CN107779224A - A kind of gasoline processing method - Google Patents
A kind of gasoline processing method Download PDFInfo
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- CN107779224A CN107779224A CN201710240434.2A CN201710240434A CN107779224A CN 107779224 A CN107779224 A CN 107779224A CN 201710240434 A CN201710240434 A CN 201710240434A CN 107779224 A CN107779224 A CN 107779224A
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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
- 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
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Abstract
The present invention relates to field of hydrogenation, specifically, discloses a kind of gasoline processing method, this method includes：Gasoline is cut into light gasoline fraction, middle gasoline fraction and heavy naphtha, the light gasoline fraction is subjected to etherification process, the middle gasoline fraction is stripped distillation processing, the heavy naphtha is subjected to selective hydrogenation processing, wherein, the initial boiling point of the middle gasoline fraction 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 middle gasoline, and aromatic hydrocarbons and sulfide are dissolved in extractive distillation solvent and form the rich solvent in gasoline fraction during the extractive distillation processing causes.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 is had found in research process, and in gasoline process, gasoline first is cut into light petrol
Cut, middle gasoline fraction and heavy naphtha, middle gasoline fraction is then stripped distillation processing, extractive distillation, which is handled, to be caused
Aromatic hydrocarbons and sulfide are dissolved in extractive distillation solvent formation rich solvent in middle gasoline fraction, and the middle gasoline after refining is distilled off,
Effectively sulfide and olefin component can be separated, partly avoided in sweetening process, octane number caused by the saturation of alkene damages
Lose, further, the rich solvent is subjected to stripping processing, solvent and aromatic hydrocarbons containing sulfide can be separated, contain sulphur
The aromatic hydrocarbons of compound can enter selective hydrodesulfurization device together with heavy naphtha and carry out desulfurization process.
Based on this, the present invention provides a kind of gasoline processing method, and this method includes：By gasoline be cut into light gasoline fraction,
Middle gasoline fraction and heavy naphtha, the light gasoline fraction is subjected to etherification process, the middle gasoline fraction is stripped
Distillation is handled, and the heavy naphtha is carried out into selective hydrogenation processing, wherein, the initial boiling point of the middle gasoline fraction is at 40 DEG C
More than, and the end point of distillation is below 170 DEG C；The extractive distillation is handled to obtain rich solvent and refined rear middle gasoline, and the extracting is steamed
Processing is evaporated so that aromatic hydrocarbons and sulfide are dissolved in extractive distillation solvent and form the rich solvent in middle gasoline fraction.
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 extractive distillation of the present invention divides polar extraction and weight distillation
From carrying out simultaneously, existing aromatic hydrocarbons, alkene, the polarity competition process of sulfide (mercaptan, thioether, thiophene) in whole process,
There is light-heavy material separated process.Solvent polarity extracted character can be so played to greatest extent, and it is light also to embody component
Weight stalling characteristic so that the sulfide that solvent is carried in aromatic component and middle gasoline forms rich solvent, the middle gasoline after refining
It is distilled off, alkene is hardly visible in rich solvent, is difficult to find sulfide in the middle gasoline after refined, and then can be
While realizing deep desulfurization of gasoline, 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.
Compared with prior art, following advantage be present in gasoline processing method provided by the invention：
(1) gasoline fraction in extractive distillation technical finesse is used, the solvent carrying problem for solving refined middle gasoline, is cancelled
The washing of gasoline, so as to the discharge for reducing plant running energy consumption, avoiding sour water, while is also just not present in refined
To the refined problem of washing water；
(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 cut into light gasoline fraction, middle gasoline evaporates
Point and heavy naphtha, by the light gasoline fraction carry out etherification process, by the middle gasoline fraction be stripped distillation processing,
The heavy naphtha is subjected to selective hydrogenation processing, wherein, the initial boiling point of the middle gasoline fraction is more than 40 DEG C, and end
Evaporate o'clock below 170 DEG C；The extractive distillation is handled to obtain rich solvent and refined rear middle gasoline, and the extractive distillation, which is handled, to be caused
Aromatic hydrocarbons and sulfide are dissolved in extractive distillation solvent and form the rich solvent in middle gasoline fraction.
In the present invention, the boiling range scope of the middle gasoline fraction is limited, those of skill in the art would appreciate that in being less than
The boiling range of gasoline fraction for light gasoline fraction, higher than middle gasoline fraction boiling range for heavy naphtha.For example, middle gasoline evaporates
The boiling range divided is 40-170 DEG C, and boiling range (does not wrap less than 40 DEG C (not including 40 DEG C) for light gasoline fraction, boiling range higher than 170 DEG C
Include 170 DEG C) for heavy naphtha.
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.
Heretofore described cutting, typically can be according to specific cutting using cutting technique commonly used in the art
The property of raw material select the condition of cutting, the terminal of cutting is as far as possible to divide the light fraction, middle cut and heavy distillat
Open and be defined.
The initial boiling point of middle gasoline fraction is more than 40 DEG C, and the purpose of the present invention can be achieved in the end point of distillation below 170 DEG C,
And when the initial boiling point of the middle gasoline fraction is more than 65 DEG C, and the end point of distillation is below 150 DEG C, it is pungent to be more beneficial for reduction gasoline
The loss of alkane value.
A preferred embodiment of the invention, the middle gasoline fraction is stripped into distillation processing includes：
Under the conditions of extractive distillation, gasoline is contacted with extractive distillation solvent.
There is no particular limitation for the mode that is contacted to the middle gasoline fraction with extractive distillation solvent of the present invention, can be according to
This area conventional meanses are carried out, it is preferable that are introduced middle gasoline fraction in the middle part of extraction distillation tower, extractive distillation solvent is from extracting
Destilling tower top introduces.
The present invention is wider to the range of choice of the extractive distillation condition, as long as so that aromatic hydrocarbons and vulcanization in middle gasoline fraction
Thing is dissolved in extractive distillation solvent, it is preferable that the extractive distillation condition includes：Enter tower temperature degree for 60-100 DEG C, be 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 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 middle gasoline forms rich solvent, and the middle gasoline after refining is distilled off, and is difficult to see in rich solvent
It is difficult to find sulfide in the middle gasoline after refined, and then can be reduced while deep desulfurization of gasoline is realized to alkene
Loss of octane number.
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 middle gasoline fraction 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, it is preferable that carry out selective hydrogenation processing after the aromatic hydrocarbons containing sulfide is mixed with the heavy naphtha jointly.
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) mixed with the heavy naphtha after common carry out selective hydrogenation processing and both can guarantee that depth
Desulfurization is spent, and can reduces the loss of octane number.
The present invention is to the heavy naphtha and the aromatic hydrocarbons containing sulfide carries out selective hydrogenation processing, by sulphur therein
Compound removes, while retains the alkene in heavy petrol to greatest extent, to avoid excessive loss of octane number.
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
Aromatic hydrocarbons, heavy naphtha and the 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.
According to gasoline processing method of the present invention, it is preferable that counted by 100 parts by weight of the total amount of gasoline, it is described light
Gasoline fraction is 15-30 parts by weight, and the middle gasoline fraction is 30-50 parts by weight, and the heavy naphtha is 20-50 weight
Part, it is further preferred that the light gasoline fraction is 20-25 parts by weight, the middle gasoline fraction is 35-45 parts by weight, described
Heavy naphtha is 30-45 parts by weight.
A preferred embodiment of the invention, this method is additionally included in gasoline is cut before, gasoline is entered
Row pre-hydrotreating, the pre-hydrotreating cause the alkadienes saturation in gasoline, and small molecule sulfide is converted into macromolecular sulphur
Compound.Before gasoline is cut, gasoline is subjected to pre-hydrotreating, is more beneficial for obtaining the relatively low light petrol of sulfur content and evaporates
Point, so as to avoid loss of octane number to greatest extent.
A preferred embodiment of the invention, gasoline is carried out to the method for pre-hydrotreating to be included：It is being hydrogenated with advance
Under treatment conditions, gasoline and hydrogen are contacted with pre-hydrotreating catalyst, the pre-hydrotreating catalyst contain carrier and
Metal active constituent, the metal active constituent contain molybdenum and/or tungsten and nickel, and on the basis of total catalyst weight, carrier
Content be 66-86%, in terms of oxide, the content of molybdenum and/or tungsten is 2-9%, and the content of nickel is 12-25%, wherein, with oxygen
The weight of compound meter, molybdenum and/or tungsten and nickel ratio is 0.1-0.5:1.
In the present invention, the content of the molybdenum and/or tungsten refers to the total content of molybdenum and tungsten, i.e., when the metal active composition is same
When Shi Hanyou molybdenums and tungsten, the content represents the total content of molybdenum and tungsten；When the metal active composition contains molybdenum and when not containing tungsten,
The content represents the content of molybdenum；When the metal active composition contains tungsten and when not containing molybdenum, the content represents the content of tungsten.
The present inventor has found in research process, if in the pre-hydrotreating catalyst containing molybdenum and/or
Tungsten and nickel, and meet that foregoing ratio can realize the purpose of the present invention, but under preferable case, be catalyzed with pre-hydrotreating
On the basis of agent gross weight, the content of the carrier is 66-86%, and in terms of oxide, the content of molybdenum and/or tungsten is 2-9%, nickel
When content is 12-25%, pre-hydrotreating catalyst it is desulphurizing activated higher.
In the case of further preferably, molybdenum and/or the weight of tungsten and nickel ratio are 0.1-0.5:1.The present inventor thinks,
Although at least one of molybdenum and tungsten, which with nickel coordinate as metal active constituent can, realizes the purpose of the present invention,
When containing molybdenum and tungsten in metal active composition, the weight ratio of particularly molybdenum and tungsten is 0.1-0.9:When 1, preferably 0.1-0.6:
When 1, the desulphurizing activated of pre-hydrotreating catalyst can further improve.
According to the present invention, the total pore volume of the pre-hydrotreating catalyst can be 0.3-1.2cm3/ g, it is preferably
0.5-1.0cm3/g。
According to the present invention, the specific surface area of the pre-hydrotreating catalyst can be 30-150m2/ g, preferably 70-
150m2/g.Specific surface area is BET specific surface area in the present invention.
The carrier can be various heat-resisting porous materials commonly used in the art.Specifically, the heat-resisting porous material
Material can be heat-resisting inorganic oxide and/or silicate.
Preferably, the carrier be aluminum oxide, it is silica, titanium oxide, magnesia, zirconium oxide, thorium oxide, beryllium oxide, viscous
One or more in soil and molecular sieve.It is highly preferred that the carrier is one kind or more in aluminum oxide, silica and molecular sieve
Kind.
According to the present invention, the present invention is to the pore volume of the carrier without particular/special requirement, preferably 0.8-1.4cm3/g。
It is prepared by the various methods that heretofore described pre-hydrotreating catalyst is referred to prior art, such as
Conventional infusion process can be used to prepare, such as dry impregnation method (i.e. equi-volume impregnating), the dry impregnation method for example may be used
To carry out as follows：Molybdenum and/or tungsten salt and nickel salt solution (such as deionized water solution) are contacted with carrier so that final
The content of molybdenum and/or tungsten is less than 10% in the pre-hydrotreating catalyst of formation, and the content of nickel is 10-30%, is then dried, roasting
Burn and can obtain pre-hydrotreating catalyst of the present invention.Wherein by molybdenum and/or tungsten salt and nickel salt solution (such as deionization
The aqueous solution) method that is contacted with carrier can carry out by the following two kinds method：(1) can be by molybdenum salt and/or tungsten salt and nickel salt
Carrier is immersed again after forming a kind of mixed aqueous solution；(2) molybdenum salt and/or tungsten salt and nickel salt can also be each made into
The aqueous solution, then carrier is contacted to (the order contacted with three kinds of solution times with molybdenum salt and/or tungsten salt and nickel salt solution successively
Meaning).
According to the present invention, the nickel salt can be various water soluble nickel salts, such as can be nickel nitrate, nickel chloride, nickel sulfate
Deng the one or more in conventional various water soluble nickel salts；Tungsten salt can be various water-soluble tungsten salts, such as can be metatungstic acid
One or more in the conventional various water-soluble tungsten salts such as ammonium, thio ammonium tungstate；Molybdenum salt can be various water-soluble molybdenum salt, such as
Can be in the conventional various water-soluble molybdenum salt such as ammonium heptamolybdate, ammonium tetramolybdate, ammonium dimolybdate in one or more.
The present invention, without particular/special requirement, is referred to prior art progress to the drying, the method for roasting and condition.Example
Such as, dry temperature can be 80-200 DEG C, and the dry time can be 1-10h.The temperature of roasting can be 300-800 DEG C,
The time of roasting can be 1-8h.
There is no particular limitation for condition of the present invention to pre-hydrotreating processing, for example, at the selective hydrogenation
Manage bar part can include：Temperature is 120-350 DEG C, liquid hourly space velocity (LHSV) 0.5-10h-1, pressure 1-10MPa, hydrogen to oil volume ratio is
200-700:1。
In the present invention, the light gasoline fraction that gasoline cuts to obtain is subjected to etherification process, the condition of the etherification process
To cause C5, C6 alkene in light gasoline fraction to change into corresponding ether (high octane gasoline component) as far as possible, so as to improve
Octane number.
There is no particular limitation for condition of the present invention to the etherification process, and those skilled in the art can be according to actual feelings
Condition is selected.
Specifically, the method for the etherification process includes：Under etherification conditions, by the light gasoline fraction and etherifying reagent
Contacted with catalyst for etherification, obtain etherification product.
According to the present invention, etherification conditions of the invention can be conventional etherification conditions, and etherification conditions of the invention are general
Including：Temperature is 30-200 DEG C, and preferably 65-85 DEG C, preferably pressure 0.1-5MPa, 0.5-2MPa, liquid hourly space velocity (LHSV) is
0.1-5h-1, preferably 0.5-2.5h-1, the volume ratio of etherifying reagent and light gasoline fraction is 0.1-10:1, preferably 0.5-5:
1。
In the present invention, the etherifying reagent can be various conventional use of various etherifying reagents, preferably methanol and/or
Ethanol.
In the present invention, the catalyst for etherification can be various conventional use of catalyst for etherification, for example, can be sun from
Sub-exchange resin and/or heteropoly acid, wherein, the cationic ion-exchange resin is preferably storng-acid cation exchange resin, described
Catalyst containing heteropoly compound can be described to contain heteropoly acid type under preferable case for heteropoly compound in itself
The catalyst of compound is solid-carrying heteropolyacid catalyst, and the solid-carrying heteropolyacid catalyst can be conventional catalyzed with solid supported heteropolyacid
Agent, such as can be (referring to document by the immobilized solid-carrying heteropolyacid catalyst on activated carbon of heteropoly compound：It is immobilized miscellaneous more
The Etherification of Light FCC Gasoline reactivity worth research, Xu Haisheng etc. of acid catalyst, in Xi'an Petroleum University's oil refining engineering and technological research
The heart).
In the present invention, the etherification product after can light gasoline fraction be etherified directly uses as needed, can also
Desulfurization product after sulfur-rich aromatic hydrocarbons and the heavy naphtha selective hydrodesulfurization that therefrom gasoline fraction is obtained enters as needed
Row directly uses, it is however generally that because the product sulfur content after sulfur-rich aromatic hydrocarbons and heavy naphtha selective hydrodesulfurization is relative
Relatively low (typically below 10 μ g/g), and the etherification product after light gasoline fraction etherificate is not because have desulfurization, possible sulfur content phase
To higher (typically in 20-60 μ g/g), it is therefore preferable that in the case of or the etherificate production after the light gasoline fraction is etherified
Desulfurization product and middle gasoline fraction extractive distillation after thing and sulfur-rich aromatic hydrocarbons and heavy naphtha selective hydrodesulfurization obtain
Raffinate oil mixed after reuse, so reconcile after product sulfur content it is appropriate, current row can be both met after burning
Standard is put, the waste of the energy will not be caused again.I.e. under preferable case, gasoline processing method of the invention is also included the light vapour
What oil distillate carried out that etherification process obtained etherification product, middle gasoline fraction be stripped that distillation handles to obtain raffinate oil and rich
Sulphur aromatic hydrocarbons and heavy naphtha carry out the product mixing that selective hydrogenation handles to obtain.
In the present invention, the definition of desulfurization degree is the sulfur content in the gasoline after the content of the sulfur in gasoline of before processing and processing
Difference and before processing sulfur in gasoline content ratio, computational methods be (after content-processing of the sulfur in gasoline of before processing
Gasoline in sulfur content)/before processing sulfur in gasoline content.
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 catalytic gasoline property of use is listed in table 1.
Table 1
| Feedstock property | |
| Density (20 DEG C), kg/m3 | 0.737 |
| Sulfur content, μ g/g | 1800 |
| Alkene, wt% | 37.8 |
| Aromatic hydrocarbons, wt% | 24.2 |
| Initial boiling point, DEG C | 42 |
| The end point of distillation, DEG C | 203 |
| Research octane number (RON) RON | 92 |
Embodiment 1
(1) pre-hydrotreating
Pre-hydrotreating catalyst is prepared according to dry impregnation method：Dry impregnation method includes using ammonium heptamolybdate and ammonium metatungstate
And the aqueous solution of nickel nitrate carries out dry impregnation.The concentration of three kinds of salting liquids in precursor solution is adjusted, it is pre- in deposited on supports
The metal oxide of phase weight, the solid obtained after dipping is cured into 4h at room temperature, in 120 DEG C of dry 6h.Finally, after drying
Air of the solid at 500 DEG C in calcine two hours, the carrier used is alumina support (pore volume 1.2cm3/ g), press
The pre-hydrotreating catalyst prepared according to preceding method contains 2.5 weight % MoO3, 5.5 weight % WO3, 18 weight %'s
NiO, and specific surface area (BET) is 70m2/ g, total pore volume (TPV) are 1.0cm3/g；
0.2 gram of pre-hydrotreating catalyst is taken, pre-hydrotreating catalyst is vulcanized, the condition of vulcanization is to use to contain
5 weight %CS2N-hexane for sulfurized oil in liquid hourly space velocity (LHSV) 36h-1Lower vulcanization 3h, feed rate are 0.3 ml/min, H2Stream
Measure as 180 ml/mins, hydrogen dividing potential drop 3.2MPa；
Pre-hydrotreating catalyst after vulcanization and catalytic gasoline (property is shown in Table 1) are subjected to pre-hydrotreating reaction, instead
Condition is answered to include：Pressure is 3.2MPa, liquid hourly space velocity (LHSV) 6h-1, feed rate is 0.2 ml/min, hydrogen to oil volume ratio 300,
Obtain product after pre-hydrotreating.
(2) product after pre-hydrotreating is cut：Product after pre-hydrotreating is subjected to distillation cutting, obtains boiling range
The middle gasoline fraction (40 parts by weight) and boiling range for being 65-150 DEG C for 150-203 DEG C of heavy naphtha (35 parts by weight), boiling range
For 42-65 DEG C of light gasoline fraction (25 parts by weight).
(3) light gasoline fraction carries out etherification process：By light gasoline fraction that boiling range obtained by step (2) is 42-65 DEG C in temperature
Spend for 75 DEG C, pressure 1MPa, liquid hourly space velocity (LHSV) 1h-1, etherifying reagent is methanol, catalyst for etherification is commercially available from the U.S. permanent ring in Shenzhen
Protect under conditions of the strong acidic ion resin of Technology Co., Ltd. and the volume ratio of methanol and light gasoline fraction are 1 and carry out ether
Change, obtain etherification product.
(4) gasoline fraction extractive distillation in：Middle gasoline fraction is introduced in the middle part of extraction distillation tower, 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),
By extractive distillation, extractive distillation condition includes：Enter tower temperature degree for 84 DEG C, tower top temperature is 76-77 DEG C, column bottom temperature 158-
160 DEG C, tower top operating pressure is 0.1MPa, and the discharge of extractive distillation column overhead is raffinated oil, and extraction distillation tower bottom of towe is rich in aromatic hydrocarbons
Stripped with the rich solvent of sulfide into stripper, specific stripping conditions include：Tower top temperature is 80-82 DEG C, bottom of towe temperature
Spend for 177-179 DEG C, backflow/charge-mass ratio is 1；Bottom of towe obtains lean solvent, and tower top obtains sulfur-rich aromatic hydrocarbons, system operation 6
After month, obtained lean solvent pH value is about 7.
(5) selective hydrodesulfurization is handled：Boiling range obtained by the sulfur-rich aromatic hydrocarbons and step (2) that step (4) is obtained is 150-
203 DEG C of heavy naphtha carries out selective hydrodesulfurization processing, and selective hydrogenation condition includes：Temperature is 280 DEG C, liquid space-time
Speed is 2.5h-1, hydrogen to oil volume ratio 250, pressure 2.5MPa, catalyst is commercially available from Research Institute of Petro-Chemical Engineering, the trade mark
RSDS-31, obtain the selective hydrodesulfurization product that sulfur content is 10 μ g/g.
(6) etherification product, raffinate oil with selective hydrogenation processing product mix：By etherification product, step obtained by step (3)
(4) gained is raffinated oil and step (5) gained selective hydrogenation processing product mixes, and obtains low-sulfur reaction oil, low-sulfur reaction
The sulfur content and research octane number (RON) of oil are shown in Table 3, and desulfurization degree and loss of octane number are shown in Table 3.
The extractive distillation solvent of table 2 forms
Note：Extractive distillation balance of solvent is water
Embodiment 2
According to the method for embodiment 1, the difference is that：
Step (1)：The pre-hydrotreating catalyst prepared according to preceding method contains 1 weight % MoO3, 3 weight %'s
WO3, 20 weight % NiO, and specific surface area (BET) is 90m2/ g, total pore volume (TPV) are 0.8cm3/g。
Step (4)：Extractive distillation solvent F-1 is replaced with extractive distillation solvent F-2, extractive distillation solvent F-2 is had
Body composition is shown in Table 2, and the mass ratio of extractive distillation solvent and middle gasoline fraction is 3:1.
Embodiment 3
According to the method for embodiment 1, the difference is that：
Step (1)：The pre-hydrotreating catalyst prepared according to preceding method contains 0.5 weight % MoO3, 4.5 weights
Measure % WO3, 25 weight % NiO, and specific surface area (BET) is 100m2/ g, total pore volume (TPV) are 0.5cm3/g。
Step (4)：Extractive distillation solvent F-1 is replaced with extractive distillation solvent F-3, extractive distillation solvent F-3 is had
Body composition is shown in Table 2, and the mass ratio of extractive distillation solvent and middle gasoline fraction is 2.5:1.
Embodiment 4
Carried out according to the method described in embodiment 1, unlike, used by step (4) in extractive distillation solvent, use
The 1-METHYLPYRROLIDONE of phase homogenous quantities substitutes triethylene glycol monomethyl ether.After system operation 6 months, obtained lean solvent pH value is about
7, and without olefin polymerization suspension in lean solvent.
Embodiment 5
Carried out according to the method described in embodiment 1, unlike, used by step (4) in extractive distillation solvent, use
The triethylene glycol monomethyl ether of phase homogenous quantities substitutes 1-METHYLPYRROLIDONE.After system operation 6 months, obtained lean solvent pH value is about
7, and without olefin polymerization suspension in lean solvent.
Embodiment 6
Carried out according to the method described in embodiment 1, unlike, used by step (4) in extractive distillation solvent, use
The diethyl hydroxylamine of phase homogenous quantities substitutes tert-butyl catechol.After system operation 6 months, obtained lean solvent pH value is about 7,
Occurs a small amount of olefin polymerization suspension in lean solvent.
Embodiment 1 is compared, and a small amount of olefin polymerization suspension occurs in system operation after 6 months, in lean solvent, that is, is lacked
Perhaps 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.After system operation 6 months, obtained lean solvent pH value drops to 5.5, under performance
Drop.
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 %.
Embodiment 9
Carried out according to the method described in embodiment 1, unlike, carry out pre-hydrotreating catalysis according to the method for embodiment 1
The preparation of agent, unlike, the concentration of three kinds of salting liquids in regulation precursor solution, in the metal oxygen of deposited on supports expection weight
Compound, property are as follows：15 weight % MoO3, 0 weight % WO3, 9 weight % NiO, and specific surface area (BET) is 90m2/
G, total pore volume (TPV) are 0.8cm3/g。
Embodiment 10
Carried out according to the method for embodiment 1, unlike, the pre-hydrotreating described in not including step (1), directly to urging
Change gasoline to be cut.
Comparative example 1
According to the method for embodiment 1, the difference is that, step is cut in (2) to product after pre-hydrotreating：By pre-add
Product carries out distillation cutting at 70 DEG C after hydrogen processing, and it is 42-70 DEG C to obtain heavy distillat that boiling range is 70-203 DEG C and boiling range
Light fraction, and do not include step (4).
Table 3
| Desulfurization degree (%) | Loss of octane number | |
| Embodiment 1 | 94.3 | 0.9 |
| Embodiment 2 | 93.6 | 0.9 |
| Embodiment 3 | 93.3 | 0.9 |
| Embodiment 4 | 90.5 | 1.3 |
| Embodiment 5 | 88.2 | 1.4 |
| Embodiment 6 | 86.1 | 1.6 |
| Embodiment 7 | 93.8 | 1.2 |
| Embodiment 8 | 84.3 | 1.8 |
| Embodiment 9 | 83.2 | 1.7 |
| Embodiment 10 | 80.0 | 2.0 |
| Comparative example 1 | 85.4 | 2.9 |
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
System run all right.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.Under preferable case, the gasoline processing method coordinates special
Fixed pre-hydrotreating catalyst is more beneficial for improving desulfurization degree, and further reduces the loss of octane number.
The preferred embodiment of the present invention described in detail above, still, the present invention is not limited thereto.In the skill of the present invention
In art concept, technical scheme can be carried out a variety of simple variants, including each technical characteristic with it is any its
His suitable method is combined, and these simple variants and combination should equally be considered as content disclosed in this invention, belong to
Protection scope of the present invention.
Claims (10)
1. a kind of gasoline processing method, it is characterised in that this method includes：Gasoline is cut into light gasoline fraction, middle gasoline evaporates
Point and heavy naphtha, by the light gasoline fraction carry out etherification process, by the middle gasoline fraction be stripped distillation processing,
The heavy naphtha is subjected to selective hydrogenation processing,
Wherein, the initial boiling point of the middle gasoline fraction is more than 40 DEG C, and the end point of distillation is below 170 DEG C；At the extractive distillation
Reason middle gasoline after obtaining rich solvent and refining, the extractive distillation, which is handled, make it that aromatic hydrocarbons and sulfide are dissolved in and taken out in middle gasoline fraction
Carry solvent distillation and form the rich solvent.
2. gasoline processing method according to claim 1, wherein, the middle gasoline fraction is stripped distillation processing bag
Include：
Under the conditions of extractive distillation, middle gasoline fraction is contacted with extractive distillation solvent；
Preferably, the extractive distillation condition includes：Enter tower temperature degree for 60-100 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 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.
3. gasoline processing method according to claim 1, wherein, the extractive distillation solvent includes sulfone compound, two
Glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, 2-Pyrrolidone, N- formyl-morpholines, 1-METHYLPYRROLIDONE, N- N-ethyl pyrrole Ns
At least one of alkanone, 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.
4. gasoline processing method according to claim 3, 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.
5. the gasoline processing method according to claim 3 or 4, 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.
6. 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；
Preferably, carried out jointly at selective hydrogenation after the aromatic hydrocarbons containing sulfide is mixed with the heavy naphtha
Reason；
Preferably, the method for the selective hydrogenation processing includes：Under the conditions of selective hydrogenation, by described containing sulfide
Aromatic hydrocarbons, heavy naphtha and hydrogen contact with catalyst for selectively hydrodesulfurizing.
7. the gasoline processing method according to any one in claim 1-6, wherein, the initial boiling point of the middle gasoline fraction
More than 65 DEG C, and the end point of distillation is below 150 DEG C.
8. the gasoline processing method according to any one in claim 1-7, wherein, the light gasoline fraction is 20-25
Parts by weight, the middle gasoline fraction are 35-45 parts by weight, and the heavy naphtha is 30-45 parts by weight.
9. the gasoline processing method according to any one in claim 1-8, wherein, this method, which is additionally included in, enters gasoline
Before row cutting, gasoline is subjected to pre-hydrotreating, the pre-hydrotreating causes the alkadienes saturation in gasoline, small molecule vulcanization
Thing is converted into macromolecular sulfide；
Preferably, gasoline is carried out to the method for pre-hydrotreating to be included：Under the conditions of pre-hydrotreating, by gasoline and hydrogen and in advance
Hydrotreating catalyst contacts, and the pre-hydrotreating catalyst contains carrier and metal active constituent, the metal active group
Divide and contain molybdenum and/or tungsten and nickel, and on the basis of total catalyst weight, the content of carrier is 66-86%, in terms of oxide,
The content of molybdenum and/or tungsten is 2-9%, and the content of nickel is 12-25%, wherein, in terms of oxide, molybdenum and/or the weight of tungsten and nickel
Than for 0.1-0.5:1；
Preferably, it is 120-350 DEG C that the pre-hydrotreating condition, which includes temperature, liquid hourly space velocity (LHSV) 0.5-10h-1, pressure 1-
10MPa, hydrogen to oil volume ratio 200-700:1.
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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