CN107779220A - A kind of gasoline processing method - Google Patents
A kind of gasoline processing method Download PDFInfo
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- CN107779220A CN107779220A CN201710240066.1A CN201710240066A CN107779220A CN 107779220 A CN107779220 A CN 107779220A CN 201710240066 A CN201710240066 A CN 201710240066A CN 107779220 A CN107779220 A CN 107779220A
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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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/22—Compounds containing sulfur, selenium, or tellurium
-
- 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
- C10G21/02—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents with two or more solvents, which are introduced or withdrawn separately
-
- 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
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/16—Oxygen-containing compounds
-
- 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
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/20—Nitrogen-containing compounds
-
- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
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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
The present invention relates to field of hydrogenation, specifically, discloses a kind of gasoline processing method, this method includes：Gasoline is stripped distillation processing, wherein, the initial boiling point of the gasoline is more than 40 DEG C, and the end point of distillation is below 170 DEG C, the extractive distillation handles to obtain rich solvent and refined rear gasoline, and the extractive distillation, which is handled, causes Aromatic Hydrocarbon in Gasoline and sulfide to be dissolved in extractive distillation solvent and form the rich solvent.The gasoline processing method energy consumption is low, desulfuration efficiency is high, and loss of octane number is relatively low.
Description
Technical field
The present invention relates to field of hydrogenation, in particular it relates to a kind of gasoline processing method.
Background technology
As people are to the pay attention to day by day of environmental protection, environmental regulation is also increasingly strict, and reduces the sulfur content quilt of gasoline
It is considered to improve one of most important measure of air quality.Most of sulphur in China's gasoline products come from hot-working petroleum tune
Charge-coupled point, such as catalytically cracked gasoline.Therefore, it is necessary to catalytically cracked gasoline is subjected to deep desulfuration, simple catalytic gasoline desulfurization
Technology can all bring a problem：The octane number of catalytic gasoline declines.
In order on the premise of certain desulfurization depth is ensured, make as far as possible few alkene saturation, at present, the work of researcher's exploitation
Skill technology mainly has：The S-zorb technologies of sinopec exploitation, the RSDS technique of sinopec Research Institute of Petro-Chemical Engineering exploitation, with
And French Prime-G+ technologies.
The S-zorb technologies of sinopec exploitation are used for full cut catalytic gasoline desulfurization, and sulfur content can control after desulfurization
Below 10ppm, the loss of octane number of full cut catalytic gasoline is in 1-2 unit.Sinopec Research Institute of Petro-Chemical Engineering develops
RSDS technique catalytic gasoline is first cut into light and heavy fractions, extraction desulfurization alcohol is passed through in light fraction, and selective hydrogenation is gone in heavy distillat
Desulfurization, when the product sulfur content of the technology is less than 10ppm, light fraction yield about 20%, largely need to be hydrogenated with, full cut vapour
About 3-4 unit of oily loss of octane number.Gasoline is hydrogenated with by French Prime-G+ technologies in advance before gasoline cutting is carried out,
Lighter sulfide and alkadienes are acted on forming high boiling sulfide by pre- hydrogenation process, and alkene is not saturated, the technology
Loss of octane number be also about 3-4 unit.
Therefore, while deep desulfurization of gasoline can be realized by needing one kind badly, the gasoline processing method of loss of octane number is reduced.
The content of the invention
A kind of the defects of purpose of the present invention is overcome in prior art sweetening process, and loss of octane number is serious, there is provided vapour
Oily processing method.The gasoline processing method energy consumption is low, desulfuration efficiency is high, and loss of octane number is relatively low.
The present inventor has found in research process, in gasoline process, by initial boiling point more than 40 DEG C, and
Gasoline of the end point of distillation below 170 DEG C is stripped distillation processing, and extractive distillation, which is handled, make it that Aromatic Hydrocarbon in Gasoline and sulfide are molten
Rich solvent is formed in extractive distillation solvent, the gasoline after refining is distilled off, can be effectively by sulfide and olefin component point
Open, partly avoid in sweetening process, loss of octane number caused by the saturation of alkene, further, the rich solvent is carried out
Stripping processing, solvent and aromatic hydrocarbons containing sulfide can be separated, the aromatic hydrocarbons containing sulfide can enter selective hydrogenation
Desulfurizer carries out desulfurization process.
Based on this, the present invention provides a kind of gasoline processing method, and this method includes：Gasoline is stripped distillation processing,
Wherein, the initial boiling point of the gasoline is more than 40 DEG C, and the end point of distillation, below 170 DEG C, the extractive distillation handles to obtain Fu Rong
Agent and it is refined after gasoline, the extractive distillation handle cause Aromatic Hydrocarbon in Gasoline and sulfide be dissolved in extractive distillation solvent formed it is described
Rich solvent.
The liquid liquid extractive process of prior art, applies in general to the extraction of the relatively simple raw material of raw material components, such as reforms
(raw material only has aromatic hydrocarbons, alkane to the Aromatics Extractive Project of oil substantially, is practically free of sulfide, nitride, oxide, only a small amount of ring
Alkane, alkene), when raw material composition is complicated, meet demand is would become hard on yield.Catalytic gasoline component is a raw material composition
Extremely complex raw material, if extracted using the liquid liquid of prior art, aromatic hydrocarbons, alkene, sulfide (mercaptan, thioether, thiophene)
Polarity competition will be very fierce.According to solvent classes selectivity and weight selected slant stack principle, strong molten of light polarity
Agent carries away, and the polarity of weight will be weak to be lost.So the sulfide of weight can be contained in the catalytic gasoline after the extracting of liquid liquid, together
When the oil that is dissolved by the solvent in will carry light alkene.And present invention is particularly directed to initial boiling point more than 40 DEG C, and the end point of distillation exists
Less than 170 DEG C of gasoline is stripped distillation processing, and described extractive distillation enters polar extraction and weight separated simultaneously
OK, existing aromatic hydrocarbons, alkene, the polarity competition process of sulfide (mercaptan, thioether, thiophene) in whole process, also there is weight thing
Expect separated process.Solvent polarity extracted character can be so played to greatest extent, and it is special also to embody the separation of component weight
Property so that the sulfide that solvent is carried in aromatic component and middle gasoline forms rich solvent, and the middle gasoline after refining is distilled out
Come, alkene is hardly visible in rich solvent, be difficult to find sulfide in the middle gasoline after refined, and then gasoline can realized
While deep desulfuration, loss of octane number is reduced.
Gasoline processing method provided by the invention coordinates preferable extractive distillation solvent can be more efficiently by sulfide
Separated with alkene, reduce the loss of alkene in sweetening process.
Gasoline processing method provided by the invention coordinates preferable catalyst for selectively hydrodesulfurizing can be more efficiently
Sulfide is removed.
Compared with prior art, following advantage be present in gasoline processing method provided by the invention：
(1) it is initial boiling point more than 40 DEG C to use extractive distillation technical finesse boiling range, and vapour of the end point of distillation below 170 DEG C
Oil, solve the solvent carrying problem of treated gasoline, eliminate the washing of treated gasoline, so as to reduce plant running energy consumption,
The discharge of sour water is avoided, while the refined problem to washing water is also just not present；
(2) extractive distillation technology is used, alkene polarity and the race problem of sulfide polarity and solvent is solved, is not present
The problem of high-octane olefin component is lost in sulfur-rich aromatic component, therefore washing oil circulation need not be returned, so energy consumption is low；
(3) the problem of present invention is lost in sulfur-rich aromatic component in the absence of high-octane olefin component, therefore be not required to
The pentane component of anti-top light olefin is added for this, so device material consumption is low；
(4) because no light component returns washing lotion circulation, eliminate and return washing lotion tower, so device, which is not present, rushes tower, foaming etc.
Problem, improve plant running stability.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The present invention provides a kind of gasoline processing method, and this method includes：Gasoline is stripped distillation processing, wherein, institute
The initial boiling point of gasoline is stated more than 40 DEG C, and the end point of distillation, below 170 DEG C, the extractive distillation is handled to obtain rich solvent and refined
Gasoline afterwards, the extractive distillation, which is handled, causes Aromatic Hydrocarbon in Gasoline and sulfide to be dissolved in extractive distillation solvent and form the rich solvent.
The present inventor has found in research process, is taken off sulphur in middle gasoline and heavy petrol to 10 using prior art
During μ g/g, middle octane number loses about 5 units, and heavy petrol loses about 0.5 unit, therefore, the present invention specifically addresses
In middle gasoline sweetening process the problem of loss of octane number.Initial boiling point is more than 40 DEG C, and the end point of distillation is at the gasoline below 170 DEG C
Reason be applicable gasoline processing method provided by the invention, the present inventor further study show that, initial boiling point 55 DEG C with
Above (preferably more than 60 DEG C), and gasoline of the end point of distillation below 150 DEG C (preferably below 125 DEG C) is especially suitable for the present invention
The method of offer.
In the present invention, the gasoline composition is complex, contains alkadienes, alkene, cycloolefin, alkane, cycloalkane, virtue
Hydrocarbon and micro sulfide, nitride, oxide and colloid etc., preferably described gasoline contain aromatic hydrocarbons, alkene, alkadienes, alkane
Hydrocarbon and sulfide.
Sulfide of the present invention is selected from least one of mercaptan, thioether, disulphide and thiophene.
Initial boiling point is more than 40 DEG C, and gasoline processing of the end point of distillation below 170 DEG C is applicable gasoline provided by the invention
Processing method, the present inventor, which studies, to be found, initial boiling point is more than 55 DEG C (preferably more than 60 DEG C), and the end point of distillation exists
The gasoline of less than 150 DEG C (preferably below 125 DEG C) is especially suitable for method provided by the invention.
A preferred embodiment of the invention, the gasoline is stripped into distillation processing includes：Steamed in extracting
Under the conditions of evaporating, gasoline is contacted with extractive distillation solvent.
There is no particular limitation for the mode that the present invention contacts to the gasoline with extractive distillation solvent, can be according to this area
Conventional meanses are carried out, it is preferable that are introduced gasoline in the middle part of extraction distillation tower, extractive distillation solvent draws from extraction distillation tower top
Enter.
The present invention is wider to the range of choice of the extractive distillation condition, as long as so that Aromatic Hydrocarbon in Gasoline and sulfide are dissolved in
Extractive distillation solvent, it is preferable that the extractive distillation condition includes：It is 60-100 DEG C to enter tower temperature degree, preferably 80-90
℃；Tower top temperature is 70-90 DEG C, preferably 75-85 DEG C；Column bottom temperature is 140-180 DEG C, preferably 155-170 DEG C；Tower top pressure
Power is 0.05-0.1MPa.
Extractive distillation of the present invention carries out polar extraction and weight separated simultaneously, existing in whole process
Aromatic hydrocarbons, alkene, the polarity competition process of sulfide (mercaptan, thioether, thiophene), also there is light-heavy material separated process.So
Solvent polarity extracted character can be played to greatest extent, can also embody component weight stalling characteristic so that solvent carries aromatic hydrocarbons
Sulfide in component and gasoline forms rich solvent, and the gasoline after refining is distilled off, and alkene is hardly visible in rich solvent
Hydrocarbon, it is difficult to find sulfide in the gasoline after refined, and then octane number can be reduced while deep desulfurization of gasoline is realized
Loss.
The feed weight of extractive distillation solvent of the present invention and the middle gasoline fraction than range of choice it is wider, it is excellent
Selection of land, the feed weight ratio of the extractive distillation solvent and the gasoline is 1-4：1, more preferably 2-3：1.
A preferred embodiment of the invention, the extractive distillation solvent include sulfone compound, diethylene glycol (DEG), three
Glycol, tetraethylene glycol, polyethylene glycol, 2-Pyrrolidone, N- formyl-morpholines, 1-METHYLPYRROLIDONE, N- ethyl pyrrolidones, N-
At least one of propyl pyrrole alkanone, propene carbonate and ethylene carbonate.
A preferred embodiment of the invention, the extractive distillation solvent include main solvent, cosolvent and alkene
Polymerization inhibitor, on the basis of the gross weight of the extractive distillation solvent, the content of the main solvent is 70-99 weight %, institute
The content for stating cosolvent is 0.999-29.9 weight %, and the content of the olefinic polymerization inhibitor is 10-1000 μ g/g；The master
Solvent is selected from sulfone compound；The cosolvent is selected from 1-METHYLPYRROLIDONE, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, chaff
At least one of aldehyde and dimethyl acetamide；The olefinic polymerization inhibitor is selected from p-tert-Butylcatechol, diethyl hydroxyl
At least one of amine, dipropyl azanol, 2- sec-butyl -4,6- dinitrophenol and natrium nitrosum.This kind of preferable extracting is steamed
Evaporating solvent has higher dissolubility and selectivity, while can ensure the selectivity to sulfide, further reduction pair
The selectivity of alkene, and the olefinic polymerization inhibitor in extractive distillation solvent has the function that to suppress olefinic polymerization so that extracting
Solvent distillation performance is more excellent.
The present inventor has found that sulfone compound as main solvent, coordinates of the present invention help in research process
Solvent and olefinic polymerization inhibitor, solvent can be not only improved to arenes selectivity, also overcome solvent and aromatic hydrocarbons is not easy to point
From the defects of.In addition, main solvent, cosolvent and olefinic polymerization inhibitor are used in conjunction with, one-component function will not be caused
Disappear.
In order to further improve selectivity of the extractive distillation solvent to aromatic hydrocarbons and sulfide, the selectivity to alkene is reduced,
Preferably, on the basis of the gross weight of extractive distillation solvent, the content of the main solvent is 80-95 weight %, the cosolvent
Content be 4.99-19.9 weight %, the content of the olefinic polymerization inhibitor is 100-1000 μ g/g, it is further preferred that
On the basis of the gross weight of double solvents, the content of the main solvent is 85-90 weight %, and the content of the cosolvent is
9.95-14.9 weight %, the content of the olefinic polymerization inhibitor is 500-1000 μ g/g.
According to the present invention, the content of olefinic polymerization inhibitor is referred to relative to every g extractive distillations solvent, olefinic polymerization
The amount of inhibitor.
A preferred embodiment of the invention, the cosolvent are 1-METHYLPYRROLIDONE and triethylene glycol monomethyl ether
And/or the mixture of tetraethylene glycol monomethyl ether.Main solvent is more beneficial for using this kind of preferred embodiment and cosolvent collaboration plays
Effect, while the selectivity to sulfide is ensured, further reduce the selectivity to alkene.
In the present invention, it is preferred in terms of the 1-METHYLPYRROLIDONE of 100 parts by weight, the triethylene glycol monomethyl ether and/or
The dosage of tetraethylene glycol monomethyl ether is 10-200 parts by weight, more preferably 50-100 parts by weight.Using this kind of side of being preferable to carry out
Formula, it is more beneficial for playing the effect of 1-METHYLPYRROLIDONE and triethylene glycol monomethyl ether and/or tetraethylene glycol monomethyl ether, is ensureing to sulphur
While the selectivity of compound, the selectivity to alkene reduce further.
It should be noted that when the cosolvent is simultaneously sweet containing 1-METHYLPYRROLIDONE and triethylene glycol monomethyl ether and four
During alcohol monomethyl ether, the dosage of triethylene glycol monomethyl ether and/or the tetraethylene glycol monomethyl ether refers to triethylene glycol monomethyl ether and tetraethylene glycol
Total dosage of monomethyl ether.
A preferred embodiment of the invention, the olefinic polymerization inhibitor be tert-butyl catechol and/or
2- sec-butyl -4,6- dinitrophenol, the preferable olefinic polymerization inhibitor and the main solvent and hydrotropy in extractive distillation solvent
When agent is used cooperatively, have the function that preferably to suppress olefinic polymerization, extractive distillation solvent nature is more excellent.
The present invention is wider to the range of choice of the sulfone compound, can be various sulfone class chemical combination commonly used in the art
Thing, such as the sulfone compound can be in sulfolane, 3- methyl sulfolanes, dimethyl sulfone and diη-propyl sulfones at least
One kind, preferably sulfolane.Solubility of the sulfolane in hydrocarbon is preferable, more excellent to the selectivity of aromatic hydrocarbons.
Extractive distillation solvent based on sulfone compound in the process of running, due to O in system2Be mixed into, easily occur
Oxidation generates acid compound and acidic polymer, when the pH value in system drops to below 4.5, that is, shows sulfone class
Compound solvent is degraded, and such case can produce certain corrosion to equipment, in order to which control system is acid so that the pH value in system
6.0 or so are maintained at, preferably described extractive distillation solvent also includes corrosion inhibiter.
There is no particular limitation to the corrosion inhibiter by the present invention, as long as energy control system is acid, while ensures the slow of addition
Erosion agent does not influence the performance of extractive distillation solvent, it is preferable that the corrosion inhibiter is selected from MEA, diethanol amine, N- first
At least one of base MEA and N methyldiethanol amine, most preferably MEA.
In the present invention, it is preferable that the corrosion inhibiter coordinates other substance migrations in extractive distillation solvent, can effectively control
Systemic acidity, so that it is guaranteed that the acid stable of whole system, also functions to the effect for suppressing olefinic polymerization to a certain extent.
The present invention is wider to the range of choice of the dosage of the corrosion inhibiter, it is preferable that with the gross weight of extractive distillation solvent
On the basis of, the content of the corrosion inhibiter is 10-1000 μ g/g, more preferably 100-1000 μ g/g, still more preferably for
500-1000μg/g。
A preferred embodiment of the invention, the rich solvent can be subjected to stripping processing, obtain solvent and
Aromatic hydrocarbons containing sulfide.The solvent can be recycled.
The present invention has no particular limits to the steam stripped condition, and those skilled in the art can enter according to actual conditions
The appropriate selection of row, such as steam stripped condition can include：Tower top temperature is 80-90 DEG C, and column bottom temperature is 170-178 DEG C；Tower
Pressure on top surface is -40 to -60KPa, and backflow/charge-mass ratio is 0.5-1:1.
A preferred embodiment of the invention, the aromatic hydrocarbons containing sulfide is carried out at selective hydrogenation
Reason.Gasoline processing method provided by the present invention so that almost all of sulfide dissolves in aromatic hydrocarbons and (is practically free of alkene in gasoline
Hydrocarbon), extraction process is applied in gasoline sweetening process, efficiently separated alkene and sulfide, sulfide will be contained
Aromatic hydrocarbons (being practically free of alkene) carry out selective hydrogenation processing and both can guarantee that deep desulfuration, and can reduces the damage of octane number
Lose.
There is no particular limitation for condition of the present invention to selective hydrogenation processing, all selective hydrogenations of prior art
Processing method is used equally for the present invention.
In the present invention, the method for the selective hydrogenation processing includes：Under the conditions of selective hydrogenation, contain by described in
The aromatic hydrocarbons and hydrogen of sulfide contact with catalyst for selectively hydrodesulfurizing.
A preferred embodiment of the invention, the selective hydrogenation condition include：Temperature is 250-600 DEG C,
Liquid hourly space velocity (LHSV) is 1-10h-1, hydrogen to oil volume ratio 200-700, pressure 2-8MPa；It is further preferred that temperature is 260-400
DEG C, liquid hourly space velocity (LHSV) 2-6h-1, hydrogen to oil volume ratio 250-400, pressure 2-6MPa.
According to the present invention, the catalyst for selectively hydrodesulfurizing can be that various selectivity commonly used in the art add
Hydrogen desulphurization catalyst, carrier and selective hydrodesulfurization active component are typically contained, wherein, urged with the selective hydrodesulfurization
On the basis of the total amount of agent, the content of the selective hydrodesulfurization active component is 1-40 weight %, and the content of carrier is 60-
99 weight %.The selective hydrodesulfurization active component typically can be one kind or more in VI B races, VIII race's element
Kind, under preferable case, the selective hydrodesulfurization active component is generally the one or more in tungsten, nickel, molybdenum, cobalt.It is described
Carrier can be conventional use of various carriers, you can think various heat-resisting porous materials commonly used in the art, specifically, institute
It can be heat-resisting inorganic oxide and/or silicate to state heat-resisting porous material.
In the present invention, the octane number is research octane number (RON), survey of the assay method with reference to conventional research octane number (RON)
Determine method, the present invention is without particular/special requirement.
The implementation process of the present invention and caused beneficial effect are described in detail below by way of specific embodiment, it is intended to are helped
Where reader more clearly understands the Spirit Essence of the present invention, but any restriction can not be formed to the practical range of the present invention.
In following examples, the raw material of gasoline processing method uses boiling range as 60-125 DEG C of middle gasoline fraction, in described
Gasoline fraction is cut to obtain by catalytically cracked gasoline, and boiling range is 60-125 DEG C of middle gasoline fraction into being shown in Table 1.
Gasoline fraction forms in table 1
| Component | Content, weight % |
| Alkane | 49.3 |
| Cycloalkane | 6.3 |
| Alkene | 41.635 |
| Aromatic hydrocarbons | 2.75 |
| Sulphur | 0.015 |
| Amount to | 100 |
Embodiment 1
(1) by middle gasoline fraction introduce extraction distillation tower in the middle part of, by extractive distillation solvent F-1 (concrete composition is shown in Table 2) from
Top is introduced into extraction distillation tower, and (mass ratio of extractive distillation solvent and middle gasoline fraction is 2:1), steamed by extractive distillation, extracting
The condition of evaporating includes：Enter tower temperature degree for 84 DEG C, tower top temperature is 76-77 DEG C, and column bottom temperature is 158-160 DEG C, tower top operating pressure
For 0.1MPa, the discharge of extractive distillation column overhead is raffinated oil, and the rich solvent rich in aromatic hydrocarbons and sulfide of extraction distillation tower bottom of towe enters
Enter stripper to be stripped, specific stripping conditions include：Tower top temperature is 80-82 DEG C, and column bottom temperature is 177-179 DEG C, backflow/
Charge-mass ratio is 1；Bottom of towe obtains lean solvent, and tower top obtains sulfur-rich aromatic hydrocarbons, and system operation is after 6 months, obtained lean solvent PH
Value about 7, and raffinate oil without olefin polymerization suspension in lean solvent and be listed in table 3 with the analysis result of sulfur-rich aromatic hydrocarbons；
(2) it is 280 DEG C in temperature, liquid hourly space velocity (LHSV) 2.5h-1, hydrogen to oil volume ratio 250, pressure is 2.5MPa selectivity
Under hydroconversion condition, by urging for the sulfur-rich aromatic hydrocarbons that step (1) obtains and the RSDS-31 trades mark commercially available from Research Institute of Petro-Chemical Engineering
Agent contacts, and obtains the selective hydrodesulfurization product that sulfur content is 10 μ g/g, loss of octane number 0.2.
The extractive distillation solvent of table 2 forms
Note：Extractive distillation balance of solvent is water
Table 3 is raffinated oil, the analysis result of the product of sulfur-rich aromatic hydrocarbons
By calculate, only existed in raffinating oil 3.3 weight % aromatic hydrocarbons (computational methods be (0.1% ×
91.7%)/(0.1% × 91.7%+32.6% × 8.3%) × 100%), 3 weight % sulphur, and there are 94.4 weight %
Alkene；96.7 weight % aromatic hydrocarbons is there are in sulfur-rich aromatic hydrocarbons, 97 weight % sulphur, 5.6 weight % alkene, avoids alkene
Enrichment of the hydrocarbon in sulfide, reduces loss of octane number to greatest extent.
Embodiment 2
(1) by middle gasoline fraction introduce extraction distillation tower in the middle part of, by extractive distillation solvent F-2 (concrete composition is shown in Table 2) from
Top is introduced into extraction distillation tower, and (mass ratio of extractive distillation solvent and middle gasoline fraction is 3:1), steamed by extractive distillation, extracting
The condition of evaporating includes：Enter tower temperature degree for 86 DEG C, tower top temperature is 75-76 DEG C, and column bottom temperature is 156-158 DEG C, tower top operating pressure
For 0.1MPa, the discharge of extractive distillation column overhead is raffinated oil, and the rich solvent rich in aromatic hydrocarbons and sulfide of extraction distillation tower bottom of towe enters
Enter stripper to be stripped, specific stripping conditions include：Tower top temperature is 80-82 DEG C, and column bottom temperature is 177-179 DEG C, backflow/
Charge-mass ratio is 1；Bottom of towe obtains lean solvent, and tower top obtains sulfur-rich aromatic hydrocarbons, and system operation is after 6 months, obtained lean solvent PH
Value about 7, and raffinate oil without olefin polymerization suspension in lean solvent and be listed in table 4 with the analysis result of sulfur-rich aromatic hydrocarbons；
(2) with the step of embodiment 1 (2), loss of octane number 0.2.
Table 4 is raffinated oil, the analysis result of the product of sulfur-rich aromatic hydrocarbons
Embodiment 3
Carried out according to the method described in embodiment 1, unlike, the extractive distillation using the different compositions of phase homogenous quantities is molten
Agent F-3 substitutes extractive distillation solvent F-1.Extractive distillation solvent F-3 compositions are shown in Table 2.After system operation 6 months, what is obtained is poor molten
Agent pH value is about 7, and without olefin polymerization suspension in lean solvent.3 weight % aromatic hydrocarbons, 3 weight % are only existed in raffinating oil
Sulphur, and there are 93.6 weight % alkene；It there are 97 weight % aromatic hydrocarbons in sulfur-rich aromatic hydrocarbons, 97 weight % sulphur, 6.4
Weight % alkene.
Obtain the selective hydrodesulfurization product that sulfur content is 10 μ g/g, loss of octane number 0.2.
Embodiment 4
Carried out according to the method described in embodiment 1, unlike, substitute three using the 1-METHYLPYRROLIDONE of phase homogenous quantities
Glycol monomethyl ether.After system operation 6 months, obtained lean solvent pH value is about 7, and without olefin polymerization suspension in lean solvent.
4.6 weight % aromatic hydrocarbons, 5 weight % sulphur are only existed in raffinating oil, and there are 92.4 weight % alkene；Sulfur-rich aromatic hydrocarbons
In there are 95.4 weight % aromatic hydrocarbons, 95 weight % sulphur, 7.6 weight % alkene.
Obtain the selective hydrodesulfurization product that sulfur content is 10 μ g/g, loss of octane number 0.4.
Compared with Example 1, the amount of alkene being dissolved in sulfur-rich aromatic hydrocarbons increased, at identical selective hydrogenation
Reason method, loss of octane number are increased slightly.
Embodiment 5
Carried out according to the method described in embodiment 1, unlike, N- first is substituted using the triethylene glycol monomethyl ether of phase homogenous quantities
Base pyrrolidones.After system operation 6 months, obtained lean solvent pH value is about 7, and without olefin polymerization suspension in lean solvent.
4.8 weight % aromatic hydrocarbons, 4.3 weight % sulphur are only existed in raffinating oil, and there are 91.9 weight % alkene；Sulfur-rich virtue
95.2 weight % aromatic hydrocarbons, 95.7 weight % sulphur, 8.1 weight % alkene are there are in hydrocarbon.
Obtain the selective hydrodesulfurization product that sulfur content is 10 μ g/g, loss of octane number 0.4.
Compared with Example 1, the amount of alkene being dissolved in sulfur-rich aromatic hydrocarbons increased, at identical selective hydrogenation
Reason method, loss of octane number are increased slightly.
Embodiment 6
Carried out according to the method described in embodiment 1, unlike, the tert-butyl group is substituted using the diethyl hydroxylamine of phase homogenous quantities
Catechol.After system operation 6 months, obtained lean solvent pH value is about 7, occurs a small amount of olefin polymerization in lean solvent and suspends
Thing.3.9 weight % aromatic hydrocarbons, 4 weight % sulphur are only existed in raffinating oil, and there are 92.9 weight % alkene；It is sulfur-rich
96.1 weight % aromatic hydrocarbons, 96 weight % sulphur, 7.1 weight % alkene are there are in aromatic hydrocarbons.
Compared with Example 1, there is a small amount of olefin polymerization suspension in system operation after 6 months, in lean solvent, i.e., there occurs
A little olefinic polyreaction.
Embodiment 7
Carried out according to the method described in embodiment 1, unlike, corrosion inhibiter is not contained in the extractive distillation solvent, is delayed
Agent is lost to be substituted with the sulfolane of phase homogenous quantities.The distribution of sulphur, alkene and aromatic hydrocarbons only has minor variations, but system operation is after 6 months,
Obtained lean solvent pH value drops to 5.5, hydraulic performance decline.
Embodiment 8
Carried out according to the method described in embodiment 1, unlike, the extractive distillation solvent is used described in CN1262264A
Using sulfolane as main solvent, ortho-xylene for cosolvent double solvents substitute, using the gross weight of the double solvents as base
Standard, the content of the sulfolane is 94 weight %, and the content of the ortho-xylene is 6 weight %.21 weights are there are in raffinating oil
% aromatic hydrocarbons is measured, 43 weight % sulphur, there are 58.7 weight % alkene；79 weight % virtue is there are in sulfur-rich aromatic hydrocarbons
Hydrocarbon, 57 weight % sulphur, 41.3 weight % alkene.Obtain the selective hydrodesulfurization product that sulfur content is 10 μ g/g, octane
Value loss 1.4.Contain substantial amounts of alkene in this method in sulfur-rich aromatic hydrocarbons, and contain substantial amounts of sulphur in raffinating oil, have not been able to effectively
Ground separates alkene and sulfide.
Solves alkene polarity and sulfide using gasoline processing method provided by the invention it can be seen from the above
The race problem of polarity and solvent, the problem of being lost in the absence of high-octane olefin component in sulfur-rich aromatic component, therefore
Washing oil circulation need not be returned, so energy consumption is low；Gasoline processing provided by the invention is not present high-octane olefin component and lost
The problem of into sulfur-rich aromatic component, therefore the pentane component of anti-top light olefin need not be added for this, so device material consumption is low；
Because no light component returns washing lotion circulation, eliminate and return washing lotion tower, so the problems such as rushing tower, foaming is not present in device, improve
Plant running stability.Gasoline processing method provided by the invention coordinate preferable extractive distillation solvent can more efficiently by
Sulfide and alkene are separated, and reduce the loss of alkene in sweetening process.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of gasoline processing method, it is characterised in that this method includes：Gasoline is stripped distillation processing, wherein, it is described
The initial boiling point of gasoline is more than 40 DEG C, and the end point of distillation, below 170 DEG C, the extractive distillation is handled after obtaining rich solvent and refining
Gasoline, the extractive distillation, which is handled, causes Aromatic Hydrocarbon in Gasoline and sulfide to be dissolved in extractive distillation solvent and form the rich solvent.
2. gasoline processing method according to claim 1, wherein, the gasoline is stripped into distillation processing includes：
Under the conditions of extractive distillation, gasoline is contacted with extractive distillation solvent.
3. gasoline processing method according to claim 2, wherein, the extractive distillation condition includes：It is 60- to enter tower temperature degree
100 DEG C, preferably 80-90 DEG C；Tower top temperature is 70-90 DEG C, preferably 75-85 DEG C；Column bottom temperature is 140-180 DEG C, preferably
For 155-170 DEG C；Tower top pressure is 0.05-0.1MPa；
Preferably, the feed weight ratio of the extractive distillation solvent and the gasoline is 1-4：1, more preferably 2-3：1.
4. the gasoline processing method according to any one in claim 1-3, wherein, the extractive distillation solvent includes sulfone
Class compound, diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, polyethylene glycol, 2-Pyrrolidone, N- formyl-morpholines, N- crassitudes
At least one of ketone, N- ethyl pyrrolidones, N- propyl pyrroles alkanone, propene carbonate and ethylene carbonate；
Preferably, the extractive distillation solvent includes main solvent, cosolvent and olefinic polymerization inhibitor, molten with the extractive distillation
On the basis of the gross weight of agent, the content of the main solvent is 70-99 weight %, and the content of the cosolvent is 0.999-29.9 weights
% is measured, the content of the olefinic polymerization inhibitor is 10-1000 μ g/g；The main solvent is selected from sulfone compound；The hydrotropy
Agent in 1-METHYLPYRROLIDONE, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, furfural and dimethyl acetamide at least one
Kind；The olefinic polymerization inhibitor is selected from p-tert-Butylcatechol, diethyl hydroxylamine, dipropyl azanol, 2- sec-butyls -4,6-
At least one of dinitrophenol and natrium nitrosum.
5. gasoline processing method according to claim 4, wherein, the content of the main solvent is 80-95 weight %, described
The content of cosolvent is 4.99-19.9 weight %, and the content of the olefinic polymerization inhibitor is 100-1000 μ g/g,
Preferably, the content of the main solvent is 85-90 weight %, and the content of the cosolvent is 9.95-14.9 weight %, institute
The content for stating olefinic polymerization inhibitor is 500-1000 μ g/g；
It is further preferred that the sulfone compound is in sulfolane, 3- methyl sulfolanes, dimethyl sulfone and diη-propyl sulfone
At least one, preferably sulfolane；The cosolvent is 1-METHYLPYRROLIDONE and triethylene glycol monomethyl ether and/or tetraethylene glycol list
The mixture of methyl ether；The olefinic polymerization inhibitor is p-tert-Butylcatechol and/or 2- sec-butyl -4,6- dinitro benzenes
Phenol；
It is further preferred that in terms of the 1-METHYLPYRROLIDONE of 100 parts by weight, the triethylene glycol monomethyl ether and/or tetraethylene glycol
The dosage of monomethyl ether is 10-200 parts by weight, preferably 50-100 parts by weight.
6. the gasoline processing method according to claim 4 or 5, wherein, the extractive distillation solvent also includes corrosion inhibiter, institute
State corrosion inhibiter and be selected from least one of MEA, diethanol amine, (2-hydroxyethyl)methylamine) and N methyldiethanol amine；
Preferably, on the basis of the gross weight of extractive distillation solvent, the content of the corrosion inhibiter is 10-1000 μ g/g, is preferably
100-1000 μ g/g, more preferably 500-1000 μ g/g.
7. gasoline processing method according to claim 1, wherein, the rich solvent is subjected to stripping processing, obtains solvent
With the aromatic hydrocarbons containing sulfide；
Preferably, the aromatic hydrocarbons containing sulfide is subjected to selective hydrogenation processing；
It is further preferred that the method for the selective hydrogenation processing includes：Under the conditions of selective hydrogenation, contain sulphur by described
The aromatic hydrocarbons and hydrogen of compound contact with catalyst for selectively hydrodesulfurizing.
8. gasoline processing method according to claim 7, wherein, the selective hydrogenation condition includes：Temperature is 250-
600 DEG C, liquid hourly space velocity (LHSV) 1-10h-1, hydrogen to oil volume ratio 200-700, pressure 2-8MPa.
9. the gasoline processing method according to any one in claim 1-8, wherein, the initial boiling point of the gasoline is at 55 DEG C
More than, and the end point of distillation is below 150 DEG C.
10. the gasoline processing method according to any one in claim 1-9, wherein, the gasoline contains aromatic hydrocarbons, alkene
Hydrocarbon, alkadienes, alkane and sulfide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2709514C1 (en) * | 2019-10-26 | 2019-12-18 | Общество с ограниченной ответственностью «Компания Петромаруз» | Method of producing a plasticizer |
| CN115491222A (en) * | 2022-09-23 | 2022-12-20 | 上海兖矿能源科技研发有限公司 | Composite extracting agent and Fischer-Tropsch synthesis distillate oil separation method using same |
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| CN103160310A (en) * | 2013-03-15 | 2013-06-19 | 西南石油大学 | Composite solvent and extraction method for extracting and separating aromatic hydrocarbons |
| CN103360201A (en) * | 2012-03-30 | 2013-10-23 | 中国石油化工股份有限公司 | Method for extracting, distilling and recovering styrene from hydrocarbon mixture |
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| US20100243533A1 (en) * | 2009-03-25 | 2010-09-30 | Indian Oil Corporation Limited | Extraction of aromatics from hydrocarbon oil using n-methyl 2-pyrrolidone and co-solvent |
| CN103360201A (en) * | 2012-03-30 | 2013-10-23 | 中国石油化工股份有限公司 | Method for extracting, distilling and recovering styrene from hydrocarbon mixture |
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| CN115491222A (en) * | 2022-09-23 | 2022-12-20 | 上海兖矿能源科技研发有限公司 | Composite extracting agent and Fischer-Tropsch synthesis distillate oil separation method using same |
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