CN105255516B - A kind of combined method of gasoline desulfurization - Google Patents
A kind of combined method of gasoline desulfurization Download PDFInfo
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- CN105255516B CN105255516B CN201510643066.7A CN201510643066A CN105255516B CN 105255516 B CN105255516 B CN 105255516B CN 201510643066 A CN201510643066 A CN 201510643066A CN 105255516 B CN105255516 B CN 105255516B
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Abstract
The present invention provides a kind of combined method of gasoline desulfurization.The combined method comprises the following steps：Gasoline stocks are cut into light fraction and heavy distillat；Extractive distillation is carried out to the heavy distillat using organic solvent, the raffinate oil containing alkene and the extract containing sulfide and aromatic hydrocarbons is obtained；Organic solvent in the extract is separated, extraction oil is obtained；Selective hydrodesulfurization is carried out to the extraction oil, desulfurization heavy distillat is obtained；The light fraction, raffinate oil and desulfurization heavy distillat are mixed, sulfur-free gasoline is obtained；Wherein, the cutting temperature of the light fraction and heavy distillat is 35 60 DEG C.The combined method of the present invention can also be substantially reduced gasoline products loss of octane number while deep desulfuration is realized, and product yield is up to more than 95%.
Description
Technical field
The present invention relates to a kind of method of gasoline desulfurization, more particularly to a kind of combined method of gasoline desulfurization.
Background technology
With pay attention to day by day of the people to environmental protection, the requirement of the new environmental regulations 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 sulphur 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).It is only possible to reach therefore, it is necessary to carry out deep desulfuration to gasoline
Related request.
Adsorb influence of the desulfurization to gasoline products octane number while sulfide in removing gasoline stocks smaller, therefore be
Relatively one of sulfur method of tool potentiality, also there is more report at present.For example, by Black＆Veatch Pritchard Inc. with
The IRVAD technologies that Alcoa Industrial Chemicals are developed jointly use multistage fluidized bed suction type, use oxidation
Aluminum matrix selectivity solid absorbent treatment liquid hydro carbons, in adsorption process, adsorbent adverse current is in contact with liquid hydrocarbon, makes
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 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 used under conditions of hydrogen is faced
Carry out desulfurization, the adsorbent using zinc oxide, silica, aluminum oxide as the metal component such as carrier and load C o, Ni, Cu,
It 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 and alkene are 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 in absorption sweetening process into branch, so as to cause the reduction of absorption desulfuration efficiency, 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 that
Two or more cut is cut into, wherein desulfurization is carried out to light fraction in non-hydrodesulfurization mode, so as to avoid octane number from damaging
Lose；Desulfurization generally is carried out in selective hydrodesulfurization mode to heavy distillat, so as to realize deep desulfuration.
For example, Research Institute of Petro-Chemical Engineering is in the FCC gasoline selective hydrogenation desulfurization process (RSDS- of exploitation in 2001
I), first under 90 DEG C of cutting temperature by FCC gasoline cut into gently, heavy distillat, then to light fraction progress alkali density removal of mercaptans,
And selective hydrodesulfurization is carried out to heavy distillat using major catalyst RSDS- I and protective agent RGO-2；And enter to above-mentioned technique
The improved second 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 use the second generation hydrogenation catalyst RSDS-21, RSDS-22 in heavy distillat selective hydrodesulfurization part.
The Prime-G+ techniques of (IFP) Axens companies of IFP exploitation, are hydrogenated with, weight in advance using full cut
Gasoline cuts the technological process with heavy distillat selective hydrodesulfurization, and cutting temperature is set to by it according to the desired value of sulfur content
93-149 DEG C, and during full cut in advance hydrogenation, act on forming height by trechmannite compound and alkadienes using HR845 catalyst
The sulfide of boiling point, therefore alkene is not saturated；In addition, using HR806 and HR841 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 cuts, wherein carrying out removal of mercaptans to light fraction, heavy distillat is combined using FGH-20/FGH-11 and is catalyzed
Agent carries out selective hydrodesulfurization.
The HDDO series that extra large Shuande is developed takes off the serial deep hydrodesulfurizationof catalyst of diene hydrocarbon catalyst, HDOS, HDMS
Serial mercaptan-eliminating catalyst and corresponding FCC gasoline selective hydrogenation desulfurization process (CDOS), first by FCC gasoline compared with low temperature
Degree, dialkene removal reaction is carried out under hydro condition, then by FCC gasoline be cut into gently, two components are weighed, and to heavy distillat progress
Heavy distillat after deep hydrodesulfurizationof, hydrogenation reconciles with light fraction and obtains low sulfur clean gasoline.
The above method is universal to the cutting temperatures of gasoline stocks higher, cuts in formed light fraction sulfur content 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 stills need hydrodesulfurization, thus the loss of octane number amount of full distillation gasoline
Higher (being for example up to 3.0-4.0).Although in addition, above-mentioned hydrodesulfurization mode can substantially reduce the sulfur content of gasoline, so
And there is investment and operating cost height, substantial amounts of alkene is saturated while sulfide is removed, hydrogen consumption has both been added, also made
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 combined method of gasoline desulfurization, multiple for solving sulfur method operation of the prior art
It is miscellaneous, and be difficult to while realizing deep desulfuration and reducing the technological deficiencies such as loss of octane number.
The present invention provides a kind of combined method of gasoline desulfurization, comprises the following steps：
Gasoline stocks are cut into light fraction and heavy distillat；
Extractive distillation is carried out to the heavy distillat using organic solvent, the oil of the raffinate containing alkene is obtained and contains sulfide
And the extract of aromatic hydrocarbons；
Organic solvent in the extract is separated, extraction oil is obtained；
Selective hydrodesulfurization is carried out to the extraction oil, desulfurization heavy distillat is obtained；
The light fraction, raffinate oil and desulfurization heavy distillat are mixed, sulfur-free gasoline is obtained；
Wherein, the cutting temperature of the light fraction and heavy distillat is 35-60 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 cuts；The cutting can be carried out using this area conventional method, for example, distilled
Deng.Further, the cutting temperature of the light fraction and heavy distillat is 40-50 DEG C.
The present inventor it has been investigated that, when gasoline stocks are cut into light fraction and heavy distillat, inevitable that
The unsaturated hydrocarbons composition such as a part of alkene is retained in heavy distillat, in process subsequently to the selective hydrodesulfurization of heavy distillat
In, the unsaturated hydrocarbons composition such as alkene is saturated, so as to cause a large amount of losses of octane number of gasoline products and hydrogen to be largely lost.
In view of this problem, the present inventor first carries out extractive distillation to heavy distillat, so that by the unsaturated hydrocarbons such as alkene composition from heavy distillat
In separate, other compositions carry out not resulting in octane number not only during selective hydrodesulfurizations in subsequently to heavy distillat
A large amount of losses, additionally it is possible to total desulfurization load is greatly reduced, therefore can also be notable while deep desulfuration is realized
Reduce gasoline products loss of octane number.
Further, according to gasoline stocks quality or the difference of cutting temperature, the light fraction after the cutting is carried out
Sulfur content could possibly be higher than 10ppm, in this case, can also be using the non-hydrodesulfurization mode of routine of this area to light fraction
Desulfurization is carried out, the sulfur content of light fraction is less than 10ppm.For example：First the gasoline stocks can be carried out after removal of mercaptans processing
Light fraction and heavy distillat are cut into again；Or, to the light fraction carry out removal of mercaptans processing after again with the raffinate oil and desulfurization
Heavy distillat is mixed.Removal of mercaptans processing can make the sulfur content of light fraction be reduced to below 10ppm.
In the present invention, can carry out the removal of mercaptans processing using the conventional method of this area, for example alkali density method or
Mercaptan conversion method etc..Alkali density method is removed mercaptan extracting into alkali lye using alkali lye, and the mass content of alkali can be in alkali lye
5-50%, oily alkali volume ratio can be (1-15)：1, operation temperature can be 10-60 DEG C；Mercaptan conversion method is to turn small molecule mercaptan
Turn to other sulfide and remove, can be using modes such as the pre- hydrogenation in conventional alkali-free sweetening technique, Prime-G+ techniques
Carry out, wherein alkali-free sweetening process conditions can be：Reactor operating pressure 0.2-1.0MPa, 20-60 DEG C of reaction temperature, charging
Air speed 0.5-2.0h-1, the volume ratio of air mass flow and inlet amount is 0.2-1.0, and used catalyst and co-catalyst can be
Catalyst commonly used in the art.
Further, the light fraction is carried out forming removal of mercaptans light fraction and tapped oil after removal of mercaptans processing, can be by institute
State after tapped oil merges with the extraction oil and carry out selective hydrodesulfurization, by the removal of mercaptans light fraction and raffinate oil and desulfurization
Heavy distillat is mixed, and obtains sulfur-free gasoline.
In the present invention, the purpose of extractive distillation is by the compositions such as the alkene in heavy distillat, alkane, cycloalkane and vulcanization
Thing, the other composition separation of most of aromatic hydrocarbons and cyclenes etc., so as to avoid the unsaturated hydrocarbons such as alkene in subsequent selective hydrodesulfurization
During be saturated and cause gasoline products octane number reduction.Those skilled in the art can select suitable to have according to the purpose
Machine solvent and extractive distillation technique.For example, the organic solvent can selected from diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, dimethyl sulfoxide,
One or more in sulfolane, N- N-formyl morpholine Ns, 1-METHYLPYRROLIDONE, polyethylene glycol and propene carbonate, further for
The mixed solvent of one or more in triethylene glycol, tetraethylene glycol and sulfolane, such as triethylene glycol and sulfolane, its sulfolan with
The volume ratio of triethylene glycol can be (6-9)：(4-1).Control water content (i.e. the weight content of water) ＜ of the organic solvent
1.0% is favourable, can be further 0.6-0.8%.
In one embodiment, the extractive distillation includes：The heavy distillat is entered from extraction distillation column middle and lower part, have
Machine solvent enters from extraction distillation column top；Wherein, the theoretical cam curve of the extraction distillation column is 25-45, and tower top temperature is
70-110 DEG C, column bottom temperature is 150-190 DEG C, and absolute pressure of top of the tower is 0.1-0.5MPa, organic solvent and heavy distillat charging
It is 1.0-5.0 than (i.e. volume ratio), reflux ratio is 0.1-4.0.Under the conditions of the extractive distillation, alkene and aromatic hydrocarbons in heavy distillat
Separation degree can reach more than 90%, good separating effect.
During above-mentioned extractive distillation, heavy distillat is contacted with organic solvent in extraction distillation column through multi-stage countercurrent, weight
Cut from extractive distillation top of tower flow out when partial vulcanization thing, most of composition such as aromatic hydrocarbons and cyclenes be extracted removing so that shape
Into the extract remainder containing compositions such as alkene, alkane, cycloalkane, after the condensed device condensation of extract remainder, part backflow, to maintain extraction
The heat balance in destilling tower tower is taken, and ensures stable progress and the separation accuracy of product of extractive distillation, wherein reflux ratio
(i.e. for the volume ratio between the extract remainder and the extract remainder that distillates of backflow) is 0.1-4.0；The vulcanization in heavy distillat is extracted
The solvent of thing and aromatic hydrocarbons flows out from bottom of towe, forms extract, wherein containing sulfur-rich component (including sulfide, aromatic hydrocarbons, cyclenes etc.),
Water and solvent.
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, the charge ratio of organic solvent and heavy distillat is 2.0-3.0, backflow
Than for 0.2-2.0.
Furthermore, it is possible to be washed to above-mentioned extract remainder, so as to remove organic solvent therein, raffinate oil is formed；In water
When washing, the consumption (amount based on extract remainder) that can control water is 1-10%, for example, 2-4%.
It is possible to further carry out separating treatment to above-mentioned extract, so that sulfur-rich component, water in extract, having
Machine solvent is separated, and the water isolated can be used for washing extract remainder, and the organic solvent isolated can be used for above-mentioned extraction
Distillation is taken, the sulfur-rich component (i.e. extraction oil) isolated then carries out selective hydrodesulfurization.
In one embodiment, the separation includes：The extract is set to enter from solvent recovery tower middle and upper part, steam
(water vapour) enters from solvent recovery tower bottom；Wherein, the theoretical cam curve of the solvent recovery tower is 10-30, tower top temperature
For 50-100 DEG C, column bottom temperature is 150-200 DEG C, and absolute pressure of top of the tower is 0.03-0.07MPa, the charging of steam and extract
It is (0.1-0.5) than (i.e. mass ratio)：100, reflux ratio is 0.2-4.0.
In above-mentioned solvent recovery tower, sulfur-rich component is separated with solvent, and wherein solvent can enter after bottom of towe outflow
Utilization is circulated in extraction distillation column；Sulfur-rich component and steam flow out from tower top, it is condensed after, using usual manner (for example
Vacuumize) dehydration, extraction oil (i.e. sulfur-rich component) is obtained, extraction oil then carries out selective hydrodesulfurization, part removing
Water is used to flow back, to maintain the heat balance in solvent recovery tower tower, it is ensured that the stable progress of separation process, wherein reflux ratio are (i.e.
For the volume ratio between the water and the water that distillates of backflow) it is 0.2-4.0, remaining water is used for the washing to extract remainder.
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 the charge ratio of steam and extract is (0.3-0.4)：100, return
Stream is than being 0.5-2.0.
In one embodiment, the extractive distillation and separation can include：
Heavy distillat is set to enter from extraction distillation column middle and lower part, organic solvent enters from extraction distillation column top, extractive distillation
Extract remainder of the column overhead effluent formation containing alkene, extraction of the extraction distillation column bottom stream formation containing sulfide and aromatic hydrocarbons
Take thing；
Enter above-mentioned extract remainder to be washed in water scrubber, obtain the raffinate oil containing alkene；
Above-mentioned extract is set to enter from solvent recovery tower middle and upper part, steam enters from solvent recovery tower bottom, solvent recovery
Tower bottom stream formation organic solvent, solvent recovery tower tower top effluent forms sulfur-rich component (containing sulfide, aromatic hydrocarbons, ring
Alkene etc.) and water mixture；
Enter said mixture to be separated in sulfur-rich oil tank, form extraction oil and water, a water part for formation is returned
To solvent recovery tower, 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
Going out thing (micro-content organism being stripped off from water) can then be separated into return tank, water stripper bottom stream
(i.e. solvent-laden water) can then enter solvent recovery tower bottom of towe and carry out solvent recovery.Water stripper bottom is typically provided with reboiling
Device, its produce stripped vapor can as solvent recovery tower steam source.
In return tank, organic matter can by conventional methods be separated with water and (for example vacuumized), and that isolates is organic
Thing subsequently enters extraction distillation column bottom of towe, and the water isolated enters after can merging with water scrubber bottom of towe water outlet into water stripper tower top
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, then with the extract heat exchange of extraction distillation column bottom of towe, is returned again to extractive distillation column overhead；Another part organic solvent can
In the middle part of into solvent regeneration tower, while the steam that water stripper bottom of towe is produced enters water-filling to solvent into solvent reclamation tower bottom and steamed
Steam distillation, solvent regeneration tower tower top effluent enters 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 circulation solvent
With performance, while being conducive to economizing on resources and the energy.
In the present invention, the selective hydrodesulfurization can be carried out using the conventional method of this area, such as S-zorb,
The selective desulfurization such as RSDS, OCT-M, Prime-G+, CODS method or other selective process for deep desulphurization, or above-mentioned
The combination of two or more methods in method.
In one embodiment, the extraction oil can be entered in the presence of catalyst for selectively hydrodesulfurizing with hydrogen
The row selective hydrodesulfurization；Wherein it is possible to which the temperature for controlling the selective hydrodesulfurization is 200-300 DEG C, pressure is
1.5-2.5MPa, 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 aluminium), the active metal can be able to be 5-20% including the total load amount of Co and Mo, Co and Mo on the carrier.More
Further, the Co and Mo of supported on carriers mass ratio are (0.2-0.6)：1.
In the present invention, can also first to the raffinate oil carry out absorption desulfurization after again with the light fraction and desulfurization double distilled
Divide mixing.Specifically, it is possible to use desulfuration adsorbent carries out the absorption desulfurization, the present invention to the desulfuration adsorbent that is used 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 molecular sieve and activated carbon through alkali process respectively as compound
Carrier loaded active metal components and obtain；Wherein, the active metal is in periodic table IA, VIII, IB, IIB and group vib
One or more elements, load capacity of the active metal on complex carrier be 2-30%, preferably 5-25%, further
Preferably 5-20%.
Further, in the complex carrier, the mass ratio of molecular sieve and activated carbon is (20-80):(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 use X-type with
Type ZSM 5 molecular sieve and activated carbon are without strict limitation, and the ratio surface of activated carbon generally can be 1000m2/ g or so；The Y types
The framework silicon-aluminum atomic ratio of molecular sieve is not less than 3.0 (XRD methods measure).
In addition, the active metal is at least two kinds of in Ni, Fe, Ag, Co, Mo, Zn and K.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, the load capacity is the total load of 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 K and Ni mass ratio loaded on complex carrier
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 Zn and Fe matter loaded on complex carrier
Amount is than being (0.5-1)：1.
The method that above-mentioned desulfuration adsorbent can refer to disclosed in Publication No. CN104667861A Chinese patent is carried out
Prepare and regenerate.
Further, the absorption desulfurization is carried out using fixed bed atmospheric pressure, and can control to adsorb the temperature of desulfurization
For 20-100 DEG C, such as 30-80 DEG C, the flow velocity of extraction oil is 0.3-1mL/min.The absorption desulfurization of the present invention through extraction only to steaming
Evaporate formed raffinate oil to carry out, due to eliminating aromatic hydrocarbons in raffinate oil, therefore it is possible to prevente effectively from aromatic hydrocarbons is in absorption desulfurization
Caused competitive Adsorption in journey, desulfuration efficiency may be up to 100%, and can also extend the service life of adsorbent.
In addition, the sulfur-rich oil formed after absorption desulfurization can be incorporated into above-mentioned extraction oil and carry out selective hydrodesulfurization.
The implementation of the present invention, at least has the advantage that：
1st, the combined method of gasoline desulfurization of the present invention, based on to the composition such as sulphur, alkene and aromatic hydrocarbons distribution in gasoline stocks
Gasoline stocks are first cut into light fraction and heavy distillat under specific cutting temperature, then heavy distillat are extracted by research
Distillation, makes the compositions such as alkene be separated from heavy distillat while partial desulfurization, and other compositions are carried out in subsequently to heavy distillat
A large amount of losses of octane number are not resulted in during selective hydrodesulfurization not only, additionally it is possible to total desulfurization is greatly reduced and bears
Lotus.
2nd, gasoline stocks are not only cut into different fractions by the combined method of gasoline desulfurization of the present invention according to cutting temperature, also
Its component is divided with reference to the composition characteristic of heavy distillat, and targetedly desulfurization is carried out to each component after division,
Whole sweetening process is more fine and efficient.
3rd, the combined method of gasoline desulfurization of the present invention is by Optimized Extraction distillation technique, so as to make alkene high with aromatic hydrocarbons
Degree separation, separating degree is up to more than 90%；Also, the separation of alkene and aromatic hydrocarbons, which is also helped, to be avoided in subsequent adsorbtion sweetening process
In caused competitive Adsorption, absorption desulfuration efficiency may be up to 100%, and the service life of adsorbent is greatly prolonged.
4th, sulfur content reaches below 10ppm, octane number in the sulfur-free gasoline of the combined method production of gasoline desulfurization of the present invention
Almost do not lose not only or even slightly improve, in addition product yield ＞ 95%, the quality of sulfur-free gasoline product is high.
Brief description of the drawings
Fig. 1 is the process chart of the combined method for the gasoline desulfurization that the embodiment of the present invention 1 is provided；
Fig. 2 is the process chart of the combined method for the gasoline desulfurization that the embodiment of the present invention 2 is provided；
Fig. 3 is the process chart of the combined method for the gasoline desulfurization that the embodiment of the present invention 4 is provided；
Fig. 4 is the process chart of the combined method for the gasoline desulfurization that the embodiment of the present invention 5 is provided；
Fig. 5 is extractive distillation in the combined method of one embodiment of the invention and the process chart separated.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, accompanying drawing and implementation below in conjunction with the present invention
Example, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is the present invention
A part of embodiment, rather than whole embodiments.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 creative work is made, the scope of protection of the invention is belonged to.
Embodiment 1
1st, catalyst for selectively hydrodesulfurizing is prepared
First use CoSO4Solution carries out incipient impregnation, scrubbed, dry and roasting to type ZSM 5 molecular sieve (carrier)
Afterwards, then using (NH4)6Mo7O24.4H2The O aqueous solution is to having impregnated CoSO4The type ZSM 5 molecular sieve of solution is soaked in equal volume
Stain, after scrubbed, dry and roasting, is made catalyst for selectively hydrodesulfurizing.
The catalyst for selectively hydrodesulfurizing of above-mentioned preparation is always 168m than surface2/ g or so, total pore volume is
The load capacity of 0.378mL/g or so, Co on carrier is about that load capacity of 7%, the Mo on carrier is about 10%, supported on carriers
Co and Mo mass ratio be 0.7：1.
2nd, gasoline desulfurization
The catalytic gasoline produced by catalytic cracking using grand celebration atmospheric residue is 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 Figure 1 and Figure 5.
2.1 gasoline stocks are cut
Above-mentioned gasoline stocks are cut into light fraction and heavy distillat, wherein gently, the cutting temperature of heavy distillat be 50 DEG C, i.e.,：
Light fraction is 50 DEG C of ＜ cut, and double distilled is divided into 50 DEG C of ＞ cut.
The processing of 2.2 removal of mercaptans
Light fraction is set to contact progress removal of mercaptans processing with aqueous slkali in extraction system, the alkali employed in it contains for quality
The volume ratio of the NaOH solution of amount 20%, light fraction and NaOH solution is 5：1, operation temperature is 30 DEG C, collects removal of mercaptans and gently evaporates
Divide and tapped oil.
2.3 extractive distillations and separation
Extractive distillation is carried out to above-mentioned heavy distillat using organic solvent, the oil of the raffinate containing alkene is obtained and contains sulfide
And the extract of aromatic hydrocarbons；Organic solvent in extract is separated, extraction oil is obtained；Wherein, technological process such as Fig. 5 institutes
Show, specifically include：
Above-mentioned heavy distillat is set to enter from the middle and lower part of extraction distillation column 101, organic solvent enters from the top of extraction distillation column 101
Enter, heavy distillat is contacted with organic solvent in extraction distillation column 101 through multi-stage countercurrent, carry out desulfurizing and dearomatizing；Wherein, You Jirong
Agent is the double solvents that is mixed by sulfolane and triethylene glycol, and the volume ratio of double solvents sulfolan and triethylene glycol is 8：2,
The water content ＜ 1.0% of double solvents, the theoretical cam curve of extraction distillation column 101 is 30, and the tower top temperature of extraction distillation column 101
For 80 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 and heavy distillat are entered
Material is than being 3.0 or so.
Gasoline fraction through desulfurizing and dearomatizing is drawn from the tower top of extraction distillation column 101, obtains the extract remainder containing alkene, is extracted
Excess part backflow, wherein reflux ratio are 0.6 or so；And the rich solvent of sulfide and aromatic hydrocarbons has been extracted from extraction distillation column
101 bottom is drawn, and obtains extract, and it contains sulfur-rich component (including sulfide, aromatic hydrocarbons, cyclenes etc.), water and solvent.In extraction
Take in destilling tower 101, the separating degree of alkene and aromatic hydrocarbons reaches 92%.
Above-mentioned extract remainder subsequently enters water scrubber 102 and is washed to remove organic solvent therein, water scrubber tower top stream
Go out raffinate oil of the thing formation containing alkene, the bottom stream of water scrubber 102 formation water (washing water)；When being washed, control
The consumption (amount based on extract remainder) of water is 3% or so.
Above-mentioned extract subsequently enters the middle part of solvent recovery tower 103, and the stripped vapor for being simultaneously from water stripper 105 enters
Enter to the bottom of solvent recovery tower 103 to carry out the vacuum distillation operation of rough vacuum, to reduce column bottom temperature, solvent recovery tower 103
Bottom stream formation organic solvent, its water content is 0.6-0.65%, and tower top effluent forms the mixing of sulfur-rich component and water
Thing；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 the charge ratio of steam and extract is 0.3：100 or so.
The tower top effluent of solvent recovery tower 103 enters sulfur-rich oil tank 104 after being condensed by condenser, to sulfur-rich oil tank 104
Vacuumize, separated sulfur-rich component and water, extraction oil of the sulfur-rich component formation containing sulfide and aromatic hydrocarbons isolated, with
Laggard selectable hydrodesulfurizationunit unit carries out selective hydrodesulfurization, and the water part isolated is back to solvent recovery tower
103 tops are flowed back, and wherein reflux ratio is 0.8 or so, and another part, which is then back in water scrubber 102, is used for the water of extract remainder
Wash.
The bottom of towe water outlet of water scrubber 102 is stripped into the tower top of water stripper 105, so that micro organic in separation water
Thing, the tower top effluent of water stripper 105 subsequently enters return tank 106 and separated, and the bottom stream of water stripper 105 (contains
The water of solvent) subsequently enter the bottom of towe of solvent recovery tower 103 progress solvent recovery.The bottom of water stripper 105 is typically provided with reboiler,
Its produce stripped vapor can as solvent recovery tower 103 steam source.
Return tank 106 is vacuumized, organic matter is separated with water, the organic matter isolated subsequently enters extraction
The bottom of towe of destilling tower 101, the hydration and the rear tower top of water stripper 105 that enters that the water isolated flows out with the bottom of towe of water scrubber 102 is carried out
Stripping.
A part in the organic solvent of the bottom of towe of solvent recovery tower 103 outflow is first as the bottom reboiler of water stripper 105
Thermal source, then exchange heat, returned again to the tower top of extraction distillation column 101, so as to complete with the extract of the bottom of towe of extraction distillation column 101
The circulation of organic solvent；Another part then enters the middle part of solvent regeneration tower 107, while the steam that the bottom of towe of water stripper 105 is produced
Into the bottom of solvent regeneration tower 107, reduced steam distillation is carried out to organic solvent, solvent vapo(u)r and vapor are from solvent reclamation
Enter the bottom of towe of solvent recovery tower 103, the irregular deslagging of the bottom of towe of solvent regeneration tower 107, to remove solvent drop after the outflow of the tower top of tower 107
Thing is solved, safeguards system circulates the performance of solvent.
2.4 selective hydrodesulfurizations
After above-mentioned tapped oil and extraction oil are merged, enter with hydrogen in the presence of above-mentioned catalyst for selectively hydrodesulfurizing
Row selective hydrodesulfurization；Wherein, controlling reaction temperature is 260 DEG C, and reaction pressure is 1.8MPa, volume space velocity 3.0h-1, hydrogen oil
Volume ratio (i.e. the volume ratio of hydrogen and the miscella formed by tapped oil and extraction oil) is 500, obtains desulfurization heavy distillat.
2.5 mixing
Above-mentioned removal of mercaptans light fraction, raffinate oil and desulfurization heavy distillat are mixed, 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, the difference is that：
Absorption desulfurization is carried out to the raffinate oil of embodiment 1, the oily and sulfur-rich oil of desulfurization raffinate is obtained, then by sulfur-rich oil and in fact
Apply example 1 tapped oil and extraction oil merge after carry out selective hydrodesulfurization, obtain desulfurization heavy distillat, its technological process such as Fig. 2
It is shown.
Above-mentioned absorption desulfurization is carried out using desulfuration adsorbent, desulfuration adsorbent is by the ZSM-5 type molecules through alkali process respectively
Sieve and activated carbon are obtained as composite carrier load active metal components；Wherein, the mass ratio of molecular sieve and activated carbon is 1：
1, active metal is about that load capacity of 5%, the Ni on complex carrier is about for the load capacity of K and Ni, K on complex carrier
10%, the K and Ni mass ratio loaded on complex carrier is 0.5：1.
After testing, the Sulfur capacity of above-mentioned desulfuration adsorbent is 0.514, and long lifespan 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 Sulfur capacity by 1g desulfuration adsorbents 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 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 30 DEG C and condition of normal pressure, with
0.5mL/min flow velocity carries out absorption desulfurization to raffinate oil, obtains desulfurization raffinate oil；After absorption desulfurization, using 150 DEG C of water
Desulfuration adsorbent 3h after purge vapor absorption desulfurization is washed, and collects sulfur-rich oil, the sulfur-rich oil is incorporated into taking out for embodiment 1
Selective hydrodesulfurization is carried out in fuel-displaced and extraction oil, desulfurization heavy distillat is obtained.
Removal of mercaptans light fraction, desulfurization raffinate oil and desulfurization heavy distillat are mixed, sulfur-free gasoline is obtained, its yield is 95%,
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 the charge ratio of organic solvent and heavy distillat is 0.8 or so,
Now the separating degree of alkene and aromatic hydrocarbons reaches 80% or so in extraction distillation column；
Adsorb in desulfurization, the life-span of desulfuration adsorbent is 3.5h, and absorption desulfuration efficiency reaches outside 85% or so that 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, catalyst for selectively hydrodesulfurizing is prepared
Catalyst for selectively hydrodesulfurizing is prepared according to the method for embodiment 1, unlike, loads of the control Co on carrier
Amount is about that load capacity of 4%, the Mo on carrier is about 10%, and the Co and Mo of supported on carriers mass ratio are 0.4：1.
2nd, gasoline desulfurization
Using the catalytic gasoline in Jinan as raw material (its composition is shown in Table 2), the technological process of desulfurization is carried out such as to the gasoline stocks
Shown in Fig. 3.
The processing of 2.1 removal of mercaptans
Removal of mercaptans processing is carried out to above-mentioned gasoline stocks using mercaptan conversion method (alkali-free sweetening technique), wherein control reaction
The operating pressure of device is 0.5MPa or so, and reaction temperature is 40 DEG C or so, and Feed space velocities are 1.0h-1, air mass flow and inlet amount
Volume ratio be 0.5 or so, collect removal of mercaptans gasoline.
2.2 gasoline are cut
Above-mentioned removal of mercaptans gasoline is cut into light fraction and heavy distillat, wherein gently, the cutting temperature of heavy distillat be 40 DEG C,
I.e.：Light fraction is 40 DEG C of ＜ cut, and double distilled is divided into 40 DEG C of ＞ cut.
2.3 extractive distillations and separation
Using the method for embodiment 1, extractive distillation is carried out to heavy distillat, the raffinate oil containing alkene is obtained and containing vulcanization
The extract of thing and aromatic hydrocarbons；Organic solvent in extract is separated, extraction oil is obtained；Wherein, unlike：
In extractive distillation, organic solvent is the double solvents mixed by sulfolane and tetraethylene glycol, double solvents middle ring
The volume ratio of fourth sulfone and tetraethylene glycol is 8.5：1.5；Extraction distillation column theoretical cam curve is 35, and extractive distillation column overhead temperatures
For 100 DEG C or so, column bottom temperature is 180 DEG C or so, and absolute pressure of top of the tower is 0.4MPa or so, and organic solvent and heavy distillat are entered
Material is than being 3.0 or so, and reflux ratio is 3.0 or so, and now the separating degree of alkene and aromatic hydrocarbons reaches 90% or so in extraction distillation column；
When being washed to extract remainder, the consumption for controlling water is 4% or so.
In separation, the theoretical cam curve of solvent recovery tower is 25, and tower top temperature is 60 DEG C or so, and column bottom temperature is 160 DEG C
Left and right, absolute pressure of top of the tower is 0.03MPa or so, and the charge ratio of steam and extract is 0.4：100 or so, reflux ratio is 1.5
Left and right；The organic solvent water content of solvent recovery tower bottom of towe is 0.8-0.9%.
2.4 selective hydrodesulfurizations
Above-mentioned extraction oil is carried out into selective hydrogenation in the presence of above-mentioned catalyst for selectively hydrodesulfurizing with hydrogen to take off
Sulphur；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, taken off
Sulphur heavy distillat.
2.5 mixing
Above-mentioned light fraction, raffinate oil and desulfurization heavy distillat are mixed, sulfur-free gasoline is obtained, its yield is 97%, and composition is shown in
Table 2.
Embodiment 5
The present embodiment is improved on the basis of embodiment 4, the difference is that：
Absorption desulfurization is carried out to the raffinate oil of embodiment 4, the oily and sulfur-rich oil of desulfurization raffinate is obtained, then by sulfur-rich oil and in fact
Selective hydrodesulfurization is carried out after the extraction oil merging for applying example 4, desulfurization heavy distillat is obtained, its technological process is as shown in Figure 4.
Carry out above-mentioned absorption desulfurization using desulfuration adsorbent, desulfuration adsorbent by Y type molecular sieve respectively through alkali process 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 that load capacity of 10%, the Fe on complex carrier is about 10%, the Zn and Fe quality loaded on complex carrier
Than for 1：1.The Sulfur capacity of the desulfuration adsorbent is 0.481, and long lifespan 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 30 DEG C and condition of normal pressure, with
0.3mL/min flow velocity carries out absorption desulfurization to raffinate oil, obtains desulfurization raffinate oil；After absorption desulfurization, using 180 DEG C of water
Desulfuration adsorbent 1h after purge vapor absorption desulfurization is washed, and collects sulfur-rich oil, the sulfur-rich oil is incorporated to the extraction of embodiment 4
Take and selective hydrodesulfurization is carried out in oil.
Light fraction, desulfurization raffinate oil and desulfurization heavy distillat are mixed, sulfur-free gasoline is obtained, its yield is 95%, and composition is shown in
Table 2.
Reference examples 1
Except the extractive distillation and separation without embodiment 1, and after directly merging the tapped oil of embodiment 1 and heavy distillat
Selective hydrodesulfurization is carried out, desulfurization heavy distillat is obtained；Removal of mercaptans light fraction and desulfurization heavy distillat are mixed, sulfur-free gasoline is obtained
(composition is shown in Table 1), its yield is 94%, and sulfur-free gasoline sulfur content is 9.5ppm, and loss of octane number reaches 3 units.
The composition of gasoline before and after the desulfurization of table 1
Reference examples 2
Except the extractive distillation and separation without embodiment 4, and the heavy distillat directly to embodiment 4 carries out selective hydrogenation
Desulfurization, obtains desulfurization heavy distillat；Light fraction and desulfurization heavy distillat are mixed, sulfur-free gasoline (composition is shown in Table 2) is obtained, its yield is
92%, sulfur-free gasoline sulfur content is 9.8ppm, and loss of octane number reaches 3 units.
The composition of gasoline before and after the desulfurization of table 2
Reference examples 3
Except the gasoline cutting without embodiment 1 and removal of mercaptans are handled, and directly using the method for embodiment 1 to embodiment 1
Gasoline stocks carry out extractive distillation and separation, obtain extraction oil and raffinate oil, then extraction oil entered using the method for embodiment 1
Row selective hydrodesulfurization, obtains 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 is 8.9ppm, and loss of octane number reaches 1.5 units.
From the above results：
When the 1st, carrying out desulfurization to gasoline stocks using various embodiments of the present invention method, sulfur content reaches in sulfur-free gasoline
Below 10ppm, octane number reduction by 1 unit of ＜, product yield ＞ 95% (except embodiment 3)；And reference examples 1 and reference examples 2
Method directly carries out selective hydrodesulfurization without extractive distillation and separation of the invention to heavy distillat, now octane number
Loss reaches 3 units；The method of reference examples 3 without gasoline cut and directly to the full cut of gasoline stocks carry out extractive distillation and
Separation, loss of octane number reaches 1.5 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, the separation of alkene and aromatic hydrocarbons, which is also helped, avoids the institute in subsequent adsorbtion sweetening process
Caused competitive Adsorption, 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 is merely illustrative of the technical solution of the present invention, rather than its limitations；To the greatest extent
The present invention is described in detail with reference to foregoing embodiments for pipe, it will be understood by those within the art that：Its according to
The technical scheme described in foregoing embodiments can so be modified, or which part or all technical characteristic are entered
Row equivalent；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology
The scope of scheme.
Claims (9)
1. a kind of combined method of gasoline desulfurization, it is characterised in that comprise the following steps：
Gasoline stocks are cut into light fraction and heavy distillat；
Extractive distillation is carried out to the heavy distillat using organic solvent, the raffinate oil containing alkene is obtained and containing sulfide and virtue
The extract of hydrocarbon；
Organic solvent in the extract is separated, extraction oil is obtained；
Selective hydrodesulfurization is carried out to the extraction oil, desulfurization heavy distillat is obtained；
The light fraction, raffinate oil and desulfurization heavy distillat are mixed, sulfur-free gasoline is obtained；
Wherein, the cutting temperature of the light fraction and heavy distillat is 35-60 DEG C；
The extractive distillation includes：The heavy distillat is set to enter from extraction distillation column middle and lower part, organic solvent is from extraction distillation column
Top enters；Wherein, the theoretical cam curve of the extraction distillation column is 25-45, and tower top temperature is 70-110 DEG C, and column bottom temperature is
150-190 DEG C, absolute pressure of top of the tower is 0.1-0.5MPa, and the input material volume ratio of organic solvent and heavy distillat is 1.0-5.0, backflow
Than for 0.1-4.0.
2. combined method according to claim 1, it is characterised in that first the gasoline stocks are carried out after removal of mercaptans processing
Light fraction and heavy distillat are cut into again；Or, to the light fraction carry out removal of mercaptans processing after again with the raffinate oil and desulfurization
Heavy distillat is mixed.
3. combined method according to claim 1, it is characterised in that the organic solvent is selected from diethylene glycol (DEG), triethylene glycol, four
Glycol, dimethyl sulfoxide, sulfolane, N- N-formyl morpholine Ns, 1-METHYLPYRROLIDONE, polyethylene glycol and one kind in propene carbonate or
It is a variety of.
4. combined method according to claim 1, it is characterised in that the separation includes：Make the extract from solvent
Recovery tower middle and upper part enters, and steam enters from solvent recovery tower bottom；Wherein, the theoretical cam curve of the solvent recovery tower is
10-30, tower top temperature is 50-100 DEG C, and column bottom temperature is 150-200 DEG C, and absolute pressure of top of the tower is 0.03-0.07MPa, steam
Charge-mass ratio with extract is (0.1-0.5)：100, reflux ratio is 0.2-4.0.
5. combined method according to claim 1, it is characterised in that take off the extraction oil and hydrogen in selective hydrogenation
The selective hydrodesulfurization is carried out in the presence of sulfur catalyst；Wherein, the temperature for controlling the selective hydrodesulfurization is
200-300 DEG C, pressure is 1.5-2.5MPa, and volume space velocity is 1-5h-1, hydrogen to oil volume ratio is 400-600.
6. combined method according to claim 5, it is characterised in that the catalyst for selectively hydrodesulfurizing is born by carrier
Carry active metal components and obtain；Wherein, the carrier be molecular sieve or metal oxide, the active metal include Co and
Mo, and the total load amount of Co and Mo on the carrier is 5-20%.
7. according to any described combined method of claim 1 to 6, it is characterised in that first carry out absorption to raffinate oil de-
Mixed again with the light fraction and desulfurization heavy distillat after sulphur.
8. combined method according to claim 7, it is characterised in that carry out the absorption desulfurization using desulfuration adsorbent,
The desulfuration adsorbent is obtained by molecular sieve and activated carbon through alkali process respectively as composite carrier load active metal components
Arrive；Wherein, one or more elements of the active metal in periodic table IA, VIII, IB, IIB and group vib, the work
Property load capacity of the metal on complex carrier be 2-30%.
9. combined method according to claim 8, it is characterised in that the absorption desulfurization is entered using fixed bed atmospheric pressure
OK, and control adsorb desulfurization temperature be 20-100 DEG C, raffinate oil flow velocity be 0.3-1mL/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201186917Y (en) * | 2008-01-29 | 2009-01-28 | 丁冉峰 | System for preparing high-quality petrol |
| CN101376842A (en) * | 2007-08-31 | 2009-03-04 | 中国石油化工股份有限公司 | Method for reducing sulfur content in gasoline |
| CN101899326A (en) * | 2010-05-14 | 2010-12-01 | 大连理工大学 | Shale oil catalytic upgrading method |
| CN102337153A (en) * | 2010-07-22 | 2012-02-01 | 中国石油天然气股份有限公司 | Hydrotreatment method of gasoline distillate oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376842A (en) * | 2007-08-31 | 2009-03-04 | 中国石油化工股份有限公司 | Method for reducing sulfur content in gasoline |
| CN201186917Y (en) * | 2008-01-29 | 2009-01-28 | 丁冉峰 | System for preparing high-quality petrol |
| CN101899326A (en) * | 2010-05-14 | 2010-12-01 | 大连理工大学 | Shale oil catalytic upgrading method |
| CN102337153A (en) * | 2010-07-22 | 2012-02-01 | 中国石油天然气股份有限公司 | Hydrotreatment method of gasoline distillate oil |
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