CN107779220B - A kind of gasoline processing method - Google Patents

A kind of gasoline processing method Download PDF

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Publication number
CN107779220B
CN107779220B CN201710240066.1A CN201710240066A CN107779220B CN 107779220 B CN107779220 B CN 107779220B CN 201710240066 A CN201710240066 A CN 201710240066A CN 107779220 B CN107779220 B CN 107779220B
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Prior art keywords
gasoline
solvent
processing method
weight
extractive distillation
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CN107779220A (en
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曲良龙
耿新水
姚伟
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BEIJING ENERGY ENGINEERING TECHNOLOGIES Co Ltd
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BEIJING ENERGY ENGINEERING TECHNOLOGIES Co Ltd
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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in the absence of hydrogen, by extraction with selective solvents with two or more solvents, which are introduced or withdrawn separately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

Abstract

The present invention relates to field of hydrogenation, specifically, disclose a kind of gasoline processing method, this method comprises: gasoline is stripped distillation processing, wherein, the initial boiling point of the gasoline is at 40 DEG C or more, and the end point of distillation is at 170 DEG C or less, the extractive distillation handles gasoline after obtaining rich solvent and refining, and the extractive distillation processing is so that Aromatic Hydrocarbon in Gasoline and sulfide are dissolved in extractive distillation solvent and form the rich solvent.Low energy consumption for the gasoline processing method, desulfuration efficiency is high, and loss of octane number is lower.

Description

A kind of gasoline processing method
Technical field
The present invention relates to field of hydrogenation, and in particular, to a kind of gasoline processing method.
Background technique
As people are to the pay attention to day by day of environmental protection, environmental regulation is also increasingly stringent, and reduces the sulfur content quilt of gasoline It is considered to improve one of the most important measure of air quality.Most of sulphur in China's gasoline products are from hot-working petroleum tune It is combined point, such as catalytically cracked gasoline.Therefore, it is necessary to which catalytically cracked gasoline is carried out deep desulfuration, simple catalytic gasoline desulfurization Technology can all bring problem: the octane number decline of catalytic gasoline.
In order to be saturated alkene few as far as possible under the premise of guaranteeing certain desulfurization depth, currently, the work of researcher's exploitation Skill technology mainly has: the RSDS technique that the S-zorb technology of middle petrochemical industry exploitation, middle petrochemical industry Research Institute of Petro-Chemical Engineering develop, with And France's Prime-G+ technology.
The S-zorb technology of middle petrochemical industry exploitation is used for full fraction catalytic gasoline desulfurization, and sulfur content can control after desulfurization 10ppm is hereinafter, the loss of octane number of fraction catalytic gasoline is in 1-2 unit entirely.Middle petrochemical industry Research Institute of Petro-Chemical Engineering exploitation 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 needs to add hydrogen, full fraction vapour About 3-4 unit of oily loss of octane number.French Prime-G+ technology carries out pre-add hydrogen before carrying out gasoline cutting, by gasoline, Pre- hydrogenation process acts on lighter sulfide and alkadienes to form high boiling sulfide, and alkene is not saturated, the technology Loss of octane number be also about 3-4 unit.
Therefore, while needing one kind and can be realized deep desulfurization of gasoline, the gasoline processing method of loss of octane number is reduced.
Summary of the invention
The purpose of the present invention is overcoming in prior art sweetening process, the serious defect of loss of octane number provides a kind of vapour Oily processing method.Low energy consumption for the gasoline processing method, desulfuration efficiency is high, and loss of octane number is lower.
The present inventor has found in the course of the research, in gasoline process, by initial boiling point at 40 DEG C or more, and The end point of distillation is stripped distillation processing in 170 DEG C of gasoline below, and extractive distillation processing is so that Aromatic Hydrocarbon in Gasoline and sulfide are molten Rich solvent is formed in extractive distillation solvent, the gasoline after purification is distilled off, can be effectively by sulfide and olefin component point It opens, partially avoids in sweetening process, loss of octane number caused by the saturation of alkene further carries out the rich solvent Stripping processing can separate solvent and aromatic hydrocarbons containing sulfide, and 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, this method comprises: gasoline is stripped distillation processing, Wherein, the initial boiling point of the gasoline is at 40 DEG C or more, and the end point of distillation at 170 DEG C hereinafter, the extractive distillation handles to obtain Fu Rong Gasoline after agent and purification, the extractive distillation processing so that Aromatic Hydrocarbon in Gasoline and sulfide be dissolved in extractive distillation solvent formed it is described Rich solvent.
The liquid liquid extractive process of the 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 constitutes complexity, it would become hard to meet demand on yield.Catalytic gasoline component is a raw material composition Extremely complex raw material, if the liquid liquid using the prior art extracts, 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 by can be containing the sulfide of weight, together in the catalytic gasoline after the extracting of liquid liquid When the oil that is dissolved by the solvent in will carry light alkene.And present invention is particularly directed to initial boiling points at 40 DEG C or more, and the end point of distillation exists 170 DEG C of gasoline below be stripped distillation processing, the extractive distillation by polar extraction and weight distillation separation simultaneously into Row, the polarity competition process of existing aromatic hydrocarbons, alkene, sulfide (mercaptan, thioether, thiophene), also there is weight object in the whole process Material distillation separation process.Solvent polarity extracted character can be played to greatest extent in this way, it is special also to embody the separation of component weight Property, so that solvent carries the sulfide in aromatic component and middle gasoline and forms rich solvent, the middle gasoline after purification is distilled out Come, alkene is hardly visible in rich solvent, is difficult to find sulfide in the middle gasoline after purification, and then can realize gasoline While deep desulfuration, loss of octane number is reduced.
Gasoline processing method provided by the invention cooperates preferred extractive distillation solvent can be more efficiently by sulfide It is separated with alkene, reduces the loss of alkene in sweetening process.
Gasoline processing method provided by the invention cooperates preferred catalyst for selectively hydrodesulfurizing can be more efficiently Sulfide is removed.
Compared with prior art, there are following advantages for gasoline processing method provided by the invention:
(1) using extractive distillation technical treatment boiling range is initial boiling point at 40 DEG C or more, and the end point of distillation is in 170 DEG C of vapour below Oil solves the solvent carrying problem of treated gasoline, eliminates the washing of treated gasoline, thus reduce device operation energy consumption, The discharge of sour water is avoided, while also just there is no the purification problems to washing water；
(2) extractive distillation technology is used, the race problem of alkene polarity and sulfide polarity and solvent is solved, is not present High-octane olefin component is lost to the problems in sulfur-rich aromatic component, therefore does not need to return washing oil circulation, so low energy consumption；
(3) present invention is lost to the problems in sulfur-rich aromatic component there is no high-octane olefin component, therefore is not required to The pentane component that add anti-top light olefin thus, so device material consumption is low；
(4) it due to there is no light component to return washing lotion circulation, eliminates and returns washing lotion tower, so there is no rush tower, foaming etc. to device Problem improves device operation stability.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of gasoline processing method, this method comprises: gasoline is stripped distillation processing, wherein institute The initial boiling point of gasoline is stated at 40 DEG C or more, and the end point of distillation at 170 DEG C hereinafter, the extractive distillation handles to obtain rich solvent and purification Gasoline afterwards, the extractive distillation processing is so that Aromatic Hydrocarbon in Gasoline and sulfide are dissolved in extractive distillation solvent and form the rich solvent.
The present inventor has found in the course of the research, is taken off sulphur in middle gasoline and heavy petrol to 10 using the prior art When 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 at 40 DEG C or more, and the end point of distillation is at 170 DEG C of gasoline below Reason be applicable in gasoline processing method provided by the invention, the present inventor further study show that, initial boiling point 55 DEG C with Upper (preferably at 60 DEG C or more), and the end point of distillation 150 DEG C or less (preferably at 125 DEG C or less) gasoline 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., the 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 at 40 DEG C or more, and the end point of distillation is applicable in gasoline provided by the invention in 170 DEG C of gasoline processing below Processing method, the inventors of the present invention discovered through researches that, initial boiling point is 55 DEG C or more (preferably at 60 DEG C or more), and the end point of distillation exists The gasoline of 150 DEG C or less (preferably at 125 DEG C or less) is especially suitable for method provided by the invention.
A preferred embodiment of the invention, it includes: to steam in extracting that the gasoline, which is stripped distillation processing, Under the conditions of evaporating, gasoline is contacted with extractive distillation solvent.
There is no particular limitation to the mode that the gasoline is contacted with extractive distillation solvent by the present invention, can be according to this field Conventional means carry out, it is preferable that introduce 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 being dissolved in Aromatic Hydrocarbon in Gasoline and sulfide Extractive distillation solvent, it is preferable that it is 60-100 DEG C that the extractive distillation condition, which includes: into 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 is by polar extraction and weight distillation separation while carrying out, existing in the whole process The polarity competition process of aromatic hydrocarbons, alkene, sulfide (mercaptan, thioether, thiophene) also has light-heavy material to distill separation process.In this way 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 purification is distilled off, and alkene is hardly visible in rich solvent Hydrocarbon is difficult in the gasoline after purification to find sulfide, and then can be while realizing deep desulfurization of gasoline, reduction octane number Loss.
The range of choice of extractive distillation solvent of the present invention and the feed weight ratio of the middle gasoline fraction is wider, excellent The feed weight ratio of selection of land, the extractive distillation solvent and the gasoline is 1-4:1, further 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-morpholine, N-Methyl pyrrolidone, N- ethyl pyrrolidone, 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 total 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 N-Methyl pyrrolidone, 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 sodium nitrite.This kind of preferred extracting is steamed It evaporates solvent with higher dissolubility and selectivity, while can guarantee the selectivity to sulfide, further decreases pair The selectivity of alkene, and the olefinic polymerization inhibitor in extractive distillation solvent has the function of inhibiting olefinic polymerization, so that extracting Solvent distillation performance is more excellent.
The present inventor has found that sulfone compound as main solvent, cooperates of the present invention help in the course of the research Solvent not only can be improved to arenes selectivity in solvent and olefinic polymerization inhibitor, also overcomes solvent and aromatic hydrocarbons is not easy to point From defect.In addition, main solvent, cosolvent and olefinic polymerization inhibitor are used in conjunction with, one-component function not will cause Subside.
In order to further increase extractive distillation solvent to the selectivity of aromatic hydrocarbons and sulfide, the selectivity to alkene is reduced, Preferably, on the basis of the total 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 total 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 are 500-1000 μ g/g.
According to the present invention, the content of olefinic polymerization inhibitor is referred to relative to every g extractive distillation solvent, olefinic polymerization The amount of inhibitor.
A preferred embodiment of the invention, the cosolvent are N-Methyl pyrrolidone and triethylene glycol monomethyl ether And/or the mixture of tetraethylene glycol monomethyl ether.Main solvent is more advantageous to using this kind of preferred embodiment and cosolvent collaboration plays Effect further decreases the selectivity to alkene while guaranteeing the selectivity to sulfide.
In the present invention, it is preferred in terms of the N-Methyl pyrrolidone 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, further preferably 50-100 parts by weight.Using this kind of preferred implementation side Formula is more advantageous to the effect for playing N-Methyl pyrrolidone and triethylene glycol monomethyl ether and/or tetraethylene glycol monomethyl ether, is guaranteeing to sulphur While the selectivity of compound, the selectivity to alkene further reduced.
It should be noted that when the cosolvent contains N-Methyl pyrrolidone and triethylene glycol monomethyl ether and four sweet simultaneously When alcohol monomethyl ether, the dosage of the triethylene glycol monomethyl ether and/or 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 Main solvent and hydrotropy in 2- sec-butyl -4,6- dinitrophenol, the preferred olefinic polymerization inhibitor and extractive distillation solvent When agent is used cooperatively, have the function of preferably inhibiting 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 Object, such as the sulfone compound can be in sulfolane, 3- methyl sulfolane, 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, Yi Fasheng Oxidation generates acid compound and acidic polymer shows sulfone class when the pH value in system drops to 4.5 or less Compound solvent degradation, such case can generate certain corrosion to equipment, for control system acidity, so that the pH value in system 6.0 or so are maintained at, the preferably described extractive distillation solvent further includes corrosion inhibiter.
There is no particular limitation to the corrosion inhibiter by the present invention, as long as can control systemic acidity, while ensuring to add slow Erosion agent does not influence the performance of extractive distillation solvent, it is preferable that the corrosion inhibiter is selected from monoethanolamine, diethanol amine, N- first At least one of base monoethanolamine and N methyldiethanol amine, most preferably monoethanolamine.
In the present invention, it is preferable that other substance migrations in the corrosion inhibiter cooperation extractive distillation solvent can be controlled effectively Systemic acidity, so that it is guaranteed that the acid stable of whole system, also functions to the effect for inhibiting 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 total weight of extractive distillation solvent On the basis of, the content of the corrosion inhibiter is 10-1000 μ g/g, further preferably 100-1000 μ g/g, still more preferably for 500-1000μg/g。
The rich solvent can be carried out stripping processing by a preferred embodiment of the invention, obtain solvent and Aromatic hydrocarbons containing sulfide.The solvent can be recycled.
The present invention is not particularly limited the steam stripped condition, those skilled in the art can according to the actual situation into Row selection appropriate, such as it is 80-90 DEG C that steam stripped condition, which may include: tower top temperature, column bottom temperature is 170-178 DEG C；Tower Pressure on top surface is -40 to -60KPa, and reflux/charge-mass ratio is 0.5-1:1.
A preferred embodiment of the invention carries out the aromatic hydrocarbons containing sulfide 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, is efficiently separated alkene and sulfide, sulfide will be contained Aromatic hydrocarbons (being practically free of alkene) carry out selective hydrogenation processing and not only can guarantee deep desulfuration, but also can be reduced the damage of octane number It loses.
There is no particular limitation to the condition that the selective hydrogenation is handled by the present invention, all selective hydrogenations of the prior art Processing method is used equally for the present invention.
In the present invention, the method for the selective hydrogenation processing includes: to contain by described under the conditions of selective hydrogenation The aromatic hydrocarbons and hydrogen of sulfide are contacted with catalyst for selectively hydrodesulfurizing.
A preferred embodiment of the invention, the selective hydrogenation condition include: that 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 add for various selectivity commonly used in the art Hydrogen desulphurization catalyst typically contains carrier and selective hydrodesulfurization active component, wherein is 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 generally can be for selected from one of VI B race, VIII race's element or more Kind, under preferable case, the selective hydrodesulfurization active component is generally one of tungsten, nickel, molybdenum, cobalt or a variety of.It is described Carrier can be conventional use of various carriers, it can be various heat-resisting porous materials commonly used in the art, specifically, institute Stating heat-resisting porous material can be heat-resisting inorganic oxide and/or silicate.
In the present invention, the octane number is research octane number (RON), survey of the measuring method referring to conventional research octane number (RON) Determine method, the present invention is without particular/special requirement.
Below by way of the specific embodiment implementation process that the present invention will be described in detail and generated beneficial effect, it is intended to help Where reader more clearly understands Spirit Essence of the invention, but any restriction cannot be constituted to practical range of the invention.
In following embodiment, the raw material of gasoline processing method uses boiling range for 60-125 DEG C of middle gasoline fraction, it is described in Gasoline fraction is cut to obtain by catalytically cracked gasoline, and the middle gasoline fraction that boiling range is 60-125 DEG C is at 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
It amounts 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 (mass ratio of extractive distillation solvent and middle gasoline fraction is 2:1), and by extractive distillation, extracting is steamed It is 84 DEG C that the condition of evaporating, which includes: into tower temperature degree, and 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, the rich solvent rich in aromatic hydrocarbons and sulfide of extraction distillation tower tower bottom into Entering stripper to be stripped, specific stripping conditions include: that tower top temperature is 80-82 DEG C, and column bottom temperature is 177-179 DEG C, reflux/ Charge-mass ratio is 1；Tower bottom obtains lean solvent, and tower top obtains sulfur-rich aromatic hydrocarbons, after system is run 6 months, obtained lean solvent PH Value about 7, and without olefin polymerization suspended matter in lean solvent, it raffinates oil and is listed in table 3 with the analysis result of sulfur-rich aromatic hydrocarbons；
It (2) is 280 DEG C in temperature, liquid hourly space velocity (LHSV) 2.5h-1, hydrogen to oil volume ratio 250, pressure is the selectivity of 2.5MPa Under hydroconversion condition, by urging for sulfur-rich aromatic hydrocarbons that step (1) obtains and the RSDS-31 trade mark that is commercially available from Research Institute of Petro-Chemical Engineering Agent contact obtains the selective hydrodesulfurization product that sulfur content is 10 μ g/g, loss of octane number 0.2.
2 extractive distillation solvent of table composition
Note: extractive distillation balance of solvent is water
Table 3 raffinates oil, the analysis result of the product of sulfur-rich aromatic hydrocarbons
By calculate it is found that only existed in raffinating oil 3.3 weight % aromatic hydrocarbons (calculation method be (0.1% × 91.7%)/(0.1% × 91.7%+32.6% × 8.3%) × 100%), the sulphur of 3 weight %, and there are 94.4 weight % Alkene；There are the aromatic hydrocarbons of 96.7 weight % in sulfur-rich aromatic hydrocarbons, the sulphur of 97 weight %, the alkene of 5.6 weight % 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 (mass ratio of extractive distillation solvent and middle gasoline fraction is 3:1), and by extractive distillation, extracting is steamed It is 86 DEG C that the condition of evaporating, which includes: into tower temperature degree, and 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, the rich solvent rich in aromatic hydrocarbons and sulfide of extraction distillation tower tower bottom into Entering stripper to be stripped, specific stripping conditions include: that tower top temperature is 80-82 DEG C, and column bottom temperature is 177-179 DEG C, reflux/ Charge-mass ratio is 1；Tower bottom obtains lean solvent, and tower top obtains sulfur-rich aromatic hydrocarbons, after system is run 6 months, obtained lean solvent PH Value about 7, and without olefin polymerization suspended matter in lean solvent, it raffinates oil and is listed in table 4 with the analysis result of sulfur-rich aromatic hydrocarbons；
(2) with 1 step of embodiment (2), loss of octane number 0.2.
Table 4 raffinates oil, the analysis result of the product of sulfur-rich aromatic hydrocarbons
Embodiment 3
It is carried out according to 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 composition is shown in Table 2.After system is run 6 months, what is obtained is poor molten Agent pH value is about 7, and without olefin polymerization suspended matter in lean solvent.The aromatic hydrocarbons of 3 weight %, 3 weight % are only existed in raffinating oil Sulphur, and there are the alkene of 93.6 weight %；There are the aromatic hydrocarbons of 97 weight % in sulfur-rich aromatic hydrocarbons, the sulphur of 97 weight %, 6.4 The alkene of weight %.
Obtain the selective hydrodesulfurization product that sulfur content is 10 μ g/g, loss of octane number 0.2.
Embodiment 4
It is carried out according to method described in embodiment 1, unlike, three are substituted using the N-Methyl pyrrolidone of phase homogenous quantities Glycol monomethyl ether.After system is run 6 months, obtained lean solvent pH value is about 7, and without olefin polymerization suspended matter in lean solvent. The aromatic hydrocarbons of 4.6 weight %, the sulphur of 5 weight % are only existed in raffinating oil, and there are the alkene of 92.4 weight %；Sulfur-rich aromatic hydrocarbons In there are the aromatic hydrocarbons of 95.4 weight %, the sulphur of 95 weight %, the alkene of 7.6 weight %.
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
It is carried out according to method described in embodiment 1, unlike, N- first is substituted using the triethylene glycol monomethyl ether of phase homogenous quantities Base pyrrolidones.After system is run 6 months, obtained lean solvent pH value is about 7, and without olefin polymerization suspended matter in lean solvent. The aromatic hydrocarbons of 4.8 weight %, the sulphur of 4.3 weight % are only existed in raffinating oil, and there are the alkene of 91.9 weight %；Sulfur-rich virtue There are the aromatic hydrocarbons of 95.2 weight %, the sulphur of 95.7 weight %, the alkene of 8.1 weight % 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
It is carried out according to method described in embodiment 1, unlike, tert-butyl is substituted using the diethyl hydroxylamine of phase homogenous quantities Catechol.After system is run 6 months, obtained lean solvent pH value is about 7, occurs a small amount of olefin polymerization in lean solvent and suspends Object.The aromatic hydrocarbons of 3.9 weight %, the sulphur of 4 weight % are only existed in raffinating oil, and there are the alkene of 92.9 weight %；It is sulfur-rich There are the aromatic hydrocarbons of 96.1 weight %, the sulphur of 96 weight %, the alkene of 7.1 weight % in aromatic hydrocarbons.
Compared with Example 1, after system is run 6 months, occur a small amount of olefin polymerization suspended matter in lean solvent, that is, have occurred A little olefin polymerization.
Embodiment 7
It is carried out according to method described in embodiment 1, unlike, corrosion inhibiter is not contained in the extractive distillation solvent, is delayed Lose the sulfolane substitution of agent phase homogenous quantities.After the distribution of sulphur, alkene and aromatic hydrocarbons only has minor change, but system is run 6 months, Obtained lean solvent pH value drops to 5.5, performance decline.
Embodiment 8
It is carried out according to method described in embodiment 1, unlike, the extractive distillation solvent uses described in CN1262264A Using sulfolane as main solvent, ortho-xylene be cosolvent double solvents substitute, using the total weight of the double solvents as base Standard, the content of the sulfolane are 94 weight %, and the content of the ortho-xylene is 6 weight %.There are 21 weights in raffinating oil The aromatic hydrocarbons of % is measured, the sulphur of 43 weight %, there are the alkene of 58.7 weight %；There are the virtues of 79 weight % in sulfur-rich aromatic hydrocarbons Hydrocarbon, the sulphur of 57 weight %, the alkene of 41.3 weight %.Obtain the selective hydrodesulfurization product that sulfur content is 10 μ g/g, octane Value loss 1.4.Contain a large amount of alkene in this method in sulfur-rich aromatic hydrocarbons, and containing a large amount of sulphur in raffinating oil, has 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 above content The race problem of polarity and solvent, there is no high-octane olefin components to be lost to the problems in sulfur-rich aromatic component, therefore It does not need to return washing oil circulation, so low energy consumption；There is no high-octane olefin components to lose for gasoline processing provided by the invention The problems in sulfur-rich aromatic component, therefore the pentane component for adding anti-top light olefin thus is not needed, so device material consumption is low； Due to there is no light component to return washing lotion circulation, eliminates and return washing lotion tower, so device is improved there is no tower, foaming is rushed Device operation stability.Gasoline processing method provided by the invention cooperate preferred extractive distillation solvent can more efficiently by Sulfide and alkene are separated, and the loss of alkene in sweetening process is reduced.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, it can be combined in any appropriate way.
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 also be regarded as the disclosure of the present invention.

Claims (19)

1. a kind of gasoline processing method, which is characterized in that this method comprises: gasoline is stripped distillation processing, wherein described The initial boiling point of gasoline at 40 DEG C or more, and the end point of distillation at 170 DEG C hereinafter, after the extractive distillation handles to obtain rich solvent and purification Gasoline, the extractive distillation processing is so that Aromatic Hydrocarbon in Gasoline and sulfide are dissolved in extractive distillation solvent and form the rich solvent；
It includes: to contact gasoline with extractive distillation solvent under the conditions of extractive distillation that the gasoline, which is stripped distillation processing, It is 60-100 DEG C that the extractive distillation condition, which includes: into tower temperature degree,；Tower top temperature is 70-90 DEG C；Column bottom temperature is 140-180 ℃；Tower top pressure is 0.05-0.1MPa；
The feed weight ratio of the extractive distillation solvent and the gasoline is 1-4:1；
The extractive distillation solvent includes main solvent, cosolvent and olefinic polymerization inhibitor, with the total of the extractive distillation solvent On the basis of weight, the content of the main solvent is 70-99 weight %, and the content of the cosolvent is 0.999-29.9 weight %, The content of the olefinic polymerization inhibitor is 10-1000 μ g/g；
The main solvent is selected from sulfone compound；
The cosolvent is the mixture of N-Methyl pyrrolidone and triethylene glycol monomethyl ether and/or tetraethylene glycol monomethyl ether；
The olefinic polymerization inhibitor is p-tert-Butylcatechol and/or 2- sec-butyl -4,6- dinitrophenol.
2. gasoline processing method according to claim 1, wherein it is 80- that the extractive distillation condition, which includes: into tower temperature degree, 90℃；Tower top temperature is 75-85 DEG C；Column bottom temperature is 155-170 DEG C.
3. gasoline processing method according to claim 1, wherein the charging weight of the extractive distillation solvent and the gasoline Amount is than being 2-3:1.
4. gasoline processing method described in any one of -3 according to claim 1, wherein the content of the main solvent is 80- 95 weight %, the content of the cosolvent are 4.99-19.9 weight %, and the content of the olefinic polymerization inhibitor is 100-1000 μg/g。
5. gasoline processing method described in any one of -3 according to claim 1, wherein the content of the main solvent is 85- 90 weight %, the content of the cosolvent are 9.95-14.9 weight %, and the content of the olefinic polymerization inhibitor is 500-1000 μg/g。
6. gasoline processing method described in any one of -3 according to claim 1, wherein the sulfone compound is selected from ring fourth At least one of sulfone, 3- methyl sulfolane, dimethyl sulfone and diη-propyl sulfone.
7. gasoline processing method according to claim 6, wherein the sulfone compound is sulfolane.
8. gasoline processing method described in any one of -3 according to claim 1, wherein with the N- methyl pyrrole of 100 parts by weight The dosage of pyrrolidone meter, the triethylene glycol monomethyl ether and/or tetraethylene glycol monomethyl ether is 10-200 parts by weight.
9. gasoline processing method according to claim 8, wherein described in terms of the N-Methyl pyrrolidone of 100 parts by weight The dosage of triethylene glycol monomethyl ether and/or tetraethylene glycol monomethyl ether is 50-100 parts by weight.
10. gasoline processing method described in any one of -3 according to claim 1, wherein the extractive distillation solvent also wraps Include corrosion inhibiter, the corrosion inhibiter in monoethanolamine, diethanol amine, (2-hydroxyethyl)methylamine) and N methyldiethanol amine extremely Few one kind.
11. gasoline processing method according to claim 10, wherein on the basis of the total weight of extractive distillation solvent, institute The content for stating corrosion inhibiter is 10-1000 μ g/g.
12. gasoline processing method according to claim 10, wherein on the basis of the total weight of extractive distillation solvent, institute The content for stating corrosion inhibiter is 100-1000 μ g/g.
13. gasoline processing method according to claim 10, wherein on the basis of the total weight of extractive distillation solvent, institute The content for stating corrosion inhibiter is 500-1000 μ g/g.
14. gasoline processing method according to claim 1, wherein the rich solvent is carried out stripping processing, obtains solvent With the aromatic hydrocarbons containing sulfide.
15. gasoline processing method according to claim 14, wherein the aromatic hydrocarbons containing sulfide is carried out selectivity Hydrotreating.
16. gasoline processing method according to claim 15, wherein the method for the selective hydrogenation processing includes: In Under the conditions of selective hydrogenation, the aromatic hydrocarbons containing sulfide and hydrogen are contacted with catalyst for selectively hydrodesulfurizing.
17. gasoline processing method according to claim 16, wherein the selective hydrogenation condition includes: that temperature is 250-600 DEG C, liquid hourly space velocity (LHSV) 1-10h-1, hydrogen to oil volume ratio 200-700, pressure 2-8MPa.
18. gasoline processing method described in any one of -3 according to claim 1, wherein the initial boiling point of the gasoline is 55 DEG C or more, and the end point of distillation is at 150 DEG C or less.
19. gasoline processing method described in any one of -3 according to claim 1, wherein the gasoline contains aromatic hydrocarbons, alkene Hydrocarbon, alkadienes, alkane and sulfide.
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