CN106147839A - A kind of method reducing content of sulfur in gasoline - Google Patents
A kind of method reducing content of sulfur in gasoline Download PDFInfo
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- CN106147839A CN106147839A CN201510158729.6A CN201510158729A CN106147839A CN 106147839 A CN106147839 A CN 106147839A CN 201510158729 A CN201510158729 A CN 201510158729A CN 106147839 A CN106147839 A CN 106147839A
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Abstract
A kind of method reducing content of sulfur in gasoline, gasoline stocks is fractionated into light fraction gasoline and heavy distillat gasoline, light fraction gasoline enters alkali density unit, obtain refined light fraction gasoline, after heavy distillat gasoline mixes with hydrogen, sequentially enter the first hydrogenation reactor, second hydrogenation reactor, 3rd hydrogenation reactor, diene catalyst is taken off respectively with selective hydrogenation, catalyst for selectively hydrodesulfurizing I contacts with catalyst for selectively hydrodesulfurizing II and reacts, catalyst for selectively hydrodesulfurizing I and catalyst for selectively hydrodesulfurizing II all carries out selective regulation process, obtain after the reaction effluent of the 3rd hydrogenation reactor is separated being hydrogenated with heavy distillat gasoline.The refined light fraction gasoline of mixing and hydrogenation heavy distillat gasoline, obtain super low-sulfur oil product.The present invention can process the catalytically cracked gasoline of high-sulfur height alkene, and product sulfur content is less than 10 μ g/g, and loss of octane number is little, and yield of gasoline reaches more than 99%.
Description
Technical field
A kind of method that the present invention relates to refined hydrocarbon ils, specifically, is a kind of reduction content of sulfur in gasoline,
The method producing super low-sulfur oil.
Background technology
Along with China's automobile pollution increases sharply, motor vehicle exhaust emission causes atmosphere polluting problem day by day
Seriously.The pollutant of motor vehicle exhaust emission mainly include SOx and NOx.This pollutant not only can
Cause acid rain, also can damage the ozone layer, and NOx also can make human carcinogen, to the mankind and environment
Cause the biggest harm.Sulfur in gasoline can make cleaning catalyst for tail gases of automobiles be poisoned, and has a strong impact on
Its disposal ability to discharging pollutants.Therefore, the strictest gasoline has all been formulated in countries in the world
Quality standard limits the sulfur content in gasoline.EPA requires that motor petrol sulfur in 2006 contains
Amount is less than 30 μ g/g.European Union implemented Europe V automobile exhaust emission standard in 2009, it is desirable to gasoline sulfur
Content is less than 10 μ g/g.In December, 2006 China has promulgated motor petrol state II and state's III standard,
Specify to start to implement motor petrol state-III standard (S < 150 μ g/g) in the whole country from the end of the year 2009,
And area takes the lead in implementing the capital V quality standard (S < 10 μ g/g) suitable with Europe V in Beijing etc..Gasoline
Prescription improves constantly, especially sulfur content requesting party in the face of China's oil refining industry be to choose greatly
War.Merchantable gasoline is by bases such as straight-run naphtha, reformate, catalytically cracked gasoline, gasoline alkylates
Plinth raw material is in harmonious proportion and forms.At present in domestic goods gasoline blend component, catalytically cracked gasoline is main next
Source, accounts for 70～80% (abroad accounting for 30～40%) of gasoline pool total amount, and catalytically cracked gasoline sulfur contains
Measuring higher, in gasoline products, the sulfur of more than 90% comes from catalytically cracked gasoline.Visible, reduce catalysis
Cracking gasoline sulfur content is the key producing clean gasoline.Further, from the existing processing of petroleum refining industry of China
From the point of view of flow process, within the quite a long time from now on, China's motor petrol blend component is still with catalysis
Cracking gasoline is main, and low sulfur content antiknock component (Reformed Gasoline and gasoline alkylate) is little
Present situation hardly results in essence and changes.Therefore, reducing sulfur content of catalytic cracking gasoline is to reduce finished product vapour
The key point of oil sulfur content.
The sulfur content reducing catalytically cracked gasoline generally can use catalytically cracked material weighted BMO spaces (front
Hydrogenation), catalytic gasoline hydrogenation desulfurization (back end hydrogenation) or the connected applications of two ways.Wherein,
Catalytically cracked material pretreatment can be greatly reduced the sulfur content of catalytically cracked gasoline, but needs in temperature
Operate with under pressure the most very exacting terms, simultaneously as unit capacity is big, cause hydrogen consumption also to compare
Greatly, these all will improve investment or the operating cost of device.While it is true, due to the weight of world's crude oil
Matter, increasing catalytic cracking unit starts to process the inferior raw material containing normal, decompression residuum etc.,
Therefore catalytically cracked material hydrogenation plant amount is also increasing year by year.Meanwhile, along with catalytic cracking technology
Innovation, the gradually application of catalytic cracking desulfurization auxiliary, the catalytically cracked gasoline sulfur of China's Some Enterprises contains
Amount can reach 500 below μ g/g, even 150 below μ g/g.If but to reduce further and to urge
Change the sulfur content of cracking gasoline, be less than 50 μ g/g and (meet Europe IV discharge standard to content of sulfur in gasoline
Restriction), even less than 10 μ g/g (meet the restriction to content of sulfur in gasoline of Europe V discharge standard), then
The operating severity of catalytically cracked material hydrogenation plant must be increased substantially, the most uneconomical.
The effective way solving the problems referred to above carries out hydrodesulfurization, simultaneously maximum limit to catalytically cracked gasoline exactly
Degree ground reduces the degree of saturation of wherein alkene, to reduce loss of octane number as far as possible.
Catalytic gasoline hydrogenation obviously has the advantage of its uniqueness, at plant investment, production cost and hydrogen
Consumption aspect is below catalytically cracked material weighted BMO spaces, and its different desulfurization depth can meet not
The requirement of same specification sulfur content.If but using traditional hydrodesulfurizationprocess process can make catalytically cracked gasoline
In to have high-octane olefin component the most saturated and make loss of octane number the biggest.It then becomes necessary to
The RSDS that development investment is low, loss of octane number is little.Oil
The catalytic gasoline selective hydrodesulfurizationmodification second-generation technology (RSDS-II) of work research institute exploitation
Sulfur Content in Catalytic Cracking Gasoline can be reduced to 50 below μ g/g, and loss of octane number is little.In order to
Sulfur Content in Catalytic Cracking Gasoline is reduced to more low-level, such as less than 10 μ g/g, must improve further
Reaction severity, reduces alkene saturation factor the most under severe reaction conditions, reduces the octane of product
Value loss is the key point of selective hydrodesulfurization technology.
CN101381624A discloses olefinic naphtha through two stages of reaction, and wherein first
Section, loads special-purpose catalyst, the sulfur of removing major part under mild conditions, and alkene saturation factor is not higher than
30%, second stage, carry out further desulphurization reaction under severe conditions, reduce the life of mercaptan as far as possible
Becoming, alkene saturation factor is not higher than 20%, makes the sulfur content of product less than 10 μ g/g.
WO 2007/061701 discloses a kind of method producing low-sulphur oil using two-stage reaction, should
Method carries out the removing of a large amount of sulfur-containing compound in first reactor, and an anti-effluent uses vapour
Carrying, ammonia the method such as is washed and is carried out H2S removes, and removes H2Product after S enters the second reactor and enters
One-step desulfurization reacts, and makes sulfur content be preferably minimized level.
WO0179391 describes a kind of method producing low-sulfur catalytic cracking gasoline.The first step first will be urged
Change cracking gasoline and carry out selective hydrodesulfurization, obtain intermediate products；Intermediate products are carried out by second step
Removal of mercaptans processes.Patent is mainly concerned with the removal methods of mercaptan sulfur, mainly have extraction, adsorptive fractionation,
Fixed bed oxidation, alkali density, catalytic decomposition etc..
US5906730 discloses FCC gasoline segmentation sulfur removal technology.First paragraph keeps desulfurization degree
60～90%, process conditions: temperature 200～350 DEG C, pressure 5～30kg/cm2, liquid hourly space velocity (LHSV) 2～10h-1,
Hydrogen-oil ratio 89～534v/v, H2S concentration controls < 1000ppm.Second segment controls desulfurization degree 60～90%,
Process conditions: temperature 200～300 DEG C, pressure 5～15kg/cm2, liquid hourly space velocity (LHSV) 2～10h-1, hydrogen oil
Ratio 178～534v/v, H2S concentration controls < 500ppm.If second segment desulfurization still reaches to less than expection
Purpose, continues desulfurization, its process conditions and two-stage nitration desulfurization process conditions by two-stage nitration desulfurization outlet effluent
Identical.But from the point of view of its implementation result, when its total desulfurization degree reaches 95%, alkene saturation factor is 25%,
Producing sweet gasoline according to this technology, product loss of octane number can be bigger.
Under high desulfurization rate, higher reaction temperature is more beneficial for olefins hydrogenation reaction, if only
Improving desulfurization degree further by raising reaction temperature will cause substantial amounts of alkene saturated, and mistake
High reaction temperature can reduce catalyst operation.If using relatively low reaction temperature, be conducive to
Improve the selectivity of desulphurization reaction.But, under relatively low reaction temperature, desulphurization reaction generates
H2Alkene in S and raw material is easier to reaction and generates mercaptan.Especially produce sulfur content less than 10 μ g/g
State's V gasoline time, H2S and alkene generate the reaction of mercaptan under the conditions of process for selective hydrogenation even
Close to balance.This reaction cannot produce sulfur content less than 10 μ g/g resulting even in some cases
State's V gasoline.Breaking this molecular balance, be allowed to the shifting of desulfurization direction, analysis has several in theory
Kind of method: one, be that the alkene in raw material is hydrogenated with in a large number saturated, reduce concentration of olefin, reaction then can be to
Desulfurization direction is moved, but alkene is the most saturated to be caused significantly loss of octane number we to keep away just
Exempt from；Two, the H that desulphurization reaction generates is removed2S, due to H2S is to be continuously generated in course of reaction,
In fixed bed reactors, it is difficult under operation condition directly remove H2S, it is necessary to use two-stage method,
First paragraph removes substantial amounts of sulfur, the then middle gases at high pressure tower that arranges, and cooling carries out gas-liquid separation, will
H2S removes, and carries out deep desulfuration subsequently into second stage.But, this method will certainly cause
The biggest energy consumption.
Summary of the invention
The technical problem to be solved is, while gasoline stocks deep hydrodesulfurizationof, as
What reduces product loss of octane number further, and the present invention provides a kind of with high sulfur oil for raw material production sulfur
Content is less than the method for 10 μ g/g super low-sulfur oils.
The method that the present invention provides is to comprise the steps:
(1) gasoline stocks is fractionated into light fraction gasoline and heavy distillat gasoline, wherein light fraction gasoline and weight
The cut point of distillation gasoline is 45 DEG C～75 DEG C,
(2) light fraction gasoline enters alkali density unit, through alkali cleaning refined removing mercaptan sulfur therein,
To refined light fraction gasoline；
(3) heavy distillat gasoline is together with hydrogen, enters the first hydroconversion reaction zone, takes off diene with selectivity
Catalyst contact is reacted, and the reaction effluent of the first hydroconversion reaction zone is directly entered the without isolation
Two hydroconversion reaction zones and the catalyst for selectively hydrodesulfurizing I that have passed through catalyst choice regulation and control process
Contact, carries out selective hydrodesulfurization reaction, and the reaction effluent of the second hydroconversion reaction zone is without gas-liquid
Separation fully enters the 3rd hydroconversion reaction zone, with the selectivity that have passed through catalyst choice regulation and control process
Hydrobon catalyst II contact is reacted, the reaction effluent of the 3rd hydroconversion reaction zone carries out cooling down,
Separating, isolated liquid phase stream enters stripper, and stripping tower bottom effluent is hydrogenation heavy distillat gasoline,
In described 3rd reaction zone, carry out anti-at a temperature of operating the latter stage of catalyst for selectively hydrodesulfurizing II
Should, meanwhile, by adjusting the reaction temperature of second reaction zone, compensate selective hydrodesulfurization catalysis
The loss of activity of agent II,
(4) the refined light fraction gasoline of step (2) gained and the hydrogenation heavy distillat of step (3) gained
Gasoline mixes, and obtains gasoline products.
The boiling range of described gasoline stocks is 30-205 DEG C, and the volume fraction of alkene is 5%-60%, sulfur
Content is 50-5000 μ g/g.Described gasoline stocks selected from catalytically cracked gasoline, catalytic cracking gasoline,
Coker gasoline, pressure gasoline, direct steaming gasoline any of which or several miscellas, preferably urge
Change cracking gasoline.
The reaction condition of the first described hydroconversion reaction zone is: hydrogen dividing potential drop 1.0～4.0MPa, preferably 1.0～
3.0MPa, reaction temperature 80～300 DEG C, preferably 120～270 DEG C, volume space velocity 2～10h-1, excellent
Select 6～10h-1, hydrogen to oil volume ratio 200～1000Nm3/m3, preferably 300～800Nm3/m3。
The reaction condition of the second described hydroconversion reaction zone is: hydrogen dividing potential drop 1.0～3.0MPa, preferably 1.0～
2.0MPa, reaction temperature 200～350 DEG C, preferably 220～300 DEG C, volume space velocity 2.0～8.0h-1、
Preferably 3.0～6.0h-1, hydrogen to oil volume ratio 200～1000Nm3/m3；The 3rd described hydroconversion reaction zone
Reaction condition be: hydrogen dividing potential drop 1.0～3.0MPa, reaction temperature 340～420 DEG C, preferably 350～
390 DEG C, volume space velocity 10.0～40.0h-1, preferably 12.0～30.0h-1, hydrogen to oil volume ratio 200～1000
Nm3/m3。
In the present invention, reaction logistics is in the second hydrogenation reactor, at lower temperature, relatively low sky
Carry out selective hydrodesulfurization reaction, most sulfur in removing raw material under speed, and reduce alkene as far as possible
Saturation factor.The desulfurization degree controlling the second reactor outlet logistics is 60～99%, preferably 80～98%,
RON loss is no more than 0.2～2.0, preferably 0.2～1.0).
Second hydrogenation reactor outlet material, without gas-liquid separation, fully enters Acanthopanan trifoliatus (L.) Merr. after heating up
Hydrogen reactor, owing in raw material, major part sulfur removes in the second hydrogenation reactor, the second hydrogenation reaction
In the liquid phase of device outlet material, sulfur content is the lowest, but H in gas phase2S concentration is higher.In order to keep away
Exempting from it to react generation mercaptan at the 3rd hydrogenation reactor and alkene, the present invention is by anti-for the 3rd reactor
The operating condition answered is maintained at catalyst and operates temperature latter stage and carry out.Described catalyst operation in latter stage temperature
Degree refers to that catalyst has the maximum operation (service) temperature of catalysis activity.Meanwhile, the 3rd hydrogenation reactor
Use selectivity preferably but active relatively low catalyst for selectively hydrodesulfurizing II, then by selecting
Property regulation and control process after step processes, reaction logistics, can be at high temperature in the 3rd hydrogenation reactor
Carry out further desulphurization reaction, effectively prevent mercaptan simultaneously and generate, thus sulfur content can be obtained and be less than
The heavy distillat gasoline of 10 μ g/g.The present invention is mended by the reaction temperature adjusting the second hydrogenation reactor
Repay the loss of activity of catalyst for selectively hydrodesulfurizing II.
The second preferably described hydroconversion reaction zone reaction temperature is lower than the 3rd hydroconversion reaction zone reaction temperature
60～150 DEG C.
The second preferably described hydroconversion reaction zone volume space velocity is higher than the 3rd hydroconversion reaction zone volume space velocity
2～38h-1。
Described selective hydrogenation takes off diene catalyst for being supported on alumina support and/or silica-alumina supports
On vib metals and/or group VIII metallic catalyst, wherein vib metals is selected from
Molybdenum and/or tungsten, group VIII metal is selected from cobalt and/or nickel.
Catalyst for selectively hydrodesulfurizing I be load on the alumina support containing group VIII non-noble
Metal component and vib metals component and in alcohol, organic acid and organic amine one or more
Organic catalyst, wherein group VIII base metal is selected from cobalt and/or nickel, vib metals
Selected from molybdenum and/or tungsten.
The most described catalyst for selectively hydrodesulfurizing I, counts and on the basis of catalyst by oxide,
The mass fraction of described group VIII metal component is 0.1～6%, the quality of vib metals component
Mark is 1～25%, and described Organic substance is 0.5～2.5 with the mol ratio of group VIII metal component,
Described carrier is a kind of bimodal porous aluminum oxide, with mercury injection method characterize, the pore volume of described carrier be 0.9～
1.2 mls/g, specific surface area is 50～300 meters2/ gram, a diameter of 10～the pore volume in 30nm hole
Account for the 55～80% of total pore volume, a diameter of 300～the pore volume in 500nm hole account for total pore volume 10～
35%.
Described catalyst for selectively hydrodesulfurizing II be supported on silica support containing VIII
Race's non-noble metal components and vib metals component and a kind of in alcohol, organic acid and organic amine
Or several organic catalyst, wherein group VIII base metal is selected from cobalt and/or nickel, VIB
Race's metal is selected from molybdenum and/or tungsten.
Preferably, described catalyst for selectively hydrodesulfurizing II, count and on the basis of catalyst by oxide,
The mass fraction of described group VIII metal component is 0.1～3%, the quality of vib metals component
Mark is 1～15%, and described Organic substance is 0.5～2.5 with the mol ratio of group VIII metal component,
Described carrier is a kind of silicon oxide, and pore volume is 0.5～1.0 ml/g, and specific surface area is 20～200
Rice2/ gram.
Preferably catalyst for selectively hydrodesulfurizing I and the preparation side of catalyst for selectively hydrodesulfurizing II
Method is as follows.
In the present invention, described on carrier, introduce at least one non-noble metal metal selected from VIII
Component and at least one is selected from the metal component of group vib and in alcohol, organic acid and organic amine one
Planting or several organic methods is preferably the method impregnated, described dipping method is conventional method,
Such as hole saturation dipping, excess immersion stain and spray impregnating.Wherein, described group VIII,
Group vib and in alcohol, organic acid and organic amine the Organic substance of one or more can be introduced separately into,
Can also two two or three kinds of be simultaneously introduced.When using infusion process to introduce, including preparation dipping solution,
Such as, by the compound containing the described metal component selected from least one vib, containing at least one
The compound of the metal component of group VIII or in alcohol, organic acid and organic amine one or more
Organic substance prepares dipping solution respectively, and impregnates carrier respectively with these dipping solutions；Or by containing
The described metal component selected from least one vib, the metal group containing at least one group VIII
Point compound and in alcohol, organic acid and organic amine two kinds in the Organic substance of one or more or
Three kinds of preparation hybrid infusion solution, and the method impregnating carrier respectively with these dipping solutions.When described
When dipping is for step impregnation, the order of described dipping solution dipping carrier is not limited.Although not being
Required, preferably include the step being dried after dipping every time.Described drying condition includes: be dried temperature
Spending 100～210 DEG C, preferably 120～190 DEG C, drying time 1～6 hours, preferably 2～4 is little
Time.
To reach the reaction temperature of identical desulfurization degree to weigh the activity of catalyst, selective hydrodesulfurization
The activity of the specific activity catalyst for selectively hydrodesulfurizing II of catalyst I is high 5 DEG C～60 DEG C.
Selectivity of catalyst is weighed with selectivity factor.Selectivity factor uses following definition: S
=log (Sp/Sf)/log(Op/Of).In formula: S selectivity factor；SpProduct sulfur content；Sf—
Feed sulphur content；OpProduct alkene mass content；OfRaw material olefin mass content.Selectivity adds
The selectivity of the selectivity ratios catalyst for selectively hydrodesulfurizing I of hydrogen desulphurization catalyst II is high 2～10
Unit.
Described catalyst for selectively hydrodesulfurizing I and catalyst for selectively hydrodesulfurizing II is all in sulfuration
Carry out catalyst choice regulation and control after end to process so that it is reach corresponding activity and selectivity requirement.
After over cure, there is desulphurizing activated center and olefins hydrogenation lived in catalyst for selectively hydrodesulfurizing
Property Liang Zhong active center, center.The present invention increases catalyst between sulfidation and normal productive process
Selective regulation process, can substantially shield one of which active center, thus improve selective hydrogenation
The selectivity of desulphurization catalyst.Described catalyst choice regulation process is raw material alive will to be urged to urge work
In the atmosphere of gas, contact with catalyst for selectively hydrodesulfurizing under urging reaction condition alive.This process
Can effectively make coking charcoal cover in catalyst olefins hydrogenation active center, make selective hydrogenation
Desulphurization catalyst olefins hydrogenation activity is substantially reduced, and desulphurizing activated center is valid protected, and makes
The desulphurizing activated of catalyst for selectively hydrodesulfurizing does not the most lose or loses the least.
Described catalyst for selectively hydrodesulfurizing I and the catalyst of catalyst for selectively hydrodesulfurizing II
Selective regulation processes, and comprises the following steps:
A () sulfidation terminates after, in adjustment response system, gas is for urging lively atmosphere body；
B () will urge raw material alive to introduce response system, and contact with catalyst under urging reaction condition alive
24～96 hours；
C () urges reaction alive to terminate after, adjusting process condition is normal reaction conditions, switches reaction feed
For full distillation gasoline or heavy distillat gasoline；
D () adjusts gas in response system is hydrogen-rich gas, carries out normal reaction.
Described lively atmosphere body is urged to include hydrogen, hydrogen sulfide and carbon monoxide, to urge lively atmosphere body generally benchmark,
Wherein the volume fraction of hydrogen is not less than 70%, and the volume fraction sum of hydrogen sulfide and carbon monoxide is
0.05%～5%；The volume fraction of hydrogen is not less than 80% preferably wherein, hydrogen sulfide and carbon monoxide
Volume fraction sum is 0.3%～2%.
Described the reaction condition alive is urged to be: hydrogen dividing potential drop 0.6～2.0MPa, reaction temperature 200～350 DEG C,
Volume space velocity 1～10h-1, hydrogen to oil volume ratio 50～400Nm3/m3.Raw material alive is preferably urged to urge work anti-
Contact with catalyst 48～80 hours under the conditions of Ying.
In one preferred embodiment, the described reaction temperature urging work to react is than normal reaction
Reaction temperature is high 30～100 DEG C.
In one preferred embodiment, the described volume space velocity urging work to react is than normal reaction
Volume space velocity low 2～4h-1。
The described boiling range urging raw material alive is 30～350 DEG C, wherein, the volume fraction of alkene be 5%～
60%.
Preferably described urges possibly together with aromatic hydrocarbons in raw material alive, and the volume fraction of aromatic hydrocarbons is 5%～60%.
Described step (d) hydrogen-rich gas, with hydrogen-rich gas generally benchmark, the volume fraction of hydrogen is extremely
Being 70% less, the volume fraction sum of hydrogen sulfide and carbon monoxide is less than 0.05%.The preferably body of hydrogen
Fraction is at least 80%, and the volume fraction sum of hydrogen sulfide and carbon monoxide is less than 0.02%.
In currently preferred a kind of embodiment, in step (b), first reduce gas reactor
The concentration of middle hydrogen sulfide gas, is further added by the concentration of CO (carbon monoxide converter) gas in gas reactor, finally adjusts
In whole reactor, gas is for urging lively atmosphere body.
In currently preferred a kind of embodiment, in step (d), first reduce gas reactor
The concentration of middle CO (carbon monoxide converter) gas, then reduce the concentration of hydrogen sulfide gas in gas reactor, finally adjust
In whole reactor, gas is hydrogen-rich gas.
The method using the present invention to provide, can process the catalytically cracked gasoline of high-sulfur height alkene, product
Sulfur content is less than 10 μ g/g, and loss of octane number is little, and yield of gasoline reaches more than 99%.With prior art
Compare, while reducing sulfur content further, keep the loss of octane number that product is less.Pass through simultaneously
Second reactor compensates the loss of activity of the 3rd reactor catalyst, maintains the use longevity of catalyst
Life, improves the selectivity of reaction to greatest extent and extends the device operation cycle.
Accompanying drawing explanation
Accompanying drawing is the schematic flow sheet reducing content of sulfur in gasoline method that the present invention provides.
Detailed description of the invention
Below in conjunction with the accompanying drawings method provided by the present invention is further detailed, but the most therefore
And limit the present invention.
As shown in drawings, the method reducing content of sulfur in gasoline that the present invention provides is described in detail as follows: come
Fractionating column 2 is entered, the light fraction gasoline obtained after shunting from the full distillation gasoline raw material of pipeline 1
Enter alkali density removal of mercaptans unit 4 through pipeline 3 and carry out removal of mercaptans process, through removal of mercaptans out after
Light fraction gasoline is mixed to get full fraction product through pipeline 5 with the logistics from pipeline 34.From fractional distillation
The heavy distillat gasoline that tower 2 obtains flows out from pipeline 6, after raw material pump 7 boosts and from pipeline 31
Hydrogen mixing after enter and enter the through pipeline 9 after heat exchanger 8, with the material-heat-exchanging from pipeline 22
One hydrogenation reactor 10, carries out selectivity and takes off two alkene reactions.First hydrogenation reactor effluent is through pipeline
After 11 enter heating furnace 12 heating, enter the second hydrogenation reactor 14 through pipeline 13, select
Property hydrodesulfurization reaction.Second hydrogenation reactor effluent is through pipeline 15 and the material from pipeline 21
After heat exchanger 16 heat exchange, after pipeline 17 enters heating furnace 18 heating, enter the through pipeline 19
Three hydrogenation reactors 20, the 3rd reactor effluent enters heat exchanger 16 and from pipeline through pipeline 21
Enter heat exchanger 8 through pipeline 22 after the material-heat-exchanging of 15, carry out heat exchange with the material from pipeline 7
Enter by pipeline 23 and enter high-pressure separator 26 after air cooling 24, water-cooled 25 cooling.At high pressure
After separator 26 carries out gas-liquid separation, the hydrogen-rich gas at top enters desulfurizing tower 28 through pipeline 27 and takes off
H in dehydrogenation gas2Enter circulating hydrogen compressor 30 through pipeline 29 after S to boost, the H after boosting2
Mix with raw material pump 7 outlet material through pipeline 31.The logistics warp obtained bottom high-pressure separator 26
Pipeline 32 enters stabilizer 33, and the light hydrocarbon gas of tower top is extracted out by pipeline 35, and tower bottom product is through pipeline
34, it is mixed to get full distillation gasoline product with the logistics from pipeline 5.
The method providing the present invention is further described by the following examples, but not because of
This and limit the present invention.
The trade names of hydrotreating catalyst C, D, E used in comparative example are respectively
RGO-3, RSDS-21, RSDS-22, produced by Sinopec catalyst Chang Ling branch company.
It is RGO-3 that selective hydrogenation used by embodiment takes off the trade names of diene catalyst, by
State's Effect of Catalysis In Petrochemistry agent Chang Ling branch company produces.
Catalyst for selectively hydrodesulfurizing I used by embodiment is catalyst A, and selective hydrogenation takes off
Sulfur catalyst II is catalyst B.The carrier of catalyst A is aluminium oxide, and active metal consists of:
Molybdenum oxide 13.5 weight %, cobalt oxide 4.0 weight %.The carrier of catalyst B is silicon oxide, activity gold
Genus consists of: molybdenum oxide 8.5 weight %, cobalt oxide 3.0 weight %.
To reach the reaction temperature of identical desulfurization degree to weigh the activity of catalyst, the activity of catalyst A
Activity than catalyst B is high 5～60 DEG C.
Selectivity of catalyst is weighed with selectivity factor, the selectivity ratios catalyst B's of catalyst A
High 2～10 units of selectivity.
The definition that selectivity factor employing is following: S=log (Sp/Sf)/log(Op/Of).In formula: S
Selectivity factor；SpProduct sulfur content；SfFeed sulphur content；OpProduct alkene mass content；
OfRaw material olefin mass content.
For giving full play to the hydrodesulfurization performance of catalyst, above-mentioned catalyst is equal before contacting formal raw material
Need to carry out presulfurization process.In comparative example set forth below and embodiment, the presulfurization side of each catalyst
Method is identical.
In an embodiment, catalyst A and catalyst B selective regulation process, its mistake have been carried out
Cheng Wei: after sulfuration terminates, adjusts gas in response system and, for urging lively atmosphere body, urges in lively atmosphere body, hydrogen
Volume fraction be 90%, the volume fraction sum of hydrogen sulfide and carbon monoxide is 1.8%, will urge work
Raw material introduces response system, and is hydrogen dividing potential drop 1.6MPa, hydrogen-oil ratio 100Nm urging condition alive3/m3、
Volume space velocity 4.0h-1, make to urge raw material alive to contact 72h with catalyst under conditions of reaction temperature 350 DEG C,
Catalyst is carried out selective regulation process.The boiling range urging raw material alive is 30～350 DEG C, wherein, alkene
The volume fraction of hydrocarbon is 28%, and the volume fraction of aromatic hydrocarbons is 20%.Catalyst is carried out at selective regulation
After reason terminates, being adjusted to normal reaction conditions, switching reaction feed is the heavy distillat of raw oil, and cuts
Changing gas in reactor is hydrogen-rich gas, and with hydrogen-rich gas generally benchmark, the volume fraction of hydrogen is
90%, the volume fraction sum of hydrogen sulfide and carbon monoxide is 0.005%.
Comparative example 1
By one catalytically cracked gasoline raw oil F (its raw oil character is shown in Table 1) first in fractionating column
It is cut into light fraction gasoline (boiling range C5～65 DEG C) and heavy distillat gasoline (boiling range 65 DEG C～190 DEG C).
Wherein light fraction quality of gasoline ratio is 25%, and heavy distillat quality of gasoline ratio is 75%.Light fraction
Gasoline alkali density removal of mercaptans；Heavy distillat gasoline uses the selective hydrodesulfurization method of two reactors to enter
Row hydrodesulfurization processes, and loading catalyst C in the first reactor loads in the second reactor and urges
Agent D and E, the two admission space ratio is D:E=85:15.Light fraction vapour after alkali density
Oil is mixed to get full distillation gasoline product with the heavy distillat gasoline after hydrodesulfurization.Product property and
Reaction process condition is as shown in table 2, and the sulfur content of product is 8 μ g/g as can be seen from Table 2, alkene
Volume saturation factor is 43.8%, and RON loss 3.2, product quality yield is 99.8%.
Comparative example 2
One catalytically cracked gasoline raw oil F is first segmented into light fraction gasoline (boiling range in fractionating column inscribe
C5～65 DEG C) and heavy distillat gasoline (boiling range 65 DEG C～190 DEG C).Wherein light fraction quality of gasoline ratio
Being 25%, heavy distillat quality of gasoline ratio is 75%.Light fraction gasoline alkali density removal of mercaptans；Double distilled
Gasoline is divided to use the method that three reactors carry out subregion reaction.First reactor loading catalyst C,
Second reactor and the 3rd reactor equal loading catalyst E.Concrete reaction condition and full distillation gasoline
Product property is as shown in table 2, and as can be seen from Table 2, the sulfur content of product is 8 μ g/g, and alkene is satisfied
Being 31.5% with rate, RON loss is 1.6, and product yield is 99.7 weight %.
But, owing to the activity of catalyst E is relatively low, the second reactor have employed higher reaction temperature
Keeping desulphurizing activated, after running 3000 hours, catalyst E activity is decreased obviously, and uses and continues
Improving reaction temperature and maintain the activity of catalyst E, the operation temperature of the second hydrogenation reactor is by 310
Temperature carries to 320 temperature, due to temperature raising limited space, will quickly reach catalyst and operate temperature latter stage,
The most whole plant running cycle is short.
Embodiment 1
With a kind of catalytically cracked gasoline for raw oil F, its raw oil character is as shown in table 1.Raw oil
F is first segmented into light fraction gasoline (boiling range C in fractionating column inscribe5～65 DEG C) and heavy distillat gasoline (boiling range
65 DEG C～190 DEG C).Wherein light fraction quality of gasoline ratio is 25%, and heavy distillat quality of gasoline ratio is
75%.Light fraction gasoline alkali density removal of mercaptans；Heavy distillat gasoline uses technological process in accompanying drawing of the present invention
Carry out hydrodesulfurization process.Light fraction gasoline after alkali density and the double distilled after hydrodesulfurization
Gasoline is divided to be mixed to get full distillation gasoline product.
Reaction condition that first reactor, the second reactor and the 3rd reactor are concrete and full distillation gasoline
Product property is as shown in table 3, and the sulfur content of product is 9 μ g/g as can be seen from Table 3, olefin(e) centent
Being 30.6 volume %, RON only loses 1.5, and product yield is 99.8 weight %.
The operating condition of the 3rd reactor reaction is maintained at catalyst and operates temperature latter stage and enter by the present invention
OK, and by the reaction temperature adjusting the second hydrogenation reactor catalyst for selectively hydrodesulfurizing is compensated
The loss of activity of II.Due to the catalyst A that the second reactor filling activity is higher, equally, run 3000
After hour, the operation temperature of the present invention the second hydrogenation reactor needs to be carried to 270 temperature by 260 temperature,
But, owing to the temperature raising space of the present invention the second hydrogenation reactor is big, therefore, whole device operation week
Phase is long.
Embodiment 2
With a kind of catalytically cracked gasoline for raw oil G, its raw oil character is as shown in table 1.Raw oil
G is first segmented into light fraction gasoline (boiling range C in fractionating column inscribe5～58 DEG C) and heavy distillat gasoline (boiling range
58 DEG C～205 DEG C).Wherein light fraction gasoline proportionality is 25 weight %, and heavy distillat gasoline proportionality is 75 weight %.
Light fraction gasoline alkali density removal of mercaptans；Heavy distillat gasoline uses technological process in accompanying drawing of the present invention to add
Hydrogen desulfurization processes.Light fraction gasoline after alkali density and the heavy distillat gasoline after hydrodesulfurization
It is mixed to get full distillation gasoline product at products pot.
Reaction condition that first reactor, the second reactor and the 3rd reactor are concrete and full distillation gasoline
Product property is as shown in table 3, and the sulfur content of product is 8 μ g/g as can be seen from Table 3, olefin(e) centent
Being 24.1 volume %, RON only loses 1.1, and product yield is 99.7 weight %.
Embodiment 3
With a kind of catalytically cracked gasoline for raw oil I, its raw oil character is as shown in table 1.Raw oil I
First it is segmented into light fraction gasoline (boiling range C in fractionating column inscribe5～60 DEG C) and heavy distillat gasoline (boiling range
60 DEG C～205 DEG C).Wherein light fraction gasoline proportionality is 24 weight %, and heavy distillat gasoline proportionality is 76 weight %.
Light fraction gasoline alkali density removal of mercaptans；Heavy distillat gasoline uses technological process in accompanying drawing of the present invention to add
Hydrogen desulfurization processes.Light fraction gasoline after alkali density and the heavy distillat gasoline after hydrodesulfurization
It is mixed to get full distillation gasoline product at products pot.
Reaction condition that first reactor, the second reactor and the 3rd reactor are concrete and full distillation gasoline
Product property is as shown in table 3, and the sulfur content of product is 8 μ g/g as can be seen from Table 3, olefin(e) centent
Being 22.6 volume %, RON only loses 1.0, and product yield is 99.6 weight %.
Table 1
| Material name | F | G | I |
| Density (20 DEG C), g/cm3 | 0.7234 | 0.7321 | 0.7311 |
| Sulfur, μ g/g | 1096 | 631 | 600 |
| Olefin(e) centent, volume % | 39.7 | 28.8 | 26.9 |
| Boiling range (ASTM D-86), DEG C | |||
| Initial boiling point | 26 | 37 | 31 |
| 10% | 40 | 52 | 44 |
| 50% | 85 | 96 | 82 |
| The end point of distillation | 190 | 200 | 200 |
| RON | 94.4 | 90.8 | 94.2 |
| MON | 81.6 | 80.7 | 82.2 |
| Anti-knock index | 88.0 | 85.8 | 88.2 |
Table 2
| Comparative example 1 | Comparative example 2 | |
| Raw oil | F | F |
| Reaction condition | ||
| First reactor | ||
| Catalyst | C | C |
| Reaction temperature, DEG C | 180 | 180 |
| Hydrogen dividing potential drop, MPa | 1.6 | 1.6 |
| Hydrogen to oil volume ratio, Nm3/m3 | 400 | 400 |
| Volume space velocity, h-1 | 8.0 | 8.0 |
| Second reactor | ||
| Catalyst | D+E | E |
| Reaction temperature, DEG C | 310 | 310 |
| Hydrogen dividing potential drop, MPa | 1.6 | 1.6 |
| Hydrogen to oil volume ratio, Nm3/m3 | 400 | 400 |
| Volume space velocity, h-1 | 4.0 | 4.0 |
| 3rd reactor | Nothing | |
| Catalyst | - | E |
| Reaction temperature, DEG C | - | 360 |
| Hydrogen dividing potential drop, MPa | - | 1.6 |
| Hydrogen to oil volume ratio, Nm3/m3 | - | 400 |
| Volume space velocity, h-1 | - | 12 |
| Product property | ||
| Density (20 DEG C), g/cm3 | 0.721 | 0.720 |
| S, μ g/g | 8 | 8 |
| Olefin(e) centent, volume % | 22.3 | 27.2 |
| RON | 91.2 | 92.8 |
| MON | 80.8 | 81.0 |
| Volume alkene saturation factor, % | 43.8 | 31.5 |
| Quality desulfurization degree, % | 99.3 | 99.3 |
| RON loses | 3.2 | 1.6 |
| Uprising figure penalties | 2.0 | 1.1 |
Table 3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Raw oil | F | G | I |
| Reaction condition | |||
| First hydrotreating reactor | |||
| Catalyst | C | C | C |
| Reaction temperature, DEG C | 180 | 180 | 180 |
| Hydrogen dividing potential drop, MPa | 1.6 | 1.6 | 1.6 |
| Hydrogen to oil volume ratio, Nm3/m3 | 400 | 400 | 500 |
| Volume space velocity, h-1 | 4.0 | 4.0 | 4.0 |
| Second hydrotreating reactor | |||
| Catalyst | A | A | A |
| Reaction temperature, DEG C | 260 | 260 | 270 |
| Hydrogen dividing potential drop, MPa | 1.6 | 1.6 | 1.6 |
| Hydrogen to oil volume ratio, Nm3/m3 | 400 | 400 | 400 |
| Volume space velocity, h-1 | 4.0 | 4.0 | 4.0 |
| 3rd hydrotreating reactor | |||
| Catalyst | B | B | B |
| Reaction temperature, DEG C | 360 | 380 | 390 |
| Hydrogen dividing potential drop, MPa | 1.6 | 1.6 | 1.6 |
| Hydrogen to oil volume ratio, Nm3/m3 | 400 | 400 | 400 |
| Volume space velocity, h-1 | 12 | 20 | 30 |
| Product property | |||
| Density (20 DEG C), g/cm3 | 0.7210 | 0.7250 | 0.7230 |
| S, μ g/g | 8 | 8 | 8 |
| Olefin(e) centent, volume % | 32.6 | 24.5 | 23.5 |
| RON | 92.9 | 89.8 | 93.4 |
| MON | 81.3 | 80.5 | 82.0 |
| Desulfurization degree, weight % | 99.3 | 98.7 | 98.7 |
| Alkene saturation factor, volume % | 17.8 | 14.9 | 12.6 |
| RON loses | 1.5 | 1.0 | 0.8 |
| Anti-knock index loses | 0.9 | 0.6 | 0.5 |
| Product quality yield, % | 99.8 | 99.7 | 99.6 |
Claims (21)
1. the method reducing content of sulfur in gasoline, comprises the steps:
(1) gasoline stocks is fractionated into light fraction gasoline and heavy distillat gasoline, wherein light fraction gasoline and weight
The cut point of distillation gasoline is 45 DEG C～75 DEG C；
(2) light fraction gasoline enters alkali density unit, through alkali cleaning refined removing mercaptan sulfur therein,
To refined light fraction gasoline；
(3) heavy distillat gasoline is together with hydrogen, enters the first hydroconversion reaction zone, takes off diene with selectivity
Catalyst contact is reacted, and the reaction effluent of the first hydroconversion reaction zone is directly entered the without isolation
Two hydroconversion reaction zones and the catalyst for selectively hydrodesulfurizing I that have passed through catalyst choice regulation and control process
Contact, carries out selective hydrodesulfurization reaction, and the reaction effluent of the second hydroconversion reaction zone is without gas-liquid
Separation fully enters the 3rd hydroconversion reaction zone, with the selectivity that have passed through catalyst choice regulation and control process
Hydrobon catalyst II contact is reacted, the reaction effluent of the 3rd hydroconversion reaction zone carries out cooling down,
Separating, isolated liquid phase stream enters stripper, and stripping tower bottom effluent is hydrogenation heavy distillat gasoline,
In described 3rd reaction zone, carry out anti-at a temperature of operating the latter stage of catalyst for selectively hydrodesulfurizing II
Should, meanwhile, by adjusting the reaction temperature of second reaction zone, compensate selective hydrodesulfurization catalysis
The loss of activity of agent II,
(4) the refined light fraction gasoline of step (2) gained and the hydrogenation heavy distillat of step (3) gained
Gasoline mixes, and obtains gasoline products.
Method the most in accordance with claim, it is characterised in that the boiling range of described gasoline stocks is
30-205 DEG C, the volume fraction of alkene is 5%-60%, and sulfur content is 50-5000 μ g/g.
The most in accordance with the method for claim 1, it is characterised in that the first described hydroconversion reaction zone
Reaction condition be: hydrogen dividing potential drop 1.0～4.0MPa, reaction temperature 80～300 DEG C, volume space velocity 2～
10h-1, hydrogen to oil volume ratio 200～1000Nm3/m3。
The most in accordance with the method for claim 1, it is characterised in that the second described hydroconversion reaction zone
Reaction condition be: hydrogen dividing potential drop 1.0～3.0MPa, reaction temperature 200～350 DEG C, volume space velocity 2.0～
8.0h-1, hydrogen to oil volume ratio 200～1000Nm3/m3；The reaction article of the 3rd described hydroconversion reaction zone
Part is: hydrogen dividing potential drop 1.0～3.0MPa, reaction temperature 340～420 DEG C, volume space velocity 10.0～40.0h-1、
Hydrogen to oil volume ratio 200～1000Nm3/m3。
5. according to the method described in claim 1 or 4, it is characterised in that the second described hydrogenation is anti-
Answer district's reaction temperature lower than the 3rd hydroconversion reaction zone reaction temperature 60～150 DEG C.
6. according to the method described in claim 1 or 4, it is characterised in that the second described hydrogenation is anti-
Answer district's volume space velocity than the 3rd hydroconversion reaction zone volume space velocity low 2～38h-1。
The most in accordance with the method for claim 1, it is characterised in that described selective hydrodesulfurization is urged
The selective regulation of agent I and catalyst for selectively hydrodesulfurizing II processes and comprises the steps:
A () sulfidation terminates after, in adjustment response system, gas is for urging lively atmosphere body；
B () will urge raw material alive to introduce response system, and contact with catalyst under urging reaction condition alive
24～96 hours；
C () urges reaction alive to terminate after, adjusting process condition is normal reaction conditions, switches reaction feed
For full distillation gasoline or heavy distillat gasoline；
D () adjusts gas in response system is hydrogen-rich gas, carries out normal reaction.
The most in accordance with the method for claim 7, it is characterised in that described in urge lively atmosphere body include hydrogen,
Hydrogen sulfide and carbon monoxide, to urge lively atmosphere body generally benchmark, wherein the volume fraction of hydrogen is not less than
70%, the volume fraction sum of hydrogen sulfide and carbon monoxide is 0.05%～5%.
The most in accordance with the method for claim 8, it is characterised in that described in urge in lively atmosphere body, to urge work
Gas generally benchmark, wherein the volume fraction of hydrogen is not less than 80%, hydrogen sulfide and carbon monoxide
Volume fraction sum is 0.3%～2%.
The most in accordance with the method for claim 7, it is characterised in that urge the reaction condition alive to be: hydrogen divides
Pressure 0.6～2.0MPa, reaction temperature 200～350 DEG C, volume space velocity 1～10h-1, hydrogen to oil volume ratio
50～400Nm3/m3。
11. in accordance with the method for claim 7, it is characterised in that urges raw material alive urging reaction bar of living
Contact with catalyst 48～80 hours under part.
12. in accordance with the method for claim 7, it is characterised in that the described boiling range urging raw material alive
Being 30～350 DEG C, wherein, the volume fraction of alkene is 5%～60%.
13. in accordance with the method for claim 12, it is characterised in that described urging in raw material alive also contains
Having aromatic hydrocarbons, the volume fraction of aromatic hydrocarbons is 5%～60%.
14. in accordance with the method for claim 7, it is characterised in that the hydrogen rich gas of described step (d)
Body, with hydrogen-rich gas generally benchmark, the volume fraction of hydrogen is at least 70%, hydrogen sulfide and an oxygen
Change the volume fraction sum of carbon less than 0.05%.
15. in accordance with the method for claim 1, it is characterised in that described selective hydrogenation takes off
Diene catalyst be supported on the vib metals in alumina support and/or silica-alumina supports and/or
Group VIII metallic catalyst, wherein vib metals is selected from molybdenum and/or tungsten, group VIII gold
Belong to selected from cobalt and/or nickel.
16. in accordance with the method for claim 1, it is characterised in that described selective hydrodesulfurization
Catalyst I be load on the alumina support containing group VIII non-noble metal components and vib
Metal component and in alcohol, organic acid and organic amine one or more organic catalyst, its
Middle group VIII base metal is selected from cobalt and/or nickel, and vib metals is selected from molybdenum and/or tungsten.
17. in accordance with the method for claim 16, it is characterised in that described selective hydrodesulfurization is urged
Agent I, counts and on the basis of catalyst by oxide, and the quality of described group VIII metal component is divided
Number is 0.1～6%, and the mass fraction of vib metals component is 1～25%, described Organic substance with
The mol ratio of group VIII metal component is 0.5～2.5, and described carrier is a kind of bimodal porous aluminum oxide,
Characterizing with mercury injection method, the pore volume of described carrier is 0.9～1.2 ml/g, and specific surface area is 50～300
Rice2/ gram, a diameter of 10～the pore volume in 30nm hole account for total pore volume 55～80%, a diameter of 300～
The pore volume in 500nm hole accounts for the 10～35% of total pore volume.
18. in accordance with the method for claim 1, it is characterised in that described selective hydrodesulfurization
Catalyst II be supported on silica support containing group VIII non-noble metal components and VIB
Race's metal component and in alcohol, organic acid and organic amine one or more organic catalyst,
Wherein group VIII base metal is selected from cobalt and/or nickel, and vib metals is selected from molybdenum and/or tungsten.
19. in accordance with the method for claim 18, it is characterised in that described selective hydrodesulfurization is urged
Agent II, counts and on the basis of catalyst by oxide, and the quality of described group VIII metal component is divided
Number is 0.1～3%, and the mass fraction of vib metals component is 1～15%, described Organic substance with
The mol ratio of group VIII metal component is 0.5～2.5, and described carrier is a kind of silicon oxide, and pore volume is
0.5～1.0 ml/g, specific surface area is 20～200 meters2/ gram.
20. according to described method arbitrary in claim 1,16,17,18,19, and its feature exists
In, to reach the reaction temperature of identical desulfurization degree to weigh the activity of catalyst, selective hydrodesulfurization
The activity of the specific activity catalyst for selectively hydrodesulfurizing II of catalyst I is high 5 DEG C～60 DEG C.
21. according to described method arbitrary in claim 1,16,17,18,19, and its feature exists
In, weigh selectivity of catalyst, the selection of catalyst for selectively hydrodesulfurizing II with selectivity factor
The property high 2～10 units of selectivity than catalyst for selectively hydrodesulfurizing I.
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| CN108865262A (en) * | 2018-07-20 | 2018-11-23 | 北京欧美中科学技术研究院 | A kind of sulfuration process of gasoline selective hydrodesulfurizationmodification device |
| CN114729264A (en) * | 2019-12-02 | 2022-07-08 | Ifp 新能源公司 | Method for treating plastic pyrolysis oil for use in steam cracking unit |
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| CN115725335A (en) * | 2021-08-31 | 2023-03-03 | 中国石油化工股份有限公司 | Method for treating benzene and sulfur in gasoline raw material |
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| CN114729264A (en) * | 2019-12-02 | 2022-07-08 | Ifp 新能源公司 | Method for treating plastic pyrolysis oil for use in steam cracking unit |
| CN114763493A (en) * | 2021-01-13 | 2022-07-19 | 中国石油化工股份有限公司 | Method and system for producing gasoline blend oil by using carbon five raffinate oil |
| CN114763493B (en) * | 2021-01-13 | 2024-01-12 | 中国石油化工股份有限公司 | Method and system for producing gasoline blend oil by using carbon five raffinate oil |
| CN115725335A (en) * | 2021-08-31 | 2023-03-03 | 中国石油化工股份有限公司 | Method for treating benzene and sulfur in gasoline raw material |
| CN115725334A (en) * | 2021-08-31 | 2023-03-03 | 中国石油化工股份有限公司 | Method for treating gasoline raw material |
| CN115725335B (en) * | 2021-08-31 | 2024-04-02 | 中国石油化工股份有限公司 | Method for treating benzene and sulfur in gasoline raw material |
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