CN105176581B - A kind of deep desulfurization of gasoline method - Google Patents
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Abstract
The present invention provides a kind of deep desulfurization of gasoline method, comprises the steps：Gasoline stocks are cut into into light fraction and heavy distillat；Liquid-liquid extraction is carried out to the light fraction, the oil of the light fraction raffinate containing alkene and the light fraction extraction oil containing sulfide and aromatic hydrocarbons is obtained；Extractive distillation is carried out to the heavy distillat, the oil of the heavy distillat raffinate containing alkene and the heavy distillat extraction oil containing sulfide and aromatic hydrocarbons is obtained；Selective hydrodesulfurization is carried out to the light fraction extraction oil and heavy distillat extraction oil, sweetened distillate is obtained；By light fraction raffinate oil, heavy distillat raffinate oil and sweetened distillate mixing, sulfur-free gasoline is obtained；Wherein, the light fraction and the cutting temperature of heavy distillat are 80 120 DEG C.The deep desulfurization of gasoline method of the present invention can also be substantially reduced gasoline products loss of octane number while deep desulfuration is realized and desulfurization load is greatly reduced, and product yield ＞ 95%.
Description
Technical field
The present invention relates to a kind of gasoline desulfating method, more particularly to a kind of deep desulfurization of gasoline method.
Background technology
With pay attention to day by day of the people to environmental conservation, the requirement of the new environmental regulation of countries in the world to quality of gasoline is further
Strictly.For example, the state V motor petrol standard that China will implement on January 1st, 2017 will require olefin(e) centent 25% with
Under, sulfur content is in below 10ppm；The sulfur limit value of EPA (EPA) regulation gasoline is 30ppm (TierIl)；European requirements
The sulfur content of gasoline should be less than 50ppm (Europe IV discharge standards).Therefore, it is necessary to carry out deep desulfuration to gasoline be only possible to reach
Related request.
Impact of the absorption desulfurization in gasoline stocks are removed while sulfide to gasoline products octane number is less, therefore is
Relatively one of sulfur method of tool potentiality, also has more report at present.For example, by Black＆Veatch Pritchard Inc. with
The IRVAD technologies that Alcoa Industrial Chemicals are developed jointly adopt multistage fluidized bed suction type, using oxidation
Aluminum matrix selectivity solid absorbent treatment liquid hydro carbons, in adsorption process, adsorbent adverse current is contacted with liquid hydrocarbon, is made
Used adsorbent is inversely regenerated with regeneration thermal current (such as hydrogen) reaction.The desulfurization degree of the technology up to 90% with
On, but the adsorbent selectivity is not high, absorption Sulfur capacity is limited, and regenerative process is relative complex.
The S-Zorb techniques of Phillips oil companies research and development are that a kind of specific adsorbent is adopted under conditions of hydrogen is faced
Carry out desulfurization, the adsorbent using Zinc Oxide, silicon dioxide, aluminium oxide as carrier and the metal component such as load C o, Ni, Cu,
Which can adsorb the sulphur atom in sulfide, be allowed to retain on the sorbent, and the hydrocarbon moieties of sulfide are then discharged back into
In process-stream, so as to realize sweetening process.The technique does not produce H during the course of the reaction2S, so as to avoid H2S is with alkene again
Secondary response generates mercaptan.However, the desulfurization technical matters operating condition is relatively harsh, the temperature of desulphurization reaction is 343-413 DEG C,
Pressure is 2.5-2.9MPa.
Although above-mentioned desulfurizing method by adsorption can reduce the loss of gasoline products octane number, but operation is relative complex, and
And desulfurization depth is not enough, is generally difficult to gasoline desulfurization to below 10ppm.Further, since gasolene ingredient is relative complex, and certain
It is a little to produce competitive Adsorption into branch in absorption sweetening process, so as to cause to adsorb desulfuration efficiency reduction, adsorbent service life
The defects such as shortening.
Hydrodesulfurization is to remove the maximally efficient method of sulfide in petrol.Also, in order to avoid in hydrodesulfurization
The compositions such as the alkene in gasoline are saturated and cause loss of octane number, and industrially generally first gasoline stocks are distilled, so as to
Two or more fraction is cut into, wherein desulfurization is carried out in non-hydrodesulfurization mode to light fraction, so as to avoid octane number from damaging
Lose；Desulfurization is carried out in selective hydrodesulfurization mode generally to heavy distillat, so as to realize deep desulfuration.
For example, the FCC gasoline selective hydrogenation desulfurization process (RSDS- that Research Institute of Petro-Chemical Engineering was developed in calendar year 2001
I), first under 90 DEG C of cutting temperature by FCC gasoline cut into gently, heavy distillat, alkali density removal of mercaptans is carried out to light fraction then,
And selective hydrodesulfurization is carried out to heavy distillat using major catalyst RSDS- I and protective agent RGO-2；And above-mentioned technique is being entered
The improved second filial generation FCC gasoline selective hydrodesulfurization technology (RSDS- II) of row is by cutting, the cut point of heavy distillat is down to 70 DEG C,
And the second filial generation hydrogenation catalyst RSDS-21, RSDS-22 are adopted in heavy distillat selective hydrodesulfurization part.
The Prime-G+ techniques of (IFP) Axens companies of IFP exploitation, are hydrogenated with advance using full fraction, weight
Gasoline cuts the technological process with heavy distillat selective hydrodesulfurization, and cutting temperature is set to by which according to the desired value of sulfur content
93-149 DEG C, and during full fraction is hydrogenated with advance, act on forming height by trechmannite compound and alkadienes using HR845 catalyst
The sulfide of boiling point, therefore alkene is not saturated；Additionally, HR806 and HR841 is adopted in heavy distillat selective hydrodesulfurization
Two kinds of catalyst are carried out, and are operated more flexible.
The OCT-M techniques of Sinopec Fushun Petrochemical Research Institute exploitation are under 90 DEG C of cutting temperature by FCC gasoline
Be cut into it is light, weigh two fractions, wherein carry out removal of mercaptans to light fraction, to heavy distillat using FGH-20/FGH-11 combination catalysis
Agent carries out selective hydrodesulfurization.
The HDDO series that extra large Shuande is developed takes off diene hydrocarbon catalyst, HDOS series deep hydrodesulfurizationof catalyst, HDMS
Serial mercaptan-eliminating catalyst and corresponding FCC gasoline selective hydrogenation desulfurization process (CDOS), first by FCC gasoline compared with low temperature
Degree, carry out dialkene removal reaction under hydro condition, then by FCC gasoline be cut into gently, weigh two components, and heavy distillat is carried out
Deep hydrodesulfurizationof, the heavy distillat after hydrogenation are reconciled with light fraction and obtain low sulfur clean gasoline.
Said method is universal to the cutting temperature of gasoline stocks higher, and in cutting formed light fraction, sulfur content is relatively
Greatly, only relying on the non-hydrodesulfurization mode such as removal of mercaptans is difficult to make the sulfur content of light fraction to be down to below 10ppm, in production sulfur content
During gasoline products less than 10ppm, most of light fraction remains a need for hydrodesulfurization, thus the loss of octane number amount of full distillation gasoline
Higher (being for example up to 3.0-4.0).Although additionally, above-mentioned hydrodesulfurization mode substantially reduces can the sulfur content of gasoline, so
And there is investment and operating cost height, while sulfide is removed it is saturated substantial amounts of alkene, has both increased hydrogen consumption, also makes
The octane number of gasoline is greatly reduced.Therefore, expect that one kind reduces gasoline products loss of octane number while deep desulfuration is realized
Gasoline desulfating method.
The content of the invention
The present invention provides a kind of deep desulfurization of gasoline method, for solving sulfur method complex operation of the prior art,
And it is difficult to while realizing deep desulfuration and reducing the technological deficiencies such as loss of octane number.
The present invention provides a kind of deep desulfurization of gasoline method, comprises the steps：
Gasoline stocks are cut into into light fraction and heavy distillat；
Liquid-liquid extraction is carried out to the light fraction, the oil of the light fraction raffinate containing alkene is obtained and containing sulfide and aromatic hydrocarbons
Light fraction extraction oil；
Extractive distillation is carried out to the heavy distillat, the oil of the heavy distillat raffinate containing alkene is obtained and containing sulfide and aromatic hydrocarbons
Heavy distillat extraction oil；
Selective hydrodesulfurization is carried out to the light fraction extraction oil and heavy distillat extraction oil, sweetened distillate is obtained；
By light fraction raffinate oil, heavy distillat raffinate oil and sweetened distillate mixing, sulfur-free gasoline is obtained；
Wherein, the light fraction and the cutting temperature of heavy distillat are 80-120 DEG C.
In the present invention, the gasoline stocks can be catalytically cracked gasoline etc..It is described cutting be by gasoline stocks according to
Boiling range be cut into from low to high gently, weigh two fractions；The cutting can be carried out using this area conventional method, for example, be distilled
Deng.Further, the light fraction and the cutting temperature of heavy distillat are 90-110 DEG C.
It has been investigated that：The distribution of sulfide in catalytically cracked gasoline has the characteristics that：1st, (boiling point is usual below five for carbon
40 DEG C of ＜) fraction in, mainly contain mercaptan sulfur；2nd, thiophenic sulfur is mainly contained in carbon six (boiling point is usually 40-80 DEG C) fraction；
3rd, methylthiophene sulfur is mainly contained in carbon seven (boiling point is usually 70-110 DEG C) fraction；4th, the sulfide in the fraction of carbon more than seven
Based on alkylthrophene and thioether sulfur.
Study based on more than, gasoline stocks are cut into light fraction and double distilled using specific cutting temperature by the present inventor
Point；Wherein：
1st, contain substantial amounts of alkene in above-mentioned light fraction, and contain part aromatic hydrocarbons, alkane and cycloalkane, sulfide is main
For thiophene, methylthiophene, alkylthrophene etc.；For thiophene and methylthiophene in above-mentioned light fraction, the present invention is extracted using liquid liquid
The mode of taking easily can be removed, and in above-mentioned light fraction, some are relatively low with the extracting selectivity of hydrocarbon and boiling point is higher
Sulfide, during liquid-liquid extraction, solvent reclamation is temperature required higher, and sulfide can be caused to increase with alkene rubber, therefore is difficult to realize
The removing of these sulfide.In consideration of it, the present invention carries out selective hydrodesulfurization to the extraction oil after liquid-liquid extraction, so as to realize
Deep desulfuration；Simultaneously as Liquid-liquid Extraction Processes by the sulfide in light fraction and most of aromatic hydrocarbons extraction out so as to
Alkane, alkene are separated with cycloalkane, therefore the alkene in subsequent selective hydrodesulfurization in light fraction will not be saturated, so as to
The loss of octane number of gasoline products can be avoided, and total desulfurization load can also be greatly lowered.
2nd, in above-mentioned heavy distillat, olefin(e) centent is relatively low and aromatic hydrocarbons and sulfide content are higher, therefore the present invention is first using extraction
By the separation of olefins in heavy distillat out, the subsequently heavy distillat to having separated alkene carries out selective hydrodesulfurization, both may be used for distillation
To meet deep desulfuration, while the loss of octane number of gasoline products can also be avoided.
The present invention is proposed based on the studies above achievement, which can also be substantially reduced gasoline while deep desulfuration is realized
Product loss of octane number.
In the present invention, the purpose of liquid-liquid extraction is by the alkene in light fraction, alkane, cycloalkane etc. by organic solvent
Composition and sulfide, most of aromatic hydrocarbons and cyclenes etc. other compositions are separated, so as to avoid the unsaturated hydrocarbons such as alkene subsequently selected
Property hydrodesulfurization in be saturated and cause gasoline products octane number reduce.Those skilled in the art can according to the purpose come
Select suitable organic solvent and liquid-liquid extraction process.
In one embodiment, the liquid-liquid extraction includes：
The light fraction is made to enter from extraction tower middle and lower part, organic solvent is entered from the top of extraction tower, and from extraction tower
Bottom reflux injection C5 alkane；Wherein, it is 55-100 DEG C to control to extract column overhead temperatures, and column bottom temperature is 40-80 DEG C, tower
Top absolute pressure is 0.2-0.7MPa, and the organic solvent and light fraction charge ratio (volume ratio) are 1.0-5.0, C5 alkane with it is light
Fraction charge ratio (volume ratio) is 0.1-0.5；
Extraction tower tower top effluent is collected, the light fraction raffinate containing alkene is obtained；Extraction tower bottom stream is collected,
Obtain the light fraction extract containing sulfide and aromatic hydrocarbons；
The light fraction raffinate is washed, the oil of the light fraction raffinate containing alkene is obtained；
Organic solvent and C5 alkane in the light fraction extract is separated, is obtained containing sulfide and aromatic hydrocarbons
Light fraction extraction oil.
Wherein, the organic solvent can be selected from diethylene glycol, 2,2'-ethylenedioxybis(ethanol)., tetraethylene glycol (TEG), dimethyl sulfoxide, sulfolane, N- formyls
One or more in morpholine, N-Methyl pyrrolidone, Polyethylene Glycol and Allyl carbonate is further 2,2'-ethylenedioxybis(ethanol)., tetraethylene glycol (TEG)
With one or more in sulfolane；Water content (i.e. the weight content of the water) ＜ 1.0% for controlling the organic solvent is favourable
, can be further 0.6-0.8%.
In the present invention, the C5 alkane is added to be to increase separation efficiency；In one embodiment, C5 alkane is optional
One or two from pentane and isopentane.
Further, it is 65-80 DEG C to control to extract column overhead temperatures, and column bottom temperature is 50-60 DEG C, and absolute pressure of top of the tower is
0.5-0.6MPa, the organic solvent are 2.0-3.0 with light fraction charge ratio, and C5 alkane is 0.2-0.3 with light fraction charge ratio.
Additionally, being to remove organic solvent therein to the purpose washed by the light fraction raffinate；Described in carrying out
During washing, the consumption (amount based on light fraction raffinate) that can control water is 1-10%, for example, 2-4%.
In one embodiment, the organic solvent and C5 alkane in the light fraction extract is separated, can be wrapped
Include：
Make the light fraction extract enter extractive distillation top of tower, collect extraction distillation tower overhead effluent, reclaim
To C5 alkane, extraction distillation tower bottom stream is collected, obtain containing light sulfur-rich component (dilute containing sulfide, aromatic hydrocarbons, ring), have
First mixture of machine solvent and water；Wherein, extraction distillation tower absolute pressure is controlled for 0.15-0.3MPa, extraction distillation tower tower
Bottom temperature is 150-180 DEG C；
First mixture is entered in the middle part of recovery tower, collect recovery tower tower top effluent, obtain containing light sulfur-rich group
Divide the second mixture with water, collect recovery tower bottom stream, recovery obtains organic solvent；Wherein, control recovery tower absolute
Pressure is 0.015-0.05MPa, and recovery tower column bottom temperature is 130-180 DEG C；
Oil-water separation is carried out after second mixture is condensed, water and the extraction of the light fraction containing sulfide and aromatic hydrocarbons is obtained
Take oil (i.e. light sulfur-rich component).
Further, reclaim the C5 alkane that obtains it is condensed after may return to the extracting tower bottom reflux and followed
Ring is utilized；The water part for obtaining can return to the recovery column overhead, and another part is for the water to the light fraction raffinate
Wash；The organic solvent that recovery is obtained can return to recycle at the top of the extraction tower Jing after heat exchange.
Further；Extraction distillation tower absolute pressure can be 0.2MPa, and extraction distillation tower column bottom temperature can be 160
℃；Recovery tower absolute pressure can be 0.035-0.045MPa, and recovery tower column bottom temperature can be 165-175 DEG C.
In the present invention, the purpose of extractive distillation is by the alkene in heavy distillat, alkane, cycloalkane etc. by organic solvent
Composition and sulfide, most of aromatic hydrocarbons and cyclenes etc. other compositions are separated, so as to avoid the unsaturated hydrocarbons such as alkene subsequently selected
Property hydrodesulfurization in be saturated and cause gasoline products octane number reduce；Additionally, in extractive distillation, additionally it is possible to using steaming
The separation for evaporating to realize different component.Those skilled in the art can select suitable organic solvent and extraction according to the purpose
Distillation technique.
In one embodiment, the extractive distillation includes：
The heavy distillat is made to enter from extraction distillation column middle and lower part, organic solvent is entered from extraction distillation column top；Wherein,
The theoretical cam curve for controlling extraction distillation column is 25-45, and tower top temperature is 70-110 DEG C, and column bottom temperature is 150-190 DEG C, tower top
Absolute pressure is 0.1-0.5MPa, and organic solvent is 1.0-5.0 with the charge ratio (i.e. volume ratio) of heavy distillat, and reflux ratio is 0.1-
4.0；
Extraction distillation column tower top effluent is collected, the heavy distillat raffinate containing alkene is obtained；Collect extraction distillation column tower
Bottom effluent, obtains the heavy distillat extract containing sulfide and aromatic hydrocarbons；
The heavy distillat raffinate is washed, the oil of the heavy distillat raffinate containing alkene is obtained；
Organic solvent in the heavy distillat extract is separated, the extraction of the heavy distillat containing sulfide and aromatic hydrocarbons is obtained
Take oil.
Under the conditions of above-mentioned extractive distillation, the alkene in heavy distillat can reach more than 90% with the separation degree of aromatic hydrocarbons, point
It is good from effect.Wherein, the Jing multi-stage countercurrents in extraction distillation column are contacted with organic solvent for heavy distillat, and heavy distillat is from extraction distillation column
When top is flowed out, partial vulcanization thing, most of composition such as aromatic hydrocarbons and cyclenes are extracted removing, so as to formed containing alkene, alkane,
The heavy distillat raffinate of the compositions such as cycloalkane, after the condensed device condensation of heavy distillat raffinate, part backflow, to maintain extraction to steam
The heat balance of Ta Tanei is evaporated, and ensures that stablizing for extractive distillation is carried out and product separation precision, wherein reflux ratio (is used
Volume ratio between the heavy distillat raffinate and the heavy distillat raffinate that distillates of backflow) for 0.1-4.0；Extract in heavy distillat
Sulfide and the solvent of aromatic hydrocarbons flow out from bottom of towe, form heavy distillat extract, wherein (including sulfuration containing the sulfur-rich component of weight
Thing, aromatic hydrocarbons, cyclenes etc.), water and solvent.
In above-mentioned extractive distillation, the organic solvent can be selected from diethylene glycol, 2,2'-ethylenedioxybis(ethanol)., tetraethylene glycol (TEG), dimethyl sulfoxide, ring
One or more in fourth sulfone, N- N-formyl morpholine Ns, N-Methyl pyrrolidone, Polyethylene Glycol and Allyl carbonate, is further three
The mixed solvent of one or more in glycol, tetraethylene glycol (TEG) and sulfolane, such as 2,2'-ethylenedioxybis(ethanol). and sulfolane, its sulfolan and three
The volume ratio of glycol can be (6-9)：(4-1)；Control water content (i.e. the weight content of the water) ＜ 1.0% of the organic solvent
It is favourable, can is further 0.6-0.8%.
Further, the theoretical cam curve of the extraction distillation column is 30-35, and tower top temperature is 80-100 DEG C, bottom of towe temperature
Spend for 160-180 DEG C, absolute pressure of top of the tower is 0.3-0.4MPa, and organic solvent is 2.0-3.0 with the charge ratio of heavy distillat, is flowed back
Than for 0.2-2.0.
Additionally, being to remove organic solvent therein to the purpose washed by the heavy distillat raffinate；In washing, can
To control the consumption (amount based on heavy distillat raffinate) of water as 1-10%, for example, 2-4%.
In one embodiment, the organic solvent in the heavy distillat extract is separated, can be included：
The heavy distillat extract is made to enter from solvent recovery tower middle and upper part, steam (water vapour) is from solvent recovery tower bottom
Into；Wherein, the theoretical cam curve of the solvent recovery tower is 10-30, and tower top temperature is 50-100 DEG C, and column bottom temperature is 150-
200 DEG C, absolute pressure of top of the tower is 0.03-0.07MPa, and steam is (0.1- with the charge ratio (i.e. mass ratio) of heavy distillat extract
0.5)：100, reflux ratio is 0.2-4.0.
In above-mentioned solvent recovery tower, the sulfur-rich component of weight is separated with solvent, and wherein solvent can enter from after bottom of towe outflow
Utilization is circulated in entering extraction distillation column；The sulfur-rich component of weight and steam are flowed out from tower top, it is condensed after, using usual manner
(such as evacuation) is dehydrated, and obtains the heavy distillat extraction oil containing sulfide and aromatic hydrocarbons (weighing sulfur-rich component), heavy distillat extraction
Oil subsequently carries out selective hydrodesulfurization, and the water of part removing is used to flow back, to maintain the heat in solvent recovery tower tower to put down
Weighing apparatus, it is ensured that separation process is stably carried out, wherein reflux ratio (i.e. for the volume ratio between the water for flowing back and the water for distillating) are
0.2-4.0, remaining water is for the washing to heavy distillat raffinate.
Further, the theoretical cam curve of the solvent recovery tower is 15-25, and tower top temperature is 60-80 DEG C, column bottom temperature
For 165-185 DEG C, absolute pressure of top of the tower is 0.04-0.06MPa, and steam is (0.3-0.4) with the charge ratio of heavy distillat extract：
100, reflux ratio is 0.5-2.0.
In one embodiment, the extractive distillation can include：
Heavy distillat is made to enter from extraction distillation column middle and lower part, organic solvent is entered from extraction distillation column top, extractive distillation
Column overhead effluent forms the heavy distillat raffinate containing alkene, and extraction distillation column bottom stream is formed containing sulfide and virtue
The heavy distillat extract of hydrocarbon；
Above-mentioned heavy distillat raffinate is washed in water scrubber, obtain the oil of the heavy distillat raffinate containing alkene；
Above-mentioned heavy distillat extract is made to enter from solvent recovery tower middle and upper part, steam is entered from solvent recovery tower bottom, molten
Agent recovery tower bottom stream forms organic solvent, and solvent recovery tower tower top effluent forms the mixing of the sulfur-rich component of weight and water
Thing；
Said mixture is separated in sulfur-rich oil tank, form the heavy distillat extraction oil containing sulfide and aromatic hydrocarbons
(weighing sulfur-rich component) and water, a water part for formation are back to solvent recovery tower, and another part is back to water scrubber.
It is possible to further make the water outlet of water scrubber bottom of towe be stripped into water stripper tower top, water stripper tower top stream
Go out thing (micro-content organism being stripped off from water) subsequently to be separated into return tank, water stripper bottom stream
(i.e. solvent-laden water) subsequently can carry out solvent recovery into solvent recovery tower bottom of towe.Water stripper bottom is typically provided with reboiling
Device, its stripped vapor for producing can be used as the steam source of solvent recovery tower.
In return tank, Organic substance can be separated (such as evacuation) by conventional methods with water, and that what is isolated is organic
Thing subsequently enters extraction distillation column bottom of towe, and the water isolated can be entered into water stripper tower top after being merged with water scrubber bottom of towe water outlet
Row stripping.
Furthermore, it is possible to make a part of organic solvent of solvent recovery tower bottom of towe as the heat of water stripper bottom reboiler
Source, is then exchanged heat with the extract of extraction distillation column bottom of towe, is returned again to extractive distillation column overhead；Another part organic solvent can
Into in the middle part of solvent regeneration tower, while the steam that water stripper bottom of towe is produced enters water-filling steaming into solvent reclamation tower bottom to solvent
Steam distillation, solvent regeneration tower tower top effluent enter solvent recovery tower bottom of towe.
Aforesaid way can not only be circulated utilization to organic solvent, additionally it is possible to ensure making for whole system circulating solvent
With performance, while being conducive to economizing on resources and the energy.
In the present invention, the conventional method of this area can be adopted to carry out the selective hydrodesulfurization, such as S-zorb,
The selective desulfurization such as RSDS, OCT-M, Prime-G+, CODS method or other selectivity process for deep desulphurization, or it is above-mentioned
The combination of the two or more methods in method.
In one embodiment, selecting with hydrogen after can merging the light fraction extraction oil and heavy distillat extraction oil
The selective hydrodesulfurization is carried out in the presence of property Hydrobon catalyst；Wherein, control the selective hydrodesulfurization
Temperature is 200-300 DEG C, and pressure is 1.5-2.5MPa, and volume space velocity is 1-5h-1, hydrogen to oil volume ratio is 400-600.
The present invention does not make considered critical to the catalyst for selectively hydrodesulfurizing, can be the conventional catalysis in this area
Agent.In one embodiment, the catalyst for selectively hydrodesulfurizing can be the Chinese special of Publication No. CN104673376A
Catalyst disclosed in profit.Specifically, the catalyst for selectively hydrodesulfurizing can be by carrier loaded active metal components
And obtain；Wherein, the carrier can be molecular sieve (such as X-type, Y types or ZSM-5 types) or metal-oxide (such as three oxidations
Two aluminum), the active metal can be able to be 5-20% including Co and Mo, Co and Mo total load amount on the carrier.More
Further, the mass ratio of the Co and Mo of supported on carriers is (0.2-0.6)：1.
The deep desulfurization of gasoline method of the present invention, can also further to light fraction raffinate oil and heavy distillat raffinate oil
Carry out absorption desulfurization.Specifically, absorption desulfurization can be carried out to light fraction raffinate oil and heavy distillat raffinate oil respectively, also may be used
Merging into carry out absorption desulfurization to the miscella after miscella light fraction raffinate oil and heavy distillat raffinate oil.
In one embodiment, deep desulfurization of gasoline method of the invention can include：
Absorption desulfurization is carried out to the light fraction raffinate oil, light fraction absorption sweet oil and the sulfur-rich oil of light fraction is obtained；
Absorption desulfurization is carried out to the heavy distillat raffinate oil, heavy distillat absorption sweet oil and the sulfur-rich oil of heavy distillat is obtained；
Sweet oil, heavy distillat absorption sweet oil and sweetened distillate mixing are adsorbed in the light fraction, desulfurization vapour is obtained
Oil.
Specifically, it is possible to use desulfuration adsorbent carries out the absorption desulfurization, the desulfuration adsorbent to being adopted of the invention
Do not make considered critical, can be the conventional desulfuration adsorbent in this area.
In one embodiment, the desulfuration adsorbent can be Publication No. CN104667861A Chinese patent in institute
Disclosed desulfuration adsorbent.Specifically, the desulfuration adsorbent by the molecular sieve and activated carbon of respectively Jing alkali process as compound
Carrier loaded active metal components and obtain；Wherein, the active metal is in periodic chart IA, VIII, IB, IIB and group vib
One or more element, load capacity of the active metal on complex carrier be 2-30%, preferably 5-25%, further
Preferably 5-20%.
Further, in the complex carrier, molecular sieve is (20-80) with the mass ratio of activated carbon:(80-20), preferably
For (20-60):(80-40)；Wherein, the type of molecular sieve can be X-type, Y types or ZSM-5 types, the present invention to adopt X-type with
, without strict restriction, the specific surface of activated carbon generally can be 1000m for type ZSM 5 molecular sieve and activated carbon2/ g or so；The Y types
The framework silicon-aluminum atomic ratio of molecular sieve is not less than 3.0 (xrd method measure).
Additionally, at least 2 kinds in Ni, Fe, Ag, Co, Mo, Zn and K of the active metal.Wherein, Ni is in compound load
Load capacity on body can be 10-30%；Load capacity of the Fe on complex carrier can be 5-15%；Loads of the Ag on complex carrier
Amount can be 5-10%；Load capacity of the Co on complex carrier can be 5-10%；Load capacity of the Mo on complex carrier can be 5-
10%；Load capacity of the Zn on complex carrier can be 5-15%；Load capacity of the K on complex carrier can be 5-15%.The load
Measure as the load capacity on each comfortable complex carrier of every kind of active metal.
Further, load capacity of the active metal on complex carrier be 2-30%, preferably 5-25%, further
Preferably 5-20%.When loading two or more active metals on complex carrier, total load of the load capacity for active metal
Amount.
In one embodiment, the active metal is K and Ni；Further, load capacity of the K on complex carrier is 5-
The load capacity of 15%, Ni on complex carrier is 10-25%；Further, the mass ratio of the K for loading on complex carrier and Ni
For (0.2-0.5)：1.
In another embodiment, the active metal is Zn and Fe；Further, load capacity of the Zn on complex carrier
For 5-15%, load capacity of the Fe on complex carrier is 8-15%；Further, the matter of the Zn for loading on complex carrier and Fe
Amount is than being (0.5-1)：1.
Above-mentioned desulfuration adsorbent can refer to the method disclosed in the Chinese patent of Publication No. CN104667861A and carry out
Prepare and regenerate.
Further, it is described absorption desulfurization be to be carried out using fixed bed atmospheric pressure, and control adsorb desulfurization temperature be 20-
100 DEG C, the oily flow velocity of light fraction raffinate oil or heavy distillat raffinate is 0.3-1mL/min.The absorption desulfurization of the present invention is to light fraction
Raffinate oil and heavy distillat raffinate oil are carried out, and as aromatic hydrocarbons is eliminated in each raffinate oil, therefore can be prevented effectively from aromatic hydrocarbons in absorption
Caused competitive Adsorption in sweetening process, desulfuration efficiency may be up to 100%, and also can extend the use longevity of adsorbent
Life.
Further, it is also possible to further oil sulfur-rich to the light fraction and the sulfur-rich oil of heavy distillat carry out selective hydrodesulfurization,
For example can be by the light fraction sulfur-rich oil and heavy distillat is sulfur-rich oily merges with the light fraction extraction oil and heavy distillat extraction oil
After carry out selective hydrodesulfurization.
The enforcement of the present invention, at least has the advantage that：
1st, deep desulfurization of gasoline method of the invention, based on to the composition such as sulfur, alkene and aromatic hydrocarbons distribution in gasoline stocks
Gasoline stocks first under specific cutting temperature are cut into light fraction and heavy distillat, subsequently carry out liquid liquid to light fraction by research
Extraction, carries out extractive distillation to heavy distillat, the compositions such as alkene is separated from each fraction while partial desulfurization, follow-up right
In each fraction, other compositions not only do not result in a large amount of losses of octane number during carrying out selective hydrodesulfurization, moreover it is possible to significantly
Degree ground reduces total desulfurization load.
2nd, gasoline stocks are not only cut into light fraction and weight according to cutting temperature by deep desulfurization of gasoline method of the invention
Fraction, divides to its component herein in connection with light fraction and the respective composition characteristic of heavy distillat, and to each component after division
Targetedly desulfurization is carried out, whole sweetening process is more fine and efficient.
3rd, deep desulfurization of gasoline method of the invention, by Optimized Extraction distillation technique such that it is able in making heavy distillat
Alkene and aromatic hydrocarbons high separation, separating degree is up to more than 90%；Also, alkene is separated to also help with aromatic hydrocarbons and is avoided follow-up
Caused competitive Adsorption in absorption sweetening process, absorption desulfuration efficiency may be up to 100%, and the service life of adsorbent is prolonged significantly
It is long.
4th, in the sulfur-free gasoline produced by deep desulfurization of gasoline method of the invention, sulfur content reaches below 10ppm, octane
Value is not only almost lost and is even slightly improved, in addition product yield ＞ 95%, and the quality of sulfur-free gasoline product is high.
Description of the drawings
Process charts of the Fig. 1 for the deep desulfurization of gasoline method of the embodiment of the present invention 1；
Process charts of the Fig. 2 for the deep desulfurization of gasoline method of the embodiment of the present invention 2；
Process charts of the Fig. 3 for extractive distillation in the deep desulfurization of gasoline method of one embodiment of the invention.
Specific embodiment
Accompanying drawing and enforcement to make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the present invention
Example, is clearly and completely described to the technical scheme in the embodiment of the present invention, it is clear that described embodiment is the present invention
A part of embodiment, rather than the embodiment of whole.Based on the embodiment in the present invention, those of ordinary skill in the art are not having
The every other embodiment obtained under the premise of making creative work, belongs to the scope of protection of the invention.
Embodiment 1
1st, prepare catalyst for selectively hydrodesulfurizing
CoSO is adopted first4Solution carries out incipient impregnation, scrubbed, dry and roasting to type ZSM 5 molecular sieve (carrier)
Afterwards, then using (NH4)6Mo7O24.4H2The aqueous solution of O is to impregnating CoSO4The type ZSM 5 molecular sieve of solution carries out equal-volume leaching
Stain, after scrubbed, dry and roasting, is obtained catalyst for selectively hydrodesulfurizing.
Total specific surface of the catalyst for selectively hydrodesulfurizing of above-mentioned preparation is 168m2/ g or so, total pore volume is
The load capacity of 0.378mL/g or so, Co on carrier is about load capacity of 7%, the Mo on carrier and is about 10%, supported on carriers
The mass ratio of Co and Mo be 0.7：1.
2nd, gasoline desulfurization
The catalytic gasoline produced through catalytic cracking with grand celebration atmospheric residue as raw material (its composition is shown in Table 1), to the vapour
Oily raw material carries out the technological process of desulfurization as shown in figures 1 and 3.
2.1 gasoline stocks cut
Above-mentioned gasoline stocks are cut into into light fraction and heavy distillat, wherein gently, the cutting temperature of heavy distillat be 100 DEG C, i.e.,：
Fraction of the light fraction for 100 DEG C of ＜, double distilled are divided into the fraction of 100 DEG C of ＞.
2.2 liquid-liquid extraction
Light fraction is made to enter from extraction tower middle and lower part, sulfolane (organic solvent) entered from the top of extraction tower, and from taking out
Stripper bottom reflux injection isopentane (C5 alkane), it is 65 DEG C to control to extract column overhead temperatures, and column bottom temperature is 50 DEG C, tower
Top absolute pressure is 0.5MPa, and sulfolane is 2.0 with light fraction charge ratio, and isopentane is 0.2 with light fraction charge ratio；Collection is taken out
Stripper overhead effluent, obtains the light fraction raffinate containing alkene；Extraction tower bottom stream is collected, is obtained containing sulfide
And the light fraction extract of aromatic hydrocarbons.
Above-mentioned light fraction raffinate subsequently enters water scrubber and is washed to remove organic solvent therein, washes column overhead
Effluent forms the oil of the light fraction raffinate containing alkene, and water scrubber bottom stream forms water (washing water)；When being washed,
The consumption (amount based on light fraction raffinate) of control water is 3% or so.
Above-mentioned light fraction extract subsequently enters extractive distillation top of tower, controls extraction distillation tower absolute pressure and is
0.2MPa, extraction distillation tower column bottom temperature are 160 DEG C, collect extraction distillation tower overhead effluent, and recovery obtains C5 alkane, collects
Extraction distillation tower bottom stream, obtains containing light sulfur-rich component (containing the dilute and a small amount of water of sulfide, aromatic hydrocarbons, ring), organic
First mixture of solvent and water.May return to extract tower bottom reflux after the C5 alkane that obtains of recovery is condensed and followed
Ring is utilized.
Make above-mentioned first mixture enter in the middle part of recovery tower, recovery tower absolute pressure is controlled for 0.035MPa, recovery tower tower
Bottom temperature is 165 DEG C, collects recovery tower tower top effluent, obtains the second mixture containing light sulfur-rich component and water, collects back
Tower bottom stream is received, recovery obtains organic solvent.The organic solvent that recovery is obtained Jing after heat exchange can return to follow at the top of extraction tower
Ring is used.
Oil-water separation is carried out after above-mentioned second mixture is condensed, water and the extraction of the light fraction containing sulfide and aromatic hydrocarbons is obtained
Take oil (i.e. light sulfur-rich component).The water part for obtaining can return to reclaim column overhead, and another part can be used for light fraction raffinate
The washing of thing.
2.3 extractive distillation
The technological process of extractive distillation is as shown in figure 3, specifically include：
Above-mentioned heavy distillat is made to enter from 101 middle and lower part of extraction distillation column, organic solvent enters from 101 top of extraction distillation column
Enter, the Jing multi-stage countercurrents in extraction distillation column 101 are contacted with organic solvent for heavy distillat, carry out desulfurizing and dearomatizing；Wherein, You Jirong
Agent is the double solventss mixed by sulfolane and 2,2'-ethylenedioxybis(ethanol)., and double solventss sulfolan is 8 with the volume ratio of 2,2'-ethylenedioxybis(ethanol).：2,
Water content ＜ 1.0% of double solventss, 101 theoretical cam curve of extraction distillation column are 35, and 101 tower top temperature of extraction distillation column
For 75 DEG C or so, column bottom temperature is 160 DEG C or so, and absolute pressure of top of the tower is 0.3MPa or so, and organic solvent is entered with heavy distillat
Material is than being 3.0 or so.
The gasoline fraction of Jing desulfurizing and dearomatizings is drawn from 101 tower top of extraction distillation column, obtains the extraction of the heavy distillat containing alkene
Excess, the part backflow of heavy distillat raffinate, wherein reflux ratio are 0.6 or so；And extracted the rich solvent of sulfide and aromatic hydrocarbons
Draw from the bottom of extraction distillation column 101, obtain heavy distillat extract, its contain the sulfur-rich component of weight (include sulfide, aromatic hydrocarbons,
Cyclenes etc.), water and organic solvent.In extraction distillation column 101, alkene reaches 90% with the separating degree of aromatic hydrocarbons.
Above-mentioned heavy distillat raffinate subsequently enters water scrubber 102 and is washed to remove organic solvent therein, water scrubber
Tower top effluent forms the oil of the heavy distillat raffinate containing alkene, and 102 bottom stream of water scrubber forms water (washing water)；Carry out
During washing, the consumption (amount based on heavy distillat raffinate) for controlling water is 3% or so.
Above-mentioned heavy distillat extract subsequently enters the middle part of solvent recovery tower 103, is simultaneously from the stripping of water stripper 105
Steam enters into 103 bottom of solvent recovery tower and carries out the vacuum distillation operation of rough vacuum, to reduce column bottom temperature, solvent recovery
103 bottom stream of tower forms organic solvent, and its water content is 0.6-0.65%, and tower top effluent forms the sulfur-rich component of weight and water
Mixture；Wherein, the theoretical cam curve of solvent recovery tower 103 is 20, and tower top temperature is 70 DEG C or so, and column bottom temperature is 165
DEG C or so, absolute pressure of top of the tower is 0.04Mpa or so, and steam is 0.3 with the charge ratio of heavy distillat extract：100 or so.
103 tower top effluent of solvent recovery tower enters sulfur-rich oil tank 104 after condenser condensation, to sulfur-rich oil tank 104
Evacuation, is separated the sulfur-rich component of weight and water, and the sulfur-rich component of the weight isolated forms the double distilled containing sulfide and aromatic hydrocarbons
Divide extraction oil, subsequently entering selective hydrodesulfurization unit carries out selective hydrodesulfurization, and the water part isolated is back to
Flowed back at the top of solvent recovery tower 103, wherein reflux ratio is 0.8 or so, and another part is used in being then back to water scrubber 102
The washing of heavy distillat raffinate.
102 bottom of towe water outlet of water scrubber is stripped into 105 tower top of water stripper, so as to separation water in it is micro organic
Thing, 105 tower top effluent of water stripper subsequently enter return tank 106 and are separated, and 105 bottom stream of water stripper (contains
The water of solvent) subsequently enter 103 bottom of towe of solvent recovery tower and carry out solvent recovery.105 bottom of water stripper is typically provided with reboiler,
Its stripped vapor for producing can be used as the steam source of solvent recovery tower 103.
Evacuation is carried out to return tank 106, Organic substance is separated with water, the Organic substance isolated subsequently enters extraction
101 bottom of towe of distillation column, the hydration that the water isolated is flowed out with 102 bottom of towe of water scrubber are simultaneously carried out into 105 tower top of water stripper afterwards
Stripping.
A part of elder generation in the organic solvent that 103 bottom of towe of solvent recovery tower flows out is used as 105 bottom reboiler of water stripper
Thermal source, then exchange heat with the extract of 101 bottom of towe of extraction distillation column, return again to 101 tower top of extraction distillation column, so as to complete
The circulation of organic solvent；Another part is then entered in the middle part of solvent regeneration tower 107, while the steam that 105 bottom of towe of water stripper is produced
Into 107 bottom of solvent regeneration tower, reduced steam distillation is carried out to organic solvent, solvent vapo(u)r and vapor are from solvent reclamation
107 tower top of tower enters 103 bottom of towe of solvent recovery tower, the irregular deslagging of 107 bottom of towe of solvent regeneration tower, to remove solvent drop after flowing out
Solution thing, the performance of safeguards system circulating solvent.
2.4 selective hydrodesulfurization
After above-mentioned light fraction extraction oil and heavy distillat extraction oil are merged, it is catalyzed in above-mentioned selective hydrodesulfurization with hydrogen
Selective hydrodesulfurization is carried out in the presence of agent；Wherein, controlling reaction temperature is controlled for 260 DEG C, reaction pressure is 1.8MPa, body
Product air speed 3.0h-1, hydrogen to oil volume ratio (i.e. hydrogen and the volume of miscella formed by light fraction extraction oil and heavy distillat extraction oil
Than) for 500, obtain sweetened distillate.
2.5 mixing
By above-mentioned light fraction raffinate oil, heavy distillat raffinate oil and sweetened distillate mixing, sulfur-free gasoline is obtained, its yield is
96%, composition is shown in Table 1.
Embodiment 2
The present embodiment is improved on the basis of embodiment 1, be the difference is that：
Absorption desulfurization is carried out to the light fraction raffinate oil of embodiment 1, light fraction absorption sweet oil is obtained and light fraction is sulfur-rich
Oil；And absorption desulfurization is carried out to the heavy distillat raffinate oil of embodiment 1, heavy distillat absorption sweet oil is obtained and heavy distillat is sulfur-rich
Oil.Subsequently, light fraction sulfur-rich oil, the sulfur-rich oil of heavy distillat are merged with the light fraction extraction oil and heavy distillat extraction oil of embodiment 1
After carry out selective hydrodesulfurization, obtain sweetened distillate, its technological process is as shown in Figure 2.
Above-mentioned absorption desulfurization, ZSM-5 type molecule of the desulfuration adsorbent by Jing alkali process respectively are carried out using desulfuration adsorbent
Sieve and activated carbon are obtained as composite carrier load active metal components；Wherein, molecular sieve and the mass ratio of activated carbon are 1：
1, active metal is about load capacity of 5%, the Ni on complex carrier for the load capacity of K and Ni, K on complex carrier and is about
10%, the K loaded on complex carrier are 0.5 with the mass ratio of Ni：1.
After testing, the Sulfur capacity of above-mentioned desulfuration adsorbent is 0.514, and life-span length reaches 8-9h, and absorption desulfuration efficiency reaches
100%；Wherein, what is removed when the total sulfur content in gasoline stocks is down to below 10ppmw by 1g desulfuration adsorbents by Sulfur capacity is total
When sulfur content (in gram), i.e. Sulfur capacity are 0.514, represent 1g desulfuration adsorbents and the total sulfur content in gasoline stocks is down to into 10ppmw
The total sulfur content removed when following is 0.514g.
Above-mentioned desulfuration adsorbent is filled in fixed bed reactors, in the case where temperature is for 30 DEG C and condition of normal pressure, with
The flow velocity of 0.5mL/min carries out absorption desulfurization to light fraction raffinate oil and heavy distillat raffinate oil respectively, obtains light fraction absorption de-
Sweet oil is adsorbed in sulfur oil and heavy distillat；After absorption desulfurization, using the desulfurization absorption after 150 DEG C of steam purging absorption desulfurization
Agent 3h is washed, and collects the sulfur-rich oil of light fraction and the sulfur-rich oil of heavy distillat respectively, and will be the light fraction sulfur-rich oil and heavy distillat rich
Sulfur oil carries out selective hydrodesulfurization after merging with the light fraction extraction oil and heavy distillat extraction oil of embodiment 1, obtains desulfurization and evaporates
Point.
Sweet oil, heavy distillat absorption sweet oil and sweetened distillate mixing are adsorbed in light fraction, sulfur-free gasoline is obtained, its yield
For 96%, composition is shown in Table 1.
Embodiment 3
Except, in extractive distillation, extraction distillation column theoretical cam curve is 25, extractive distillation column overhead temperatures are 80 DEG C or so, tower
Bottom temperature is 150 DEG C or so, and absolute pressure of top of the tower is 0.2MPa or so, and organic solvent is 0.5 or so with the charge ratio of heavy distillat,
Now in extraction distillation column, alkene reaches 80% or so with the separating degree of aromatic hydrocarbons；
In absorption desulfurization, the life-span of desulfuration adsorbent is 3.4h, adsorbs desulfuration efficiency and reaches outside 84% or so, and remaining is equal
It is same as Example 2, sulfur-free gasoline is obtained, its yield is 94%, and composition is shown in Table 1.
Embodiment 4
1st, prepare catalyst for selectively hydrodesulfurizing
Catalyst for selectively hydrodesulfurizing is prepared according to 1 method of embodiment, except for the difference that, loads of the Co on carrier is controlled
Amount is about load capacity of 4%, the Mo on carrier and is about 10%, and the mass ratio of the Co and Mo of supported on carriers is 0.4：1.
2nd, gasoline desulfurization
Catalytic gasoline with Jinan (its composition is shown in Table 2) as raw material, the technological process for carrying out desulfurization to the gasoline stocks is such as
Under.
2.1 gasoline stocks cut
Above-mentioned gasoline stocks are cut into into light fraction and heavy distillat, wherein gently, the cutting temperature of heavy distillat be 110 DEG C, i.e.,：
Fraction of the light fraction for 110 DEG C of ＜, double distilled are divided into the fraction of 110 DEG C of ＞.
2.2 liquid-liquid extraction
Using the method for embodiment 1, liquid-liquid extraction is carried out to light fraction, obtain the oil of the light fraction raffinate containing alkene and contain
There is the light fraction extraction oil of sulfide and aromatic hydrocarbons；Wherein, except for the difference that：
In liquid-liquid extraction, organic solvent is tetraethylene glycol (TEG), and C5 alkane is pentane；It is 80 to control to extract column overhead temperatures
DEG C, column bottom temperature is 60 DEG C, and absolute pressure of top of the tower is 0.2MPa, organic solvent and light fraction charge ratio be 2.0, C5 alkane with it is light
Fraction charge ratio is 0.2.
When washing to light fraction raffinate, the consumption (amount based on light fraction raffinate) for controlling water is left for 4%
It is right.
When organic solvent and C5 alkane in light fraction extract is separated, extraction distillation tower absolute pressure is controlled
For 0.2MPa, extraction distillation tower column bottom temperature is 180 DEG C；Recovery tower absolute pressure is controlled for 0.025MPa, recovery tower bottom of towe temperature
Spend for 150 DEG C.
2.3 extractive distillation
Using the method for embodiment 1, extractive distillation is carried out to heavy distillat, obtain the oil of the heavy distillat raffinate containing alkene and contain
There is the heavy distillat extraction oil of sulfide and aromatic hydrocarbons；Wherein, except for the difference that：
In extractive distillation, organic solvent is the double solventss mixed by sulfolane and tetraethylene glycol (TEG), in double solventss
Sulfolane is 8.5 with the volume ratio of tetraethylene glycol (TEG)：1.5；Extraction distillation column theoretical cam curve is 35, and controls extraction distillation column tower
Top temperature is 100 DEG C or so, and column bottom temperature is 180 DEG C or so, and absolute pressure of top of the tower is 0.3MPa or so, organic solvent and double distilled
The charge ratio for dividing is 2.0 or so, and reflux ratio is 2.0 or so, and now in extraction distillation column, alkene is reached with the separating degree of aromatic hydrocarbons
90% or so；When washing to heavy distillat raffinate, the consumption for controlling water is 4% or so.
When organic solvent in heavy distillat extract is separated, the theoretical cam curve of solvent recovery tower is 25, tower
Top temperature is 80 DEG C or so, and column bottom temperature is 185 DEG C or so, and absolute pressure of top of the tower is 0.06MPa or so, and steam and heavy distillat extract
The charge ratio for taking thing is 0.3：100 or so；Reflux ratio is 2.0 or so, and the organic solvent water content of solvent recovery tower bottom of towe is
0.8-0.9%.
2.4 selective hydrodesulfurization
After above-mentioned light fraction extraction oil and heavy distillat extraction oil are merged, it is catalyzed in above-mentioned selective hydrodesulfurization with hydrogen
Selective hydrodesulfurization is carried out in the presence of agent；Wherein, 300 DEG C of controlling reaction temperature, reaction pressure 2.5MPa, volume space velocity
2.0h-1, hydrogen to oil volume ratio be 400, obtain sweetened distillate.
2.5 mixing
By above-mentioned light fraction raffinate oil, heavy distillat raffinate oil and sweetened distillate mixing, sulfur-free gasoline is obtained, its yield is
96%, composition is shown in Table 2.
Embodiment 5
The present embodiment is improved on the basis of embodiment 4, be the difference is that：
Absorption desulfurization is carried out to the light fraction raffinate oil of embodiment 4, light fraction absorption sweet oil is obtained and light fraction is sulfur-rich
Oil；And absorption desulfurization is carried out to the heavy distillat raffinate oil of embodiment 4, heavy distillat absorption sweet oil is obtained and heavy distillat is sulfur-rich
Oil.Subsequently, light fraction sulfur-rich oil, the sulfur-rich oil of heavy distillat are merged with the light fraction extraction oil and heavy distillat extraction oil of embodiment 4
After carry out selective hydrodesulfurization, obtain sweetened distillate.
Carry out above-mentioned absorption desulfurization using desulfuration adsorbent, desulfuration adsorbent by the Y type molecular sieve of Jing alkali process respectively and
Activated carbon is obtained as composite carrier load active metal components, wherein, active metal is Zn and Fe, and Zn is on complex carrier
Load capacity be about load capacity of 10%, the Fe on complex carrier and be about 10%, the quality of the Zn loaded on complex carrier and Fe
Than for 1：1.The Sulfur capacity of the desulfuration adsorbent is 0.481, and life-span length reaches 7-8h, and absorption desulfuration efficiency reaches 100%.
Above-mentioned desulfuration adsorbent is filled in fixed bed reactors, in the case where temperature is for 30 DEG C and condition of normal pressure, with
The flow velocity of 0.3mL/min carries out absorption desulfurization to light fraction raffinate oil and heavy distillat raffinate oil respectively, obtains light fraction absorption de-
Sweet oil is adsorbed in sulfur oil and heavy distillat；After absorption desulfurization, using the desulfurization absorption after 180 DEG C of steam purging absorption desulfurization
Agent 1h is washed, and collects the sulfur-rich oil of light fraction and the sulfur-rich oil of heavy distillat respectively, will be the light fraction sulfur-rich oil and heavy distillat sulfur-rich
Oil carries out selective hydrodesulfurization after merging with the light fraction extraction oil and heavy distillat extraction oil of embodiment 4, obtains sweetened distillate.
Sweet oil, heavy distillat absorption sweet oil and sweetened distillate mixing are adsorbed in light fraction, sulfur-free gasoline is obtained, its yield
For 96%, composition is shown in Table 2.
Reference examples 1
Except the extractive distillation for not carrying out embodiment 1, and after directly merged the light fraction extraction oil of embodiment 1 with heavy distillat
Selective hydrodesulfurization is carried out, sweetened distillate is obtained；By light fraction raffinate oil and sweetened distillate mixing, sulfur-free gasoline (group is obtained
Into being shown in Table 1), its yield is 94%, and sulfur-free gasoline sulfur content is 8.5ppm, and loss of octane number reaches 2 units.
The composition of gasoline before and after 1 desulfurization of table
Reference examples 2
Except the extractive distillation for not carrying out embodiment 4, and after directly merging the light fraction extraction oil of embodiment 4 and heavy distillat
Selective hydrodesulfurization is carried out, sweetened distillate is obtained；By light fraction raffinate oil and sweetened distillate mixing, sulfur-free gasoline (group is obtained
Into being shown in Table 2), its yield is 94%, and sulfur-free gasoline sulfur content is 9.3ppm, and loss of octane number reaches 2 units.
The composition of gasoline before and after 2 desulfurization of table
Reference examples 3
Except the gasoline for not carrying out embodiment 1 cuts, and directly the gasoline stocks of embodiment 1 are entered using 1 method of embodiment
Row extractive distillation, obtains extraction oil and raffinate oil, subsequently carries out selective hydrodesulfurization to extraction oil using 1 method of embodiment,
Obtain sulfur-free gasoline；Raffinate oil is mixed with sulfur-free gasoline, sulfur-free gasoline is obtained, its yield is 94%, sulfur-free gasoline sulfur content
For 8.9ppm, loss of octane number reaches 1.4 units.
From the above results：
When the 1st, carrying out desulfurization to gasoline stocks using various embodiments of the present invention method, in sulfur-free gasoline, sulfur content reaches
Below 10ppm, octane number reduce by 1 unit of ＜, product yield ＞ 95% (except embodiment 3)；And reference examples 1 and reference examples 2
Method does not carry out the extractive distillation of the present invention, and selective hydrodesulfurization is carried out to heavy distillat directly, and now loss of octane number reaches
To 2 units；3 method of reference examples does not carry out gasoline cutting and directly carries out extractive distillation to the full fraction of gasoline stocks, octane number
Loss reaches 1.4 units.
2nd, the extractive distillation of various embodiments of the present invention can make the alkene and aromatic hydrocarbons high separation in heavy distillat, and separating degree is reachable
It is more than more than 80%, or even 90%；Also, alkene is separated to also help with aromatic hydrocarbons and avoids the institute in subsequent adsorbtion sweetening process
The competitive Adsorption for causing, absorption desulfuration efficiency may be up to 100%, and the service life of adsorbent is greatly prolonged.
Finally it should be noted that：Various embodiments above only to illustrate technical scheme, rather than a limitation；To the greatest extent
Pipe has been described in detail to the present invention with reference to foregoing embodiments, it will be understood by those within the art that：Its according to
So the technical scheme described in foregoing embodiments can be modified, or which part or all technical characteristic are entered
Row equivalent；And these modifications or replacement, do not make the essence of appropriate technical solution depart from various embodiments of the present invention technology
The scope of scheme.
Claims (9)
1. a kind of deep desulfurization of gasoline method, it is characterised in that comprise the steps：
Gasoline stocks are cut into into light fraction and heavy distillat；
Liquid-liquid extraction is carried out to the light fraction, the oil of the light fraction raffinate containing alkene and light containing sulfide and aromatic hydrocarbons is obtained
Fraction extraction oil；
Extractive distillation is carried out to the heavy distillat, the oil of the heavy distillat raffinate containing alkene and the weight containing sulfide and aromatic hydrocarbons is obtained
Fraction extraction oil；
Selective hydrodesulfurization is carried out to the light fraction extraction oil and heavy distillat extraction oil, sweetened distillate is obtained；
By light fraction raffinate oil, heavy distillat raffinate oil and sweetened distillate mixing, sulfur-free gasoline is obtained；
Wherein, the light fraction and the cutting temperature of heavy distillat are 80-120 DEG C；
The liquid-liquid extraction includes：
The light fraction is made to enter from extraction tower middle and lower part, organic solvent is entered from the top of extraction tower, and from extracting tower bottom
Reflux injects C5 alkane；Wherein, it is 55-100 DEG C to control to extract column overhead temperatures, and column bottom temperature is 40-80 DEG C, and tower top is exhausted
It is 0.2-0.7MPa to pressure, the organic solvent and light fraction charge ratio are 1.0-5.0, C5 alkane is with light fraction charge ratio
0.1-0.5；
Extraction tower tower top effluent is collected, the light fraction raffinate containing alkene is obtained；Extraction tower bottom stream is collected, is obtained
Light fraction extract containing sulfide and aromatic hydrocarbons；
The light fraction raffinate is washed, the oil of the light fraction raffinate containing alkene is obtained；
Organic solvent and C5 alkane in the light fraction extract is separated, gently evaporating containing sulfide and aromatic hydrocarbons is obtained
Divide extraction oil；
The extractive distillation includes：
The heavy distillat is made to enter from extraction distillation column middle and lower part, organic solvent is entered from extraction distillation column top；Wherein, it is described
The theoretical cam curve of extraction distillation column is 25-45, and tower top temperature is 70-110 DEG C, and column bottom temperature is 150-190 DEG C, and tower top is absolute
Pressure is 0.1-0.5MPa, and organic solvent is 1.0-5.0 with the charge ratio of heavy distillat, and reflux ratio is 0.1-4.0；
Extraction distillation column tower top effluent is collected, the heavy distillat raffinate containing alkene is obtained；Collect extraction distillation column bottom of towe stream
Go out thing, obtain the heavy distillat extract containing sulfide and aromatic hydrocarbons；
The heavy distillat raffinate is washed, the oil of the heavy distillat raffinate containing alkene is obtained；
Organic solvent in the heavy distillat extract is separated, the extraction of the heavy distillat containing sulfide and aromatic hydrocarbons is obtained
Oil.
2. deep desulfurization of gasoline method according to claim 1, it is characterised in that the organic solvent selected from diethylene glycol,
2,2'-ethylenedioxybis(ethanol)., tetraethylene glycol (TEG), dimethyl sulfoxide, sulfolane, N- N-formyl morpholine Ns, N-Methyl pyrrolidone, Polyethylene Glycol and Allyl carbonate
In one or more.
3. deep desulfurization of gasoline method according to claim 1, it is characterised in that having in the heavy distillat extract
Machine solvent is separated, including：The heavy distillat extract is made to enter from solvent recovery tower middle and upper part, steam is from solvent recovery tower
Bottom enters；Wherein, the theoretical cam curve for controlling solvent recovery tower is 10-30, and tower top temperature is 50-100 DEG C, and column bottom temperature is
150-200 DEG C, absolute pressure of top of the tower is 0.03-0.07MPa, and steam is (0.1-0.5) with the charge ratio of heavy distillat extract：
100, reflux ratio is 0.2-4.0.
4. deep desulfurization of gasoline method according to claim 2, it is characterised in that having in the heavy distillat extract
Machine solvent is separated, including：The heavy distillat extract is made to enter from solvent recovery tower middle and upper part, steam is from solvent recovery tower
Bottom enters；Wherein, the theoretical cam curve for controlling solvent recovery tower is 10-30, and tower top temperature is 50-100 DEG C, and column bottom temperature is
150-200 DEG C, absolute pressure of top of the tower is 0.03-0.07MPa, and steam is (0.1-0.5) with the charge ratio of heavy distillat extract：
100, reflux ratio is 0.2-4.0.
5. deep desulfurization of gasoline method according to claim 1, it is characterised in that by the light fraction extraction oil and double distilled
Divide extraction oil that the selective hydrodesulfurization is carried out in the presence of catalyst for selectively hydrodesulfurizing with hydrogen after merging；Its
In, the temperature for controlling the selective hydrodesulfurization is 200-300 DEG C, and pressure is 1.5-2.5MPa, and volume space velocity is 1-5h-1,
Hydrogen to oil volume ratio is 400-600.
6. deep desulfurization of gasoline method according to claim 5, it is characterised in that the catalyst for selectively hydrodesulfurizing
Obtained by carrier loaded active metal components；Wherein, the carrier is molecular sieve or metal-oxide, the active metal bag
Co and Mo is included, and Co and Mo total load amount on the carrier is 5-20%.
7. according to the arbitrary described deep desulfurization of gasoline method of claim 1 to 6, it is characterised in that also include：
Absorption desulfurization is carried out to the light fraction raffinate oil, light fraction absorption sweet oil and the sulfur-rich oil of light fraction is obtained；
Absorption desulfurization is carried out to the heavy distillat raffinate oil, heavy distillat absorption sweet oil and the sulfur-rich oil of heavy distillat is obtained；
Sweet oil, heavy distillat absorption sweet oil and sweetened distillate mixing are adsorbed in the light fraction, sulfur-free gasoline is obtained.
8. deep desulfurization of gasoline method according to claim 7, it is characterised in that carry out the suction using desulfuration adsorbent
Attached desulfurization, the desulfuration adsorbent by respectively Jing alkali process molecular sieve and activated carbon as composite carrier load active metal into
Divide and obtain；Wherein, one or more element of the active metal in periodic chart IA, VIII, IB, IIB and group vib,
Load capacity of the active metal on complex carrier is 2-30%.
9. deep desulfurization of gasoline method according to claim 8, it is characterised in that the absorption desulfurization is to utilize fixed bed
Normal pressure is carried out, and control adsorb desulfurization temperature be 20-100 DEG C, light fraction raffinate oil or heavy distillat raffinate oil flow velocity be
0.3-1mL/min。
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