step heat kerosene The entrance of pump 481/482 warp let-off Oil recovery process step heat kerosene heating furnace 47 again；This preheating program is persistently carried out, until The preheating of the cylinder wall interlayer temperature and Oil recovery process step of the short-distance distiller 45 of Oil recovery process step After the heat kerosene heating jacket layer of device 44 reaches default operating temperature, heat kerosene heating furnace 47 just suspends heating until after heat release The hot coal oil of backflow is just started and heated once again again at a temperature below heating furnace after preset temperature；I.e. heating furnace carries out interval again The starting of property, to maintain required operating temperature；The heating power and temperature of the heat kerosene heating furnace 47 of Oil recovery process step The control of degree is diode (Diode) type temperature controller (the Heating Fluid Controller, figure configured by system In do not show) be controlled；
C. while Oil recovery process step heating agent heating system for oil is operated, Oil recovery process step Vavuum pump 495 starts simultaneously, begins through Oil recovery process step vacuum buffer groove 493, Oil recovery process step Gas-liquid separator 494 receives temporary tank 491, Oil recovery to Oil recovery process step short-distance distiller 45, fuel oil Process step byproduct is received temporary tank 492 and is vacuumized, until the vacuum pressure inside whole pipeline reaches default work After making pressure, afterwards, Oil recovery process step vavuum pump 495 just temporarily ceases pumping, until start short distance after charging steaming The rising of the internal process pressure of device 45 is evaporated, Oil recovery process step vavuum pump 495 just starts pumping again, that is, vavuum pump is again Row is intermittent to be started to maintain required operating pressure, and this mechanism can allow whole Oil recovery process step short-distance distiller Operating pressure inside 45 maintains preset range always in operation, to maintain the stability of system；
D. being ready to complete in system can start operation, and fuel oil and a small amount of extract in centrifuging treatment step 30 When the temporary tank 34 of mixed liquor reaches high level, Oil recovery process step material-handling pump 411,412 starts to start, and will fire The indirectly heat of mixed liquor warp let-off Oil recovery process step preheater 44 of material oil and a small amount of extract；By Oil recovery The charging distribution plate of the inner upper of material incoming fuel oil recycling step short-distance distiller 45 of process step preheater 44, Fallen along the steaming of Oil recovery process step short distance in the discharging breach of diagonal configuration with bleeding point by charging distribution plate again Evaporate cylinder wall (Cylinder) incoming fuel oil recycling step short-distance distiller 45 in device 45；At Oil recovery One group of 4 face being provided with inside reason step short-distance distiller 45, sustainable rotation is driven by a motor 451 and a reductor 452 of top Scraper plate module (be also called and scrape cage, do not show in figure), scrape cage front be provided with the scraper plate (Blade) that an entire row graphite is made, stone The spring mechanism at black scraper plate rear then pushes away forward and tightly against Oil recovery process step short-distance distiller graphite scraper plate 45 inner casing wall, therefore, when material glides along cylinder wall, lasting rotary rpm is about the graphite scraper plate of 160 ~ 180RPM then By the mixed liquor of fuel oil and a small amount of extract be applied to cylinder wall surface formed a predetermined thickness film, and due to material by Position in distribution plate incoming fuel oil recycling step short-distance distiller 45 is just in the angle of 180 degree with bleeding point, because This material forms the position of film just all on the one side on bleeding point opposite；And it is original just in the state of lasting preheating in cylinder wall Under because operating pressure and the operating temperature of Oil recovery process step short-distance distiller inside 45 reached will be locked Fuel oil component is evaporated the condition of work as molecularity, therefore, fall into cylinder wall and extruded by scraper plate in material one and apply Smear after film-form is turned on cylinder wall, all fuel for being locked into target in the case of being heated in the surface moment of film Oil molecule is all evaporated and is discharged (Fly out) immediately, and because the bleeding point from diagonal relative position is still persistently taken out Gas forms an entrance for low pressure, therefore these molecules being evaporated start to follow the relatively low bleeding point of operating pressure Move in direction；But because the position in the middle of Oil recovery process step short-distance distiller 45 is provided with one group of condenser from top to bottom (not shown), therefore, the fuel oil molecule that these are evaporated first was contacted before condenser arrival bleeding point is passed through Condenser pipe on to condenser, due to there is cooling water to pass through inside condenser pipe, therefore will attach to the fuel oil of condenser surface Molecule is lowered the temperature and reverts back to liquid condensation and get off, then is followed the pipeline incoming fuel oil of lower section and received temporary tank 491, and in fuel oil Receive when reaching high level inside temporary tank 491, Oil recovery process step material-handling pump 421,422 automatics, will The fuel oil feeding product oil accumulator tank 496 of recovery is waited and transported；
E. in Oil recovery process step 40, extract bag a small amount of in the mixed liquor of fuel oil and a small amount of extract The foreign bodys such as sulfur compound, nitride and aromatic hydrocarbon (Impurities) aspect, then because in set predetermined work Method there is no to be evaporated as molecularity under pressure, operating temperature, therefore, these impurities are then still presented liquid progressively along vapour Casing wall is glided and falls into the tilting recovering hopper of the lower inside of Oil recovery process step short-distance distiller 45, then overflow is entered Enter in discharge pipe, the Oil recovery process step byproduct for finally then entering lower section receives temporary tank 492, and in fuel oil When the liquid level that recycling step byproduct receives temporary tank 492 reaches high level, the conveying of Oil recovery process step material Pump 431,432 starts, and this byproduct feeding Oil recovery process step byproduct accumulator tank 497 is stored into wait transports.
Refer to shown in Fig. 3, ionic liquid recycling step 50 is operation core with short-path distillation, and it includes：a. Ionic liquid recycling step 50 application has several ionic liquid recycling step material-handling pumps 511/512/521/522/ 531/532nd, ionic liquid recycling step preheater 54, ionic liquid recycling step short-distance distiller (Short Path Evaporator) 55, one ionic liquid recycling step heat kerosene expansion slot 56, ionic liquid recycling step heat Matchmaker's oil heating furnace 57, number ionic liquid recycling step heat kerosene delivery pump 581/582, an ionic liquid receive temporary tank 591, Ionic liquid recycling step byproduct receive temporary tank 592, ionic liquid recycling step vacuum buffer groove 593, from Sub- liquid recycling step gas-liquid separator 594, ionic liquid recycling step vavuum pump 595, an ionic liquid accumulator tank 596th, ionic liquid recycling step byproduct accumulator tank 597；
B. the ionic liquid recycles step 50 when practical operation, first starts ionic liquid recycling step heat kerosene and adds Hot stove 57 and Oil recovery process step heat kerosene delivery pump 581/582, start to recycle heat kerosene warp let-off ionic liquid The heat kerosene heating jacket layer of cylinder wall interlayer and ionic liquid recycling the step preheater 54 of step short-distance distiller 55, It is recycled back into ionic liquid recycling step heat kerosene heating furnace 57；And another strand of heat kerosene is then dutiful by-pass line feeding ion Liquid recycling step heat kerosene expansion slot 56, is recycled back into ionic liquid recycling step heat kerosene delivery pump 581,582 Warp let-off ionic liquid recycles step heat kerosene heating furnace 57 to entrance again；This preheating program is persistently carried out, until ionic liquid is returned Receive the heat kerosene of cylinder wall interlayer temperature and ionic liquid recycling the step preheater 54 of process step short-distance distiller 55 After heating jacket layer reaches default operating temperature, heat kerosene heating furnace just suspends heating, until the hot coal oil flowed back after heat release Just started once again again at a temperature below heating furnace after preset temperature and heated；Ionic liquid recycles step heat kerosene heating furnace The control of 57 heating power and temperature is diode (Diode) type temperature controller (Heating configured by system Fluid Controller and programmable controller PLC, do not show in figure) it is controlled；
C. while ionic liquid recycling step heating agent heating system for oil is operated, ionic liquid recycling step Vavuum pump 595 starts simultaneously, begins through ionic liquid recycling step vacuum buffer groove 593, ionic liquid recycling step Gas-liquid separator 594 receives the recovery of temporary tank 591, ionic liquid to Oil recovery process step short-distance distiller 55, ionic liquid Process step byproduct is received temporary tank 592 and is vacuumized, until the vacuum pressure inside whole pipeline reaches default work Untill making pressure, afterwards, ionic liquid recycling step vavuum pump 595 just temporarily ceases pumping, until after starting charging, short distance Distiller internal process pressure rises, and ionic liquid recycling step vavuum pump 595 just starts pumping again, that is, heating furnace is again Row is intermittent to be started, and with maintenance work temperature, this mechanism can allow in whole ionic liquid recycling step short-distance distiller 55 The operating pressure in portion maintains preset range always in operation, to maintain the stability of system；
D. being ready to complete in system can start operation, and mix in centrifuging treatment step 30 intermediate ion liquid and extract When the temporary tank 33 of liquid reaches high level, ionic liquid recycling step material-handling pump 511/512 starts to start, by ionic liquid And the indirectly heat of mixed liquor warp let-off ionic liquid recycling step preheater 54 of extract；Step is recycled by ionic liquid The material of preheater 54 enters the charging distribution plate of the inner upper of ionic liquid recycling step short-distance distiller 55, then by feeding Fallen along ionic liquid recycling step short-distance distiller 55 in the discharging breach of diagonal configuration with bleeding point on distribution plate Cylinder wall (Cylinder) enter ionic liquid recycling step short-distance distiller 55；Because ionic liquid recycling step is short The screed die that one group of 4 face is driven sustainable rotation by a motor 551 and a reductor 552 of top is provided with inside journey distiller 55 Group (is also called and scrapes cage, do not show in figure), scrapes cage front and is provided with the scraper plate (Blade) that an entire row graphite is made, after graphite scraper plate The spring mechanism of side then pushes away forward and tightly against ionic liquid Oil recovery process step short-distance distiller 55 graphite scraper plate Inner casing wall, therefore, when material glides along cylinder wall, continue rotary rpm and be about the graphite scraper plate of 160 ~ 180RPM then will The mixed liquor of ionic liquid and extract is applied to cylinder wall surface and forms film, and because material is returned by distribution plate into ionic liquid It is just in the angle of 180 degree with bleeding point to receive the position in process step short-distance distiller 55, therefore material forms the position of film Put just all on the one side on bleeding point opposite；And it is original just in the state of lasting preheating in cylinder wall, because ionic liquid recovery The operating pressure of process step short-distance distiller inside 55 has reached with operating temperature and has evaporated locked ionic liquid composition To turn into the condition of work of molecularity, therefore, falling into cylinder wall and be applied on cylinder wall by scraper plate extruding in material one turns into After film-form, in the case of being heated in the surface moment of film all locked ionic liquid molecules all evaporated immediately and Discharge (Fly out), and still persistently pumping forms an entrance for low pressure due to the bleeding point from diagonal relative position, because This these ionic liquid molecule being evaporated starts to follow the relatively low bleeding point direction movement of operating pressure；But because from Position in the middle of sub- liquid recycling step short-distance distiller 55 is provided with one group of condenser (not shown) from top to bottom, therefore, The ionic liquid molecule that these are evaporated first contacted the condensation to condenser before condenser arrival bleeding point is passed through Pipe, due to there is cooling water to pass through inside condenser pipe, therefore will attach to the ionic liquid molecule cooling of condenser surface and reverts back to Liquid is condensed out, then is followed the pipeline of lower section and received temporary tank 591 into ionic liquid, and is received in temporary tank 591 in ionic liquid When portion reaches high level, the automatic of ionic liquid recycling step material-handling pump 521/522, the ionic liquid feeding that will be reclaimed Ionic liquid accumulator tank 596 is waited and transported；
E. in ionic liquid recycling step 50, extract bag a small amount of in the mixed liquor of fuel oil and a small amount of extract The foreign bodys such as sulfur compound, nitride and aromatic hydrocarbon (Impurities) aspect, then because in set predetermined work Method there is no to be evaporated as molecularity under pressure and operating temperature, therefore, under these impurities are then still presented liquid progressively Slide and fall into the tilting recovering hopper of the lower inside of ionic liquid recycling step short-distance distiller 55, then overflow enters discharge In pipeline, the ionic liquid recycling step byproduct for finally then entering lower section receives temporary tank 592, and at ionic liquid recovery When the liquid level that reason step byproduct receives temporary tank 592 reaches high level, ionic liquid recycling step material-handling pump 531, 532 start, and this byproduct feeding ionic liquid recycling step byproduct accumulator tank 597 is stored into wait transports.
Refer to shown in Fig. 4, the public process step 60 is used to provide cooling water and frozen water, give Oil recovery treatment The condenser of step short-distance distiller 45 and the cold well 453 of exterior arrangement and ionic liquid recycling step short-path distillation The cold well 553 that the condenser of device 55 and outside are configured is used.
The public process step 60 application has a cooling tower 61, a frozen water unit 62, several frozen water machine cooling waters to convey Pump 631/632, a cooling water recovery pump 641/642, a cooling water delivery pump 651/652, a cooling water delivery pump 661/662 etc. Equipment.
When the public process step 60 is operated, the equipment that the above-mentioned public process step 60 is included starts one by one, allows ice Water, cooling water are via frozen water machine cooling water delivery pump 631/632, cooling water delivery pump 651/652, cooling water delivery pump 661/ 662 deliver to target device such as Oil recovery process step short-distance distiller 45 and ionic liquid recycling step short-distance distiller 55 cooling water inlet pipeline, then walk around to the pipeline of receipts and return, and cooling tower is sent back to cooling water recovery pump 641/642 again and is entered Row radiating and cooling, allow cooling water that default temperature is returned to when sending out again；According to the demand of system, the cooling water of output its temperature About 25 ~ 28 DEG C, the cooling water temperature of recovery is about 30 ~ 33 DEG C, and both temperature difference are about 5 DEG C；Therefore, cooling tower to be possessed The parameter such as radiated energy, the operating pressure of individual other cooling water delivery pump and flow need indivedual conditions according to operating system with Demand first makes design considerations, then stipulates appropriate specification according to individual other design considerations, to correspond to actual needs.
In an embodiment, the operating pressure inside Oil recovery process step short-distance distiller 45 is 20 ~ 25Pa (Pascal)。
In an embodiment, the operating temperature inside Oil recovery process step short-distance distiller 45 is 150 ~ 180 DEG C.
In an embodiment, graphite scraper plate in Oil recovery process step 40 is mixed by fuel oil and a small amount of extract Close cylinder wall surface film of one thickness of formation less than 1mm that liquid is applied to Oil recovery process step short-distance distiller 45.
In an embodiment, the operating pressure inside ionic liquid recycling step short-distance distiller 55 is 20 ~ 25Pa (Pascal)。
In an embodiment, the operating temperature inside ionic liquid recycling step short-distance distiller 55 is 110 ~ 130 DEG C.
In an embodiment, the graphite scraper plate in ionic liquid recycling step 50 is by ionic liquid and the mixed liquor of extract The cylinder wall surface for being applied to ionic liquid recycling step short-distance distiller 55 forms film of the thickness less than 1mm.
In an embodiment, the Oil recovery process step short-distance distiller 45 in the Oil recovery process step 40 It is connected with a cold well 453, an Oil recovery process step material-handling pump 454, a material storing groove 455；Due in fuel In the evaporation operation of oil recycling step short-distance distiller 45, there are least a portion of light hydrocarbon such as C7 ~ 10H16 ~ 22 Composition, its molecular weight is smaller than the default fuel oil molecular weight to be reclaimed, and molecular mean free path is longer；Therefore, make In industry, these a small amount of light hydrocarbons can be evaporated together, and escape fuel oil by longer molecule free travel The built-in condenser of recycling step short-distance distiller 45, into after bleed-off passage, enters back into cold well 453 and is captured down Come；Because these a small amount of light hydrocarbons contain escaping gas, and default operating temperature is up to 150 ~ 180 DEG C, is These light hydrocarbon molecules are avoided into causing Oil recovery process step vavuum pump 495 in the pipeline of vacuum system Damage, therefore, be provided with systems in the condenser pipe for persistently importing cold well 453 as condensed water with 5 DEG C of frozen water, and with 5 The light hydrocarbon that the low temperature moment of DEG C frozen water will be trapped in cold well 453 is condensed out；Afterwards, when cold well 453 Liquid level when reaching default high level, then with Oil recovery process step material-handling pump 454 by the material in cold well 453 Empty, the material storing groove 455 that feeding receives light hydrocarbon waits transport；Frozen water needed for this condenser system by Frozen water unit 62 set by public process step equipment is provided；During operation, the preset temperature as manufactured by frozen water unit 62 Condensed for 5 DEG C of frozen water continue to be delivered in cold well 453 by the built-in frozen water delivery pump of frozen water unit 62, it is condensed cold But water is then sent frozen water unit 62 back to and carries out cooling down to 5 DEG C again again, then sends cold well 453 back to；In addition, in order to avoid it is continuous long when Between operation, the lubricating oil of the reducing gear outside Oil recovery process step short-distance distiller 45 caused by heat transfer process Overheat causes the failure of reductor 452, therefore, the frozen water sent out by frozen water unit 62 is directed to fuel oil by a branch line The shaft sealing cooler of recycling step short-distance distiller 45 is cooled down by axle envelope, used cooling water follow again pipeline with by cold The condensed water that well 453 is discharged to conflux be back to together again and made again in frozen water unit 62.
In embodiment, the ionic liquid recycling step short-distance distiller 55 in ionic liquid recycling step 50 connects It is connected to a cold well 553, ionic liquid recycling step material-handling pump 554, a material storing groove 555；Due in ionic liquid In the evaporation operation of oil recycling step short-distance distiller 55, it is likely to contain the light of very small amount molecular weight very little in extract The composition of matter hydrocarbon such as C7 ~ 10H16 ~ 22, the work pressure of the light hydrocarbon of these molecular weight very littles in 20Pa Under power, in can be evaporated under 110 ~ 130 DEG C of working temperature environment, due to these light hydrocarbon molecular weight very littles And its molecule free travel is longer；Therefore, in operation, these minimal amount of light hydrocarbon molecules are more long by it Molecule free travel may escape the built-in condenser of ionic liquid recycling step short-distance distiller 55, into bleed-off passage Afterwards, 553 are entered back into cold well to be captured；Because these light hydrocarbons contain escaping gas, and operating temperature Up to 110 ~ 130 DEG C, to avoid these light hydrocarbon molecules into causing ionic liquid to reclaim in the pipeline of vacuum system The damage of process step vavuum pump 595, therefore, it is provided with systems with 5 DEG C of frozen water and cold well 553 is persistently imported as condensed water In condenser pipe, and condensed out with the light hydrocarbon that the low temperature moment of 5 DEG C of frozen water will be trapped in cold well 553； Afterwards, until the liquid level of cold well 553 reaches default high level, then with ionic liquid recycling step material-handling pump 554 Material in cold well 553 is emptied, the material storing groove 555 that feeding receives light hydrocarbon waits transport；This condensation The frozen water unit 62 of frozen water needed for system as set by public process step equipment is provided；During operation, by frozen water unit Preset temperature manufactured by 62 is that 5 DEG C of frozen water continues to be delivered in cold well 553 by the built-in frozen water delivery pump of frozen water unit 62 Condensed, condensed cooling water is then sent frozen water unit 62 back to and carries out cooling down to 5 DEG C again again, then sends cold well 553 back to；Separately Outward, in order to avoid continuous prolonged operation, because outside ionic liquid recycling step short-distance distiller 55 caused by heat transfer process The lubricating oil overheat of the reducing gear in portion causes the failure of reductor 552, therefore, the frozen water sent out by frozen water unit 62 is by one The shaft sealing cooler that branch line is directed to ionic liquid recycling step short-distance distiller 55 is cooled down by axle envelope, used Cooling water follow pipeline again with the condensed water discharged by cold well 553 conflux again together be back to frozen water unit 62 in made again.
In summary it is described, the present invention using ozone as oxidant to replace traditional hydrogen peroxide, and make fuel oil in Reaction can be accelerated in desulfurization, the extraction processing step of denitrogenation, it is special with the material for carrying out deep desulfuration, denitrogenation but do not change extract Property；Low-sulfur, the fuel oil of low nitrogen and recovery can be reclaimed under low temperature, low-voltage safety working environment with short-distance distiller in addition For recycling, this process step has more security and has ionic liquid with the feature and operation for not causing secondary pollution With respect to energy-conservation and the features such as manufacturing cost can be saved.
Above for the present invention for embodiment, only for ease of illustration set, when meaning of the present invention can not be limited with this, I.e. generally according to the various shift designs carried out by listed claim, in should be included in the scope of the claims of the invention.

Claims (9)

1. a kind of method that fuel oil accelerates desulfurization, denitrogenation and ionic liquid recycling, it is characterised in that the method is included Have：
(1) fuel oil extraction processing step, is used to mix the fuel oil with ionic liquid carry out the extraction journey of desulfurization and denitrogenation Sequence；And
(2) oxidation treatment step, includes：
A. the oxidation treatment step includes several material-handling pumps and includes the drainage and impurity of an air compressor machine, a gases at high pressure The ozone generator assembly of filter, an ozone generator；One venturi air and liquid mixer；One includes a gas purger Mixed liquor buffers mixing channel；One exhaust blower；One active carbon adsorption groove and an acceleration reactive tank；
B. ozone generator assembly manufacture ozone and ozone storage is standby, and with one of them material-handling pump by the fuel Fuel oil and the mixed liquor of ionic liquid in oily extraction processing step by extracting send into the venturi air and liquid mixer, and make this Venturi air and liquid mixer sucks compressed ozone and enters with the fuel oil and the mixed liquor of ionic liquid by extracting simultaneously Row gas-liquid mixed, when ozone is by the throat of venturi air and liquid mixer, ozone gas can in venturi air and liquid mixer shape Into the disturbance of bubble type；
C. then enter the mixed liquor by the mixed liquor after the gas-liquid mixed effect of the venturi air and liquid mixer and buffer mixing channel Reacted, gas purger accumulation is then risen to from the ozone of mixed liquor effusion, and by the exhaust blower by the gas Body is emitted into air after being drawn through active carbon adsorption groove, and buffers the mixed liquor of mixing channel into the mixed liquor until reaching Predetermined fluid level, restarts one of them material-handling pump, and mixed liquor is sent into the acceleration reactive tank and is persistently reacted；And
(3) one centrifuging treatment steps, are used to react the acceleration in the oxidation treatment step by means of a high-speed centrifuge Mixed liquor after groove extractive reaction carries out high-speed separation, to form the mixed liquor of an ionic liquid and extract, and a fuel oil And the mixed liquor of a small amount of extract；And
(4) one Oil recovery process steps are operation core with short-path distillation, and it includes：
A. the Oil recovery process step is included at several Oil recovery process step material-handling pumps, an Oil recovery Reason step preheater, an Oil recovery process step short-distance distiller, an Oil recovery process step heat kerosene expansion slot, One Oil recovery process step heat kerosene heating furnace, several Oil recovery process step heat kerosene delivery pumps, a fuel oil Receive temporary tank, an Oil recovery process step byproduct and receive temporary tank, an Oil recovery process step vacuum buffer Groove, an Oil recovery process step gas-liquid separator, an Oil recovery process step vavuum pump, a product oil accumulator tank, One Oil recovery process step byproduct accumulator tank；
B. will with the Oil recovery process step heat kerosene heating furnace and the Oil recovery process step heat kerosene delivery pump The cylinder wall interlayer and the Oil recovery process step of the heat kerosene warp let-off Oil recovery process step short-distance distiller The heating jacket layer of preheater, is recycled back into the Oil recovery process step heat kerosene heating furnace, and another strand of heat kerosene The Oil recovery process step heat kerosene expansion slot is then sent into, the Oil recovery process step heat kerosene is recycled back into and is added Hot stove, until the cylinder wall interlayer and the Oil recovery process step of the Oil recovery process step short-distance distiller are pre- After the heating jacket layer of hot device reaches predetermined operating temperature, heat kerosene heating furnace carries out intermittent starting again, to maintain Need operating temperature；
C. the Oil recovery process step vavuum pump is started, by Oil recovery process step vacuum buffer groove, the combustion Material oil recycles step gas-liquid separator and the Oil recovery process step short-distance distiller, the fuel oil is received temporary Groove, the Oil recovery process step byproduct are received temporary tank and are vacuumized, until reaching predetermined operating pressure, vacuum Row intermittence starts to maintain required operating pressure pump again；
D. one of them Oil recovery process step material-handling pump, the fuel that the centrifuging treatment step is formed Oil and a small amount of mixed liquor warp let-off of extract Oil recovery process step preheater heating, are re-fed at the Oil recovery Step short-distance distiller is managed, the scraper plate set by Oil recovery process step short-distance distiller inside is by the fuel oil and on a small quantity The cylinder wall surface that the mixed liquor of extract is applied to the Oil recovery process step short-distance distiller forms a predetermined thickness Film, make the film by the cylinder wall interlayer of the Oil recovery process step short-distance distiller by heat kerosene heating produced by Predetermined temperature heat and evaporate fuel oil molecule, and the fuel oil molecule is extracted into the Oil recovery process step short distance The built-in condenser of distiller, the condenser will attach to the fuel oil molecule cooling of condenser surface and to revert back to liquid cold Coagulate, the fuel oil for accumulating liquid enters back into the fuel oil and receives temporary tank and send into the product oil accumulator tank；
E. a small amount of extract in the mixed liquor of the fuel oil and a small amount of extract cannot be evaporated as molecularity, and be in Existing liquid glides along cylinder wall and falls into the Oil recovery process step short-distance distiller lower inside, enters back into the fuel oil Recycling step byproduct receives temporary tank and sends into the Oil recovery process step byproduct accumulator tank；And
(5) one ionic liquids recycling step is operation core with short-path distillation, and it includes：
A. ionic liquid recycling step comprising several ionic liquids recycling step material-handling pumps, an ionic liquid recovery at Reason step preheater, ionic liquid recycling step short-distance distiller, ionic liquid recycling step heat kerosene expansion slot, One ionic liquid recycling step heat kerosene heating furnace, several ionic liquid recycling step heat kerosene delivery pumps, an ionic liquids Receive temporary tank, ionic liquid recycling step byproduct and receive temporary tank, ionic liquid recycling step vacuum buffer Groove, ionic liquid recycling step gas-liquid separator, ionic liquid recycling step vavuum pump, an ionic liquid accumulator tank, One ionic liquid recycles step byproduct accumulator tank；
B. step heat kerosene heating furnace is recycled with the ionic liquid and ionic liquid recycling step heat kerosene delivery pump will The cylinder wall interlayer and ionic liquid recycling step of heat kerosene warp let-off ionic liquid recycling step short-distance distiller The heating jacket layer of preheater, is recycled back into ionic liquid recycling step heat kerosene heating furnace, and another strand of heat kerosene Ionic liquid recycling step heat kerosene expansion slot is then sent into, ionic liquid recycling step heat kerosene is recycled back into and is added Hot stove, until the cylinder wall interlayer and ionic liquid recycling step of ionic liquid recycling step short-distance distiller are pre- The heating jacket layer of hot device reaches predetermined operating temperature, afterwards, the heat kerosene heating furnace intermittent starting of row again, with maintenance work Temperature；
C. start ionic liquid recycling step vavuum pump, step vacuum buffer groove, ion are recycled by the ionic liquid Liquid recycles step gas-liquid separator and ionic liquid recycling step short-distance distiller, the ionic liquid is received temporary Groove, ionic liquid recycling step byproduct are received temporary tank and are vacuumized, until predetermined work pressure is reached, afterwards, Row intermittence starts to maintain required operating pressure vavuum pump again；
D. one of them ionic liquid recycles step material-handling pump, the ion that the centrifuging treatment step is formed Liquid and the mixed liquor warp let-off of extract ionic liquid recycling step preheater heating, are re-fed into ionic liquid recycling step Rapid short-distance distiller, scraper plate set by ionic liquid recycling step short-distance distiller inside is mixed by ionic liquid and extract The film that liquid is applied to cylinder wall surface one predetermined thickness of formation of ionic liquid recycling step short-distance distiller is closed, makes this Film is by the cylinder wall interlayer of ionic liquid recycling step short-distance distiller by the predetermined temperature produced by heat kerosene heating Ionic liquid molecule is heated and evaporates, and it is built-in that the ionic liquid molecule is extracted into ionic liquid recycling step short-distance distiller A condenser, the condenser will attach to condenser surface ionic liquid molecule cooling and revert back to liquid and condense out, converge The ionic liquid of integrated liquid enters back into the ionic liquid and receives temporary tank and send into the ionic liquid accumulator tank；
E. the extract in the mixed liquor of the ionic liquid and extract cannot be evaporated as molecularity, and liquid is presented Glided along cylinder wall and fall into ionic liquid recycling step short-distance distiller lower inside, entered back at the ionic liquid recovery Reason step byproduct receives temporary tank and sends into ionic liquid recycling step byproduct accumulator tank；And
(6) one public process steps, by a cooling tower and frozen water machine, to produce cooling water and frozen water, are used to provide cooling The cold well that water and frozen water are set up to the built-in condenser of the Oil recovery process step short-distance distiller and outside is used as cold Solidifying water and it is supplied to the cold well that the ionic liquid recycles the built-in condenser of step short-distance distiller and set up outside it Used as condensed water.
2. the method that fuel oil as claimed in claim 1 accelerates desulfurization, denitrogenation and ionic liquid recycling, its feature exists In the operating pressure of the Oil recovery process step short-distance distiller internal preset is 20 ~ 25Pa.
3. the method that fuel oil as claimed in claim 1 accelerates desulfurization, denitrogenation and ionic liquid recycling, its feature exists In the operating temperature of the Oil recovery process step short-distance distiller internal preset is 150 ~ 180 DEG C.
4. the method that fuel oil as claimed in claim 1 accelerates desulfurization, denitrogenation and ionic liquid recycling, its feature exists In the mixed liquor of fuel oil and a small amount of extract is applied to fuel oil and returned by the graphite scraper plate in the Oil recovery process step The cylinder wall surface for receiving process step short-distance distiller forms film of the thickness less than 1mm.
5. the method that fuel oil as claimed in claim 1 accelerates desulfurization, denitrogenation and ionic liquid recycling, its feature exists In the default operating pressure inside ionic liquid recycling step short-distance distiller is 20 ~ 25Pa.
6. the method that fuel oil as claimed in claim 1 accelerates desulfurization, denitrogenation and ionic liquid recycling, its feature exists In ionic liquid recycling step short-distance distiller internal preset operating temperature is 110 ~ 130 DEG C.
7. the method that fuel oil as claimed in claim 1 accelerates desulfurization, denitrogenation and ionic liquid recycling, its feature exists In be applied to the mixed liquor of ionic liquid and extract at ionic liquid recovery by the graphite scraper plate in ionic liquid recycling step The cylinder wall surface for managing step short-distance distiller forms film of the thickness less than 1mm.
8. the method that fuel oil as claimed in claim 1 accelerates desulfurization, denitrogenation and ionic liquid recycling, its feature exists In, the Oil recovery process step short-distance distiller in the Oil recovery process step be also associated with being set up outside this it is cold Well, an Oil recovery process step material-handling pump, a material storing groove, make the Oil recovery process step short-path distillation Produced light hydrocarbon can be captured and condense out into the cold well in device, then process step with the Oil recovery The material being condensed in the cold well is sent into the material storing groove and waits transport by rapid material-handling pump.
9. the method that fuel oil as claimed in claim 1 accelerates desulfurization, denitrogenation and ionic liquid recycling, its feature exists It is cold that ionic liquid recycling step short-distance distiller in, ionic liquid recycling step is also associated with being set up outside this Well, an Oil recovery process step material-handling pump, a material storing groove, make the ionic liquid recycle step short-path distillation Produced light hydrocarbon can be captured and condense out into the cold well in device, then recycle step with the ionic liquid The material being condensed in the cold well is sent into the material storing groove and waits transport by rapid material-handling pump.
CN201310418383.XA 2013-09-13 2013-09-13 The method that fuel oil accelerates desulfurization, denitrogenation and ionic liquid recycling Expired - Fee Related CN104449819B (en)

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