CN108659884A - The method of gasoline desulfurization - Google Patents
The method of gasoline desulfurization Download PDFInfo
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- CN108659884A CN108659884A CN201710193497.7A CN201710193497A CN108659884A CN 108659884 A CN108659884 A CN 108659884A CN 201710193497 A CN201710193497 A CN 201710193497A CN 108659884 A CN108659884 A CN 108659884A
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- gasoline
- desulfurization
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural parallel stages only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a kind of method of gasoline desulfurization, this method includes：Gasoline stocks are subjected to the first cutting, obtain the first light gasoline fraction and the first heavy naphtha；The first heavy naphtha of gained is sent into first set fluidizing reactor and is contacted with absorbing desulfurization catalyst and carries out the first desulphurization reaction in the case where facing hydrogen state, obtains the first desulfurization product；The first light gasoline fraction of gained is sent into second set of fluidizing reactor, the second desulphurization reaction is contacted and carried out with absorbing desulfurization catalyst, obtains the second desulfurization product；The first desulfurization product of gained is subjected to the second cutting, obtains the second light gasoline fraction and the second heavy naphtha；The second desulfurization product of gained and the second light gasoline fraction are subjected to etherification process together, obtain etherificate oil.Method provided by the invention can reduce sulphur and olefin(e) centent in gasoline, and can reduce octane number loss simultaneously and keep high yield of gasoline.
Description
Technical field
The present invention relates to a kind of methods of gasoline desulfurization.
Background technology
Atmosphere pollution getting worse caused by motor vehicle exhaust emission.As people are to the pay attention to day by day of environmental protection, China
The paces of vehicle fuel quality upgrading are accelerated, standard GB/T 17930-2013 requires sulfur content in gasoline to be not more than 10 μ g/
G, volume fraction of olefins are not more than 24%.
Catalytically cracked gasoline is the chief component of China's motor petrol, and 75% or so is accounted in gasoline pool, and it is special
Point is that have higher alkene and sulfur content.The deep desulfuration of gasoline is realized using hydrogen addition technology and is reduced in catalytically cracked gasoline
Olefin(e) centent it is not difficult, but since alkene is antiknock component, being greatly reduced for content will lead to octane number
Heavy losses, to influence the automobile-used performance of gasoline and the economic benefit of oil plant, therefore in the deep desulfuration for realizing gasoline
Octane number is kept to become the hot spot of China's clean gasoline production simultaneously.
Currently, the deep desulfuration of gasoline is mainly using hydrodesulfurization or the method for adsorbing desulfurization.Selective hydrodesulfurization
It is one of the major way of current removing thiophene-type sulfide, but the reactions such as alkene saturation equally largely occur, and cause octane number
It loses larger.In addition, the deep hydrogenation method for restoring octane number is similarly approved by people, it is to carry out deep desulfuration and alkene
While saturation, setting second reactor is to promote cracking hydrocarbon, isomerization and the alkylated reaction of low octane rating, to reach
Restore the purpose of octane number.Absorption method remove fuel oil in sulfur-containing compound, be using absorbing desulfurization catalyst to light oil into
Row faces hydrogen reaction absorption, generates metal sulfide or removes sulphur using sulfide polarity, and hydrogen consumption is relatively low, and desulfuration efficiency is high, can be with
Sulfur content is produced in the 10 following gasoline of μ g/g.Although absorbing process realizes the deep desulfuration of gasoline, vapour under the conditions of low hydrogen consumes
Oily product octane number still slightly loses.Especially when handling olefin(e) centent height and the high gasoline stocks of sulfur content, still make
It is lost at octane number larger.
Chinese patent CN101845322A discloses a kind of method reducing sulfur in gasoline and olefin(e) centent, and catalytic material is split
Change gasoline and first pass through pre-hydrogenator removing alkadienes, light, heavy petrol is fractionated into subsequently into fractionating column cutting, light petrol into
Row faces hydrogen absorption desulfurization, and heavy petrol enters selective hydrogenation reactor hydrodesulfurization, and it is anti-that reaction effluent enters back into hydro-upgrading
It answers device to carry out hydro-upgrading, reduces olefin(e) centent, the heavy petrol after modification reconciles with light petrol absorption desulfurization product to be met
The clean gasoline that standard requires.
The method that Chinese patent CN1766057A discloses production low sulfur, low olefin gasoline, is by full boiling range cracked naphtha
At least two fractions are separated into, polyunsaturated compounds are selectively hydrogenated, then by light gasoline fraction etherificate, heavy naphtha
Hydrodesulfurization or chemisorption carry out removal of sulphur, finally merge two kinds of fractions and obtain low sulfur, low olefin gasoline.The present invention will be handled
Low sulfur, low olefin gasoline is obtained, but gasoline product octane number is expected to reduce to a certain degree.
Since technique is when reducing sulfur content of catalytic cracking gasoline for gasoline absorbing desulfurization (abbreviation S Zorb), octane number
Lose less, while plant energy consumption is relatively low.Therefore, domestic many oil plants select S Zorb technologies to handle catalytic cracking vapour
Oil builds more set S Zorb devices, the in this way space there is optimization catalytically cracked gasoline processing technological flow.
Invention content
The object of the present invention is to provide a kind of method of gasoline desulfurization, method provided by the invention can reduce in gasoline
Sulphur and olefin(e) centent, and octane number loss can be reduced simultaneously and keep high yield of gasoline.
To achieve the goals above, the present invention provides a kind of method of gasoline desulfurization, and this method includes：By gasoline stocks into
Row first is cut, and obtains the first light gasoline fraction and the first heavy naphtha；The first heavy naphtha of gained is sent into first set
It is contacted with absorbing desulfurization catalyst in fluidizing reactor and carries out the first desulphurization reaction in the case where facing hydrogen state, obtain the first desulfurization
Product；The first light gasoline fraction of gained is sent into second set of fluidizing reactor, the is contacted and carried out with absorbing desulfurization catalyst
Two desulphurization reactions obtain the second desulfurization product；The first desulfurization product of gained is subjected to the second cutting, obtains the second light gasoline fraction
With the second heavy naphtha；The second desulfurization product of gained and the second light gasoline fraction are subjected to etherification process together, are etherified
Oil；Wherein, the condition of first desulphurization reaction includes：First reaction temperature is 380-470 DEG C, and the first reaction pressure is 2.0-
3.5MPa；The condition of second desulphurization reaction includes：Second reaction temperature is 360-450 DEG C, and the second reaction pressure is 1.5-
3.0MPa。
Optionally, second reaction temperature is 5 DEG C -30 DEG C lower than the first reaction temperature；And/or second reaction pressure
Power is lower 0.1MPa-1.0MPa than the first reaction pressure.
Optionally, this method further includes：The second heavy naphtha of gained is mixed with etherificate oil, obtains gasoline products.
Optionally, volume fraction of olefins is more than 10 body % in the gasoline stocks.
Optionally, in the gasoline stocks sulfur content more than 10 μ g/g.
Optionally, the gasoline stocks are selected from catalytically cracked gasoline, catalytic cracking gasoline, coker gasoline, thermal cracking vapour
At least one of oil and direct steaming gasoline.
Optionally, the cut point of first light gasoline fraction and the first heavy naphtha is 60-100 DEG C, the second light vapour
The cut point of oil distillate and the second heavy naphtha is 60-100 DEG C.
Optionally, the first set fluidizing reactor and second set of fluidizing reactor are each independently selected from fluidisation
Bed, riser, downstriker pipeline reactor, the compound reactor being made of riser and fluid bed, by riser and downlink
Formula pipeline constitute compound reactor, be made of two or more risers compound reactor, by two or two
A above fluid bed compound reactor constituted and the recombination reaction being made of two or more downstriker pipelines
One or more of at least one of device, preferably equal diameter riser, variable diameters riser and dense-phase fluidized bed reactor,
First set fluidizing reactor and second set of fluidizing reactor belong to gasoline absorbing desulfurization device.
Optionally, the absorbing desulfurization catalyst contains silica, aluminium oxide, zinc oxide and desulphurizing activated metal, institute
It is selected from least one of cobalt, nickel, copper, iron, manganese, molybdenum, tungsten, silver, tin and vanadium to state desulphurizing activated metal.
Optionally, on the basis of the dry weight of the absorbing desulfurization catalyst and in terms of oxide weight, the absorption
Zinc oxide described in desulphurization catalyst accounts for 10-90 weight %, and silica accounts for 5-85 weight %, and aluminium oxide accounts for 5-30 weight %；
On the basis of the dry weight of the absorbing desulfurization catalyst and in terms of element wt, taken off described in the absorbing desulfurization catalyst
The content of sulphur active metal is 5-30 weight %.
Optionally, the step of etherification process includes：By second light gasoline fraction and second desulfurization product
It is contacted with alcohols, makes the alkene in second light gasoline fraction and second desulfurization product under the action of catalyst for etherification
Etherification reaction occurs with alcohols, obtains the etherificate oil；Wherein, the temperature of the etherification reaction is 20-200 DEG C, and pressure is
0.1-5MPa, weight (hourly) space velocity (WHSV) are 0.1-20 hours -1, and the molal quantity of the alcohols and second light gasoline fraction and second are de-
The ratio of the sum of the molal quantity of sulphur product is 1：(0.1-100), the catalyst for etherification include selected from resin, molecular sieve and miscellaneous more
At least one of acid.
The present invention has the following technical effects compared with prior art：
1, gasoline stocks are divided into the first light gasoline fraction and the first heavy naphtha by method of the invention, then by two
Kind gasoline fraction is handled in two fluidizing reactors respectively, and reaction condition that is harsh or mitigating can be respectively adopted, dropping
While low gasoline component sulfur content, additionally it is possible to keep the octane number and high yield of gasoline.
2, the second light gasoline fraction and the second desulfurization product are carried out etherification process by the present invention, are not only eliminated light petrol and are evaporated
Divide pretreatment unit, moreover, wherein alkene can either be reduced, additionally it is possible to produce high-octane etherification product, improve gasoline production
The octane number of product.
3, method of the invention can also reduce the light component in gasoline, reduce gasoline vapour pressure.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is a kind of flow diagram of specific implementation mode of the method for the present invention.
Reference sign
1 gasoline stocks Cutting Tap, 2 first set fluidizing reactor, 3 first set high-pressure separator
4 second sets of fluidizing reactors, 5 second sets of 6 destilling towers of high-pressure separator
7 methyltertiarvbutyl ether reactor, 8 etherification product fractionating column, 9 mixer
10 pipeline, 11 pipeline, 12 pipeline
13 pipeline, 14 pipeline, 15 pipeline
16 pipeline, 17 pipeline, 18 pipeline
19 pipeline, 20 pipeline, 21 pipeline
22 pipeline, 23 pipeline, 24 pipeline
25 pipeline, 26 pipeline
Specific implementation mode
The specific implementation mode of the present invention is described in detail below in conjunction with attached drawing.It should be understood that this place is retouched
The specific implementation mode stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
In the present invention RIPP test methods for details, reference can be made to《Petrochemical analysis method》, Yang Cui is surely equal to be compiled, nineteen ninety version.
The present invention provides a kind of method of gasoline desulfurization, and this method includes：Gasoline stocks are subjected to the first cutting, obtain the
One light gasoline fraction and the first heavy naphtha；The first heavy naphtha of gained is sent into first set fluidizing reactor and suction
Attached hydrodesulfurization catalyst simultaneously carries out the first desulphurization reaction in the case where facing hydrogen state, obtains the first desulfurization product；Gained first is light
Gasoline fraction is sent into second set of fluidizing reactor and the second desulphurization reaction is contacted and carried out with absorbing desulfurization catalyst, obtains the
Two desulfurization products；The first desulfurization product of gained is subjected to the second cutting, obtains the second light gasoline fraction and the second heavy naphtha；
The second desulfurization product of gained and the second light gasoline fraction are subjected to etherification process together, obtain etherificate oil；Wherein, described first is de-
The condition of reaction of Salmon-Saxl includes：First reaction temperature is 380-470 DEG C, and the first reaction pressure is 2.0-3.5MPa；Described second is de-
The condition of reaction of Salmon-Saxl includes：Second reaction temperature is 360-450 DEG C, and the second reaction pressure is 1.5-3.0MPa.
According to the present invention, desulphurization reaction refer to gasoline stocks under the action of under facing hydrogen state in absorbing desulfurization catalyst into
The process of row desulfurization, condition may include：Reaction temperature is 350-500 DEG C, reaction pressure 0.5-3.5MPa, weight (hourly) space velocity (WHSV)
It is 2-50 hours-1, hydrogen is with gasoline stocks volume ratio (in the status of criterion (STP) 0 DEG C of (273K), 1.01 × 105Under Pa) it is 1-
500。
Inventor is it was unexpectedly observed that by the first heavy naphtha and the first light gasoline fraction point in gasoline stocks
Desulphurization reaction is not carried out, can improve the yield and octane number of gasoline products；For example, the first reaction temperature of the first desulphurization reaction
It can be 380-470 DEG C, preferably 410-450 DEG C, the first reaction pressure can be 2.0-3.5MPa, preferably 2.2-
3.0MPa；Second reaction temperature of the second desulphurization reaction can be 360-450 DEG C, preferably 380-430 DEG C, the second reaction pressure
Can be 1.5-3.0MPa, preferably 2.0-2.7MPa.
Further, inventor also found that the desulfurization of the first heavy naphtha of control and the first light gasoline fraction is anti-
Condition is answered, the yield and octane number of gasoline products can be further increased, for example, second reaction temperature is at least more anti-than first
Answer temperature 5 DEG C low, it is 10 DEG C preferably at least low, it is 20 DEG C more preferably at least low, it is further preferably 30 DEG C at least low, further,
Second reaction temperature is 5-30 DEG C lower than the first reaction temperature；And/or second reaction pressure is at least than the first reaction pressure
Power low 0.1MPa, preferably at least low 0.2MPa, more preferably at least low 0.5MPa, further preferably at least low 1.0MPa.
According to the present invention, in order to which direct producing country V even VI label gasoline of state, this method can also include：By gained
Two heavy naphthas are mixed with etherificate oil, obtain gasoline products.
According to the present invention, gasoline stocks are well-known to those skilled in the art, can be selected from catalytically cracked gasoline, urge
Change at least one of drippolene, coker gasoline, pressure gasoline and direct steaming gasoline.The gasoline that the present invention is handled is preferably height
Alkene and high sulfur oil, volume fraction of olefins are generally higher than 10 body %, preferably greater than 20 body %, more preferably greater than 30 body %,
Further preferably greater than 40 body % are further more than 50 body %；Sulfur content is generally more than 10 μ g/g, preferably greater than 50 μ g/
G, more preferably greater than 100 μ g/g, further preferably greater than 500 μ g/g are still more preferably more than 1000 μ g/g, having in gasoline
Machine sulfide is generally mercaptan, thioether, thiophene, alkylthrophene, benzothiophene and methyl benzothiophene etc..
The cutting mode of gasoline fraction is not limited according to the present invention.For example, for catalytically cracked gasoline,
Gasoline Cutting Tap may be used in the cutting of gasoline fraction, can also use the condensed in two stages of such as catalytic cracking main fractionating tower setting
Cooling process.The cut point and the second light gasoline fraction and the second weight of first light gasoline fraction and the first heavy naphtha
The cut point of gasoline fraction can be each independently 60-100 DEG C, preferably 60-80 DEG C, further preferably 65-80 DEG C, institute
The Engler distillation for stating the first light gasoline fraction and the second light gasoline fraction does preferably 60-100 DEG C each independently, further
Preferably 60-80 DEG C.The cutting of gasoline stocks and/or the first desulfurization product generally in fractionating column according to boiling range from low to high into
Row, for example, the operating condition of the fractionating column of gasoline stocks is：Tower top temperature is 60-80 DEG C, and column bottom temperature is 120-160 DEG C, behaviour
It is 0.05-0.3MPa to make pressure.
According to the present invention, fluidizing reactor is well-known to those skilled in the art, for example, can be selected from fluid bed,
It is riser, downstriker pipeline reactor, the compound reactor being made of with fluid bed riser, defeated by riser and downstriker
Compound reactor that line sending is constituted, the compound reactor being made of two or more risers, by two or two with
On the fluid bed compound reactor constituted and the compound reactor being made of two or more downstriker pipelines in
At least one, preferably riser reactor and/or fluidized-bed reactor, each above-mentioned reactor be segmented into two or two
A above reaction zone.The fluidized-bed reactor can be selected from fixed fluidized bed, dispersion fluidized bed, bubbling bed, turbulent bed,
Fast bed, conveying one or more of bed and dense-phase fluidized bed；The riser reactor can be to be promoted selected from equal diameter
Pipe, etc. one or more of linear speeds riser and various variable diameters risers.Preferably, the fluidizing reactor is selected from close
Phase fluidizing reactor, more preferably variable diameters riser reactor.
According to the present invention, absorbing desulfurization catalyst is well-known to those skilled in the art, for example, the absorption desulfurization is urged
Agent can contain silica, aluminium oxide, zinc oxide and desulphurizing activated metal, the desulphurizing activated metal can be selected from
At least one of cobalt, nickel, copper, iron, manganese, molybdenum, tungsten, silver, tin and vanadium.
A kind of specific implementation mode, on the basis of the dry weight of the absorbing desulfurization catalyst and with oxide weight
Meter, zinc oxide described in the absorbing desulfurization catalyst account for 10-90 weight %, and silica accounts for 5-85 weight %, and aluminium oxide accounts for
5-30 weight %；On the basis of the dry weight of the absorbing desulfurization catalyst and in terms of element wt, the absorption desulfurization is urged
The content of desulphurizing activated metal described in agent is 5-30 weight %.
According to the present invention, etherification process refers to by C in light petrol (including the second light gasoline fraction and second desulfurization product)5
Low-carbon hydro carbons (such as iso-amylene and cyclopentene) below carries out etherification reaction with alcohols, to generate high-octane etherificate oil,
For example, the step of etherification process, may include：By second light gasoline fraction and second desulfurization product and alcohols
Contact, make the alkene in second light gasoline fraction and second desulfurization product under the action of catalyst for etherification with alcohols
Etherification reaction occurs, obtains the etherificate oil；Wherein, the temperature of the etherification reaction is 20-200 DEG C, pressure 0.1-5MPa,
Weight (hourly) space velocity (WHSV) is 0.1-20 hours-1, the molal quantity of the alcohols and the second light gasoline fraction and second desulfurization product rub
The ratio of the sum of your number is 1：(0.1-100), the catalyst for etherification include in resin, molecular sieve and heteropoly acid at least
It is a kind of.
Strong acid cation exchange resin catalyst is loaded on one section of etherificate by a kind of specific implementation mode of etherification process
And/or in two sections of etherificate fixed bed reactors, pretreated second light gasoline fraction and the institutes such as desulfurization and dialkene removal will be passed through
It states the second desulfurization product to be passed through in methyltertiarvbutyl ether reactor, is 50-90 DEG C in reaction temperature, liquid hourly space velocity (LHSV) 1.0-3.0h-1, methanol and
It is sent out under conditions of active olefin (isomeric olefine, such as iso-amylene) molar ratio 1-2 in two light gasoline fractions and the second desulfurization product
Raw etherification reaction, etherification product are sent into rectifying column separation, and etherificate oil, unreacted lighter hydrocarbons and methanol loop profit are obtained in bottom of tower
With.Etherification procedure reaction temperature preferably is 55-60 DEG C of inlet temperature, and outlet temperature is less than 90 DEG C, and air speed is preferably 1-2h-1, active olefin molar ratio is preferably 1.2-1.4 in methanol and the second light gasoline fraction and second desulfurization product.Wherein, one
Section etherificate olefin(e) centent is higher, and suitable for using mixed phase bed reactor, two sections of etherificate olefin(e) centents are relatively low, suitable for using adiabatic fixed
Bed reactor.In addition, isomerization unit can also be applied to during Etherification of Light FCC Gasoline.Etherification of Light FCC Gasoline has reduction gasoline alkene
Hydrocarbon content improves octane number, reduces vapour pressure and improves added value and strengthens many advantages, such as reconciling benefit, and etherificate oil can be with
It is used, can also be mixed with heavy naphtha as full distillation gasoline product as octane number blend component.
A kind of specific implementation mode of the present invention is provided below in conjunction with attached drawing, but it is not thereby limiting the invention.
As shown in Figure 1, gasoline stocks are sent into gasoline stocks Cutting Tap 1 through pipeline 10 carries out the first cutting, tower top cutting
The first obtained light gasoline fraction introduces first set fluidizing reactor 2 through pipeline 11, is mixed with the hydrogen introduced through pipeline 12,
The first desulphurization reaction is carried out under the action of absorbing desulfurization catalyst, the reaction oil gas of generation introduces first set high pressure through pipeline 13
Separator 3, isolated first light petrol product are drawn through pipeline 14.The first heavy vapour that 1 bottom of tower of gasoline stocks Cutting Tap obtains
Oil distillate introduces second set of fluidizing reactor 4 through pipeline 16, is mixed with the hydrogen introduced through pipeline 17, in absorption desulfurization catalyst
The second desulphurization reaction is carried out under the action of agent, the reaction oil gas of generation introduces second set of high-pressure separator 5 through pipeline 18 and detaches, point
From obtaining the second desulfurization product and lead to destilling tower 6 through pipeline 19 to carry out the second cutting, the second light gasoline fraction for cutting and
Second heavy naphtha is drawn by pipeline 22 and pipeline 21 respectively, wherein the second light gasoline fraction and the second heavy naphtha
Cut point is about 60~70 DEG C.The second light gasoline fraction drawn by pipeline 22 and the first desulfurization product remittance drawn by pipeline 14
Merging is mixed with the methanol introduced through pipeline 23, is reacted into methyltertiarvbutyl ether reactor 7, and etherification product introduces etherification product through pipeline 24
Fractionating column 8 is fractionated into obtain etherificate oil and tail gas, and tail gas is drawn through pipeline 26, etherificate oil drawn through pipeline 25 and with the second weight
Gasoline fraction, which converges, introduces mixer 9, obtains gasoline products.
The following examples will be further described the present invention, but not thereby limiting the invention.
Absorbing desulfurization catalyst used in following example and comparative example is by Sinopec Group
Catalyst branch produces, and goods number FCAS, absorbing desulfurization catalyst property is listed in table 3.
In following embodiment and comparative example, NiO, ZnO, Al in catalyst2O3、SiO2Content x-ray fluorescence method
It measures, wherein Al2O3、SiO2Content measured referring specifically to RIPP 134-90, remaining composition measuring method is similar.
The octane number of gasoline is measured using RIPP 85-90 methods in the embodiment of the present invention and comparative example, gasoline PONA
(being tested using RIPP81-90 test methods) is analyzed using simulation distillation and gasoline detailed hydrocarbon, during content of sulfur in gasoline uses
Magnificent people's republic's standard GB/T/T380-1977 oil product sulphur content determination methods (Ignition Lamp Method) are measured.
Fluidizing reactor used in embodiment and comparative example is small fixed fluidized bed unit.
Embodiment 1
Gasoline fraction used in embodiment 1 is oil plant stable gasoline A, and property is listed in table 1.As shown in Figure 1, by steady
Determine gasoline A to be distilled in gasoline stocks Cutting Tap 1, be cut into the first light gasoline fraction and the first gasoline heavy distillat, controls
The first light gasoline fraction end point of distillation is 65-70 DEG C (being carried out according to ASTM D86 standards).Wherein, stable gasoline A distills
First light gasoline fraction is denoted as LCN-A-1, and the first heavy naphtha is denoted as HCN-A-1, and property is listed in table 2；By the first heavy petrol
Fraction HCN-A-1 is sent into first set fluidizing reactor 4 and is contacted with desulphurization catalyst FCAS and carry out first in the case where facing hydrogen state
Desulphurization reaction, reaction condition are listed in table 4, are cooled and separated to obtain tail gas and first by the reaction product that reactor head obtains
Desulfurization product (is denoted as gasoline after HCN-A-1 desulfurization, 4) property is shown in Table.Gasoline after HCN-A-1 desulfurization is sent into destilling tower 6, control
65 DEG C or so of 6 tower top temperature of destilling tower processed, tower top obtain the second light gasoline fraction LCN-A-2, and bottom of tower obtains the second heavy petrol and evaporates
HCN-A-2, property is divided equally to be listed in table 2；The first light gasoline fraction of gained LCN-A-1 is sent into first set fluidizing reactor 2
It is contacted with desulphurization catalyst FCAS and carries out the second desulphurization reaction in the case where facing hydrogen state, reaction condition is equally listed in table 4, by reacting
The reaction product obtained at the top of device be cooled and separated to obtain tail gas and the second desulfurization product (be denoted as gasoline after LCN-A-1 desulfurization,
4) property is shown in Table；Second light gasoline fraction LCN-A-2 is converged with gasoline after LCN-A-1 desulfurization and is mixed with methanol, into ether
Change reactor 7 to react, etherification reaction condition is 55-80 DEG C of reaction temperature, air speed 1.2h-1, methanol and the second light gasoline fraction
LCN-A-2 and gross activity alkene (isomeric olefine) molar ratio 1.2, etherification product obtained by the reaction in gasoline after LCN-A-1 desulfurization
The etherified fractionation of product fractionation tower 8 obtains bottom of tower etherificate oil and contains methanol-fueled exhaust with tower top, wherein the tower top temperature of etherificate fractionating column
It it is 60-80 DEG C, column bottom temperature is 110-140 DEG C, and etherificate oil is denoted as LCN-A-M-0, and property is listed in table 2.By the second heavy vapour of gained
Oil distillate HCN-A-2 and LCN-A-M-0 mixing, obtains the gasoline products as treated gasoline, property is shown in Table 5.
Embodiment 2
Embodiment 2 and the operation of embodiment 1 are essentially identical, the difference is that, the temperature of the second desulphurization reaction of control is
410 DEG C, gasoline products are obtained, property is shown in Table 5.
Embodiment 3
Embodiment 3 and the operation of embodiment 1 are essentially identical, the difference is that, the temperature of the second desulphurization reaction of control is
410 DEG C, pressure 1.9MPa, gasoline products are obtained, property is shown in Table 5.
Embodiment 4
Embodiment 4 and the operation of embodiment 1 are essentially identical, the difference is that, the temperature of the second desulphurization reaction of control is
415 DEG C, pressure 2.1MPa, gasoline products are obtained, property is shown in Table 5.
Comparative example 1
Stable gasoline A second set of fluidizing reactor 2 of feeding is contacted with absorbing desulfurization catalyst FCAS and is facing hydrogen shape
Desulphurization reaction is carried out under state, reaction condition is listed in table 4, is cooled and separated to obtain tail by the desulfurization product that reactor head obtains
Gasoline product (is denoted as gasoline after CN-A desulfurization, 5) property is shown in Table, gasoline product is not fractionated into and is etherified after desulfurization after gas and desulfurization
As gasoline products；For gasoline as gasoline products, property is listed in table 5 after CN-A desulfurization.
Comparative example 2
It is carried out in two steps, the first step is identical as the operation of comparative example 1, and second step is that gasoline after CN-A desulfurization is sent into distillation
Light gasoline fraction LCN-A-S and heavy naphtha HCN-A-S are cut into tower, wherein the control light gasoline fraction end point of distillation is 65-
70 DEG C (being carried out according to ASTM D86 standards).Light gasoline fraction LCN-A-S and methanol are mixed into methyltertiarvbutyl ether reactor and carry out ether
Change reaction, etherification reaction condition and operation are same as Example 1, and the corresponding oil that is etherified is denoted as LCN-A-M-S, and property equally arranges
In table 2.
Heavy naphtha HCN-A-S obtained above and etherificate oil LCN-A-M-S is mixed to get gasoline products, property row
In table 5.
It can be seen from Table 5 that embodiment 1-4 is suitable with the desulfuration efficiency of comparative example 1 and comparative example 2, but embodiment 1
Research octane number (RON) 3.3 units of loss fewer than comparative example 1,0.8 unit of loss fewer than comparative example 2；The organon of embodiment 2
Octane number 3.3 units of loss fewer than comparative example 1,0.6 unit of loss fewer than comparative example 2；The research octane number (RON) of embodiment 3
3.1 units of loss fewer than comparative example 1,0.8 unit of loss fewer than comparative example 2；The research octane number (RON) of embodiment 4 is than comparison
Example 1 loses 2.6 units, 0.1 unit of loss fewer than comparative example 2 less.
Table 1
| Gasoline stocks | Stable gasoline A |
| 20 DEG C of density, kg/m3 | 737.3 |
| 20 DEG C of refractive index | 1.4212 |
| Carbon content, % (w) | 86.36 |
| Hydrogen content, % (w) | 13.64 |
| Sulfur content, mg/L | 421 |
| Nitrogen content, mg/L | 139 |
| Induction period, min | 667 |
| Race forms (FIA methods) | |
| Aromatic hydrocarbons, % (volume fraction) | 15.4 |
| Alkene, % (volume fraction) | 54.9 |
| Saturated hydrocarbons, % (volume fraction) | 29.7 |
| Survey RON | 90.9 |
| Survey MON | 78.9 |
| Normal pressure boiling range, DEG C | |
| IBP | 44 |
| 5% | 59 |
| 10% | 63 |
| 30% | 80 |
| 50% | 106 |
| 70% | 139 |
| 90% | 175 |
| FBP | 204 |
Table 2
Table 3
| Catalyst | FCAS |
| Chemical composition, weight % | |
| Aluminium oxide | 11 |
| Nickel oxide | 20 |
| Zinc oxide | 49 |
| Silica | 20 |
| Apparent density, kg/m3 | 1130 |
| Screening composition, weight % | |
| 0~40 micron | 14.5 |
| 40~80 microns | 51.9 |
| >80 microns | 33.6 |
Table 4
Table 5
Claims (12)
1. a kind of method of gasoline desulfurization, this method include：
Gasoline stocks are subjected to the first cutting, obtain the first light gasoline fraction and the first heavy naphtha；
The first heavy naphtha of gained is sent into first set fluidizing reactor and is contacted with absorbing desulfurization catalyst and is facing hydrogen
The first desulphurization reaction is carried out under state, obtains the first desulfurization product；
The first light gasoline fraction of gained is sent into second set of fluidizing reactor, the is contacted and carried out with absorbing desulfurization catalyst
Two desulphurization reactions obtain the second desulfurization product；
The first desulfurization product of gained is subjected to the second cutting, obtains the second light gasoline fraction and the second heavy naphtha；
The second desulfurization product of gained and the second light gasoline fraction are subjected to etherification process together, obtain etherificate oil；
Wherein, the condition of first desulphurization reaction includes：First reaction temperature is 380-470 DEG C, and the first reaction pressure is
2.0-3.5MPa；The condition of second desulphurization reaction includes：Second reaction temperature is 360-450 DEG C, and the second reaction pressure is
1.5-3.0MPa。
2. according to the method described in claim 1, wherein, second reaction temperature is 5 DEG C -30 DEG C lower than the first reaction temperature；
And/or second reaction pressure is lower 0.1MPa-1.0MPa than the first reaction pressure.
3. according to the method described in claim 1, this method further includes：The second heavy naphtha of gained is mixed with etherificate oil,
Obtain gasoline products.
4. according to the method described in claim 1, wherein, volume fraction of olefins is more than 10 body % in the gasoline stocks.
5. according to the method described in claim 1, wherein, sulfur content is more than 10 μ g/g in the gasoline stocks.
6. according to the method described in claim 1, wherein, the gasoline stocks are selected from catalytically cracked gasoline, catalytic pyrolysis vapour
At least one of oil, coker gasoline, pressure gasoline and direct steaming gasoline.
7. according to the method described in claim 1, wherein, the cut point of first light gasoline fraction and the first heavy naphtha
It it is 60-100 DEG C, the cut point of the second light gasoline fraction and the second heavy naphtha is 60-100 DEG C.
8. according to the method described in claim 1, wherein, the first set fluidizing reactor and second set of fluidizing reactor
It is each independently selected from fluid bed, riser, downstriker pipeline reactor, the recombination reaction being made of riser and fluid bed
Device, the compound reactor being made of with downstriker pipeline riser, be made of two or more risers it is compound
It reactor, the compound reactor being made of two or more fluid beds and is conveyed by two or more downstrikers
At least one of the compound reactor that line is constituted.
9. the method according to claim 1 or 8, wherein the first set fluidizing reactor and second set of fluidization are anti-
Device is answered to be each independently selected from one or more of equal diameter riser, variable diameters riser and dense-phase fluidized bed reactor,
First set fluidizing reactor and second set of fluidizing reactor belong to gasoline absorbing desulfurization device.
10. according to the method described in claim 1, wherein, the absorbing desulfurization catalyst contains silica, aluminium oxide, oxygen
Change zinc and desulphurizing activated metal, the desulphurizing activated metal be in cobalt, nickel, copper, iron, manganese, molybdenum, tungsten, silver, tin and vanadium extremely
Few one kind.
11. according to the method described in claim 10, wherein, on the basis of the dry weight of the absorbing desulfurization catalyst and with
Oxide weight meter, zinc oxide described in the absorbing desulfurization catalyst account for 10-90 weight %, and silica accounts for 5-85 weights
% is measured, aluminium oxide accounts for 5-30 weight %；On the basis of the dry weight of the absorbing desulfurization catalyst and in terms of element wt, institute
The content for stating desulphurizing activated metal described in absorbing desulfurization catalyst is 5-30 weight %.
12. according to the method described in claim 1, wherein, the step of etherification process, includes：Second light petrol is evaporated
Divide and second desulfurization product is contacted with alcohols, makes the alkene in second light gasoline fraction and second desulfurization product
Etherification reaction occurs with alcohols under the action of catalyst for etherification, obtains the etherificate oil；Wherein, the temperature of the etherification reaction
It it is 20-200 DEG C, pressure 0.1-5MPa, weight (hourly) space velocity (WHSV) is 0.1-20 hours -1, and the molal quantity of the alcohols is light with described second
The ratio of the sum of the molal quantity of gasoline fraction and the second desulfurization product is 1：(0.1-100), the catalyst for etherification include being selected from
At least one of resin, molecular sieve and heteropoly acid.
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