CN106147839B - A kind of method for reducing content of sulfur in gasoline - Google Patents
A kind of method for reducing content of sulfur in gasoline Download PDFInfo
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Abstract
A kind of method for reducing content of sulfur in gasoline, gasoline stocks are 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 is mixed with hydrogen, sequentially enter the first hydrogenation reactor, second hydrogenation reactor, third hydrogenation reactor, diene catalyst is taken off with selective hydrogenation respectively, catalyst for selectively hydrodesulfurizing I and catalyst for selectively hydrodesulfurizing II contacts are reacted, catalyst for selectively hydrodesulfurizing I and catalyst for selectively hydrodesulfurizing II carry out selective regulation processing, the reaction effluent of third hydrogenation reactor is obtained after separation plus hydrogen heavy distillat gasoline.The refined light fraction gasoline of mixing obtains super low-sulfur oil product with adding hydrogen heavy distillat gasoline.The present invention can handle the catalytically cracked gasoline of the high alkene of high-sulfur, and product sulfur content is less than 10 μ g/g, and loss of octane number is small, and yield of gasoline is up to more than 99%.
Description
Technical field
The present invention relates to a kind of method of refined hydrocarbon ils, specifically, being a kind of reduction content of sulfur in gasoline, super-low sulfur is produced
The method of gasoline.
Background technology
As China's car ownership increases sharply, motor vehicle exhaust emission causes atmosphere polluting problem getting worse.Automobile
The pollutant of exhaust emissions mainly includes SOx and NOx.This pollutant not only results in acid rain, can also destroy ozone layer, and
NOx can also make human carcinogen, and very big harm is caused to the mankind and environment.Sulphur in gasoline can be catalyzed purifying vehicle exhaust
Agent is poisoned, and seriously affects it to the processing capacity that discharges pollutants.Therefore, increasingly stringenter gasoline has been formulated in countries in the world
Quality standard limits the sulfur content in gasoline.U.S.EPA requires vehicle gasoline and sulfur content in vehicle gasoline in 2006 to be less than 30 μ g/g.Europe
Alliance implemented Europe V automobile exhaust emission standards in 2009, it is desirable that content of sulfur in gasoline is less than 10 μ g/g.In December, 2006, China promulgated
Motor petrol state II and state's III standards since the end of the year 2009 in the whole country, it is specified that implement motor petrol state-III standards
(S<150 μ g/g), and take the lead in implementing and the comparable capital V quality standards (S of Europe V in areas such as Beijing<10μg/g).Quality of gasoline will
Continuous improvement is asked, it is greatly to challenge especially to face China's oil refining industry in the requesting party of sulfur content.Merchantable gasoline is by straight run
The basic materials such as naphtha, reformate, catalytically cracked gasoline, gasoline alkylate reconcile.Domestic goods gasoline reconciles at present
In component, catalytically cracked gasoline is main source, accounts for about 70~80% (foreign countries account for about 30~40%) of gasoline pool total amount, catalysis
Cracking gasoline sulfur content is higher, and more than 90% sulphur comes from catalytically cracked gasoline in gasoline products.As it can be seen that reduce catalytic cracking
Content of sulfur in gasoline is the key that production clean gasoline.It is suitable from now on also, from the point of view of the existing processing flow of petroleum refining industry of China
In long a period of time, China's motor petrol blend component is still based on catalytically cracked gasoline, low sulfur content antiknock component
(Reformed Gasoline and gasoline alkylate) seldom present situation is hardly resulted in and is sexually revised at all.Therefore, catalytically cracked gasoline sulphur is reduced to contain
Amount is to reduce the key point of gasoline product sulfur content.
Catalytically cracked material weighted BMO spaces (front-end hydrogenation), catalysis usually can be used in the sulfur content for reducing catalytically cracked gasoline
Cracking gasoline hydrodesulfurization (back end hydrogenation) or the connected applications of two ways.Wherein, catalytically cracked material pretreatment can be substantially
The sulfur content of catalytically cracked gasoline is reduced, but needs all to operate under exacting terms very much in temperature and pressure, simultaneously as device
Treating capacity is big, and hydrogen is caused to consume also bigger, these investment or the operating costs that will all improve device.Nevertheless, due to the world
The heaviness of crude oil, more and more catalytic cracking unit start to process contain the inferior raw material of normal, decompression residuum etc., therefore urge
Change cracked stock hydrogenation plant amount to be also increasing year by year.Meanwhile with the innovation of catalytic cracking technology, catalytic cracking desulfurization auxiliary
Gradual application, the sulfur content of catalytic cracking gasoline of China's Some Enterprises can reach 500 μ g/g hereinafter, even 150 μ g/g
Below.But if further to reduce the sulfur content of catalytically cracked gasoline, it is less than 50 μ g/g and (meets IV discharge standard pair of Europe
The limitation of content of sulfur in gasoline), even less than 10 μ g/g (meet limitation of V discharge standard of Europe to content of sulfur in gasoline), then must be big
Amplitude improves the operating severity of catalytically cracked material hydrogenation plant, economically very uneconomical.The effective way to solve the above problems
Diameter is exactly to carry out hydrodesulfurization to catalytically cracked gasoline, while reduce the degree of saturation of wherein alkene to the maximum extent, to the greatest extent may be used
Loss of octane number can be reduced.
Catalytic gasoline hydrogenation obviously has the advantages of its uniqueness, low in terms of plant investment, production cost and hydrogen consumption
In catalytically cracked material weighted BMO spaces, and its different desulfurization depth can meet the requirement of different size sulfur content.But such as
Fruit can make with a large amount of saturations of high-octane olefin component to make in catalytically cracked gasoline using traditional hydrodesulfurizationprocess process
Loss of octane number is very big.It then becomes necessary to the catalytic gasoline selective hydrodesulfurizationmodification that development investment is low, loss of octane number is small
Technology.The catalytic gasoline selective hydrodesulfurizationmodification second-generation technology (RSDS-II) of Research Institute of Petro-Chemical Engineering's exploitation can
Sulfur Content in Catalytic Cracking Gasoline is reduced to 50 μ g/g hereinafter, and loss of octane number it is small.In order to will be in catalytically cracked gasoline
Sulfur content is reduced to more low-level, such as less than 10 μ g/g, reaction severity must be further improved, how in harsh reaction condition
Lower reduction alkene saturation factor, the loss of octane number for reducing product is the key point of selective hydrodesulfurization technology.
CN101381624A is disclosed olefinic naphtha by two stages of reaction, wherein first segment, is loaded special
Catalyst removes most of sulphur under mild conditions, and alkene saturation factor is not higher than 30%, second stage, under severe conditions
Further desulphurization reaction is carried out, reduces the generation of mercaptan to the greatest extent, alkene saturation factor is not higher than 20%, is less than the sulfur content of product
10μg/g。
WO 2007/061701 discloses a kind of method of the production low-sulphur oil using two-stage reaction, and this method is first
Carry out the removing of a large amount of sulfur-containing compounds in a reactor, for an anti-effluent using stripping, the methods of ammonia is washed carries out H2S takes off
It removes, removes H2Product after S enters second reactor and carries out further desulphurization reaction, and sulfur content is made to be preferably minimized level.
WO0179391 describes a kind of method for producing low-sulfur catalytic cracking gasoline.The first step is first by catalytically cracked gasoline
Selective hydrodesulfurization is carried out, obtains intermediate products；Intermediate products are carried out removal of mercaptans processing by second step.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 is disclosed is segmented sulfur removal technology by FCC gasoline.First segment keeps desulfurization degree 60~90%, technique item
Part：200~350 DEG C of temperature, 5~30kg/cm of pressure2, 2~10h of liquid hourly space velocity (LHSV)-1, hydrogen-oil ratio 89~534v/v, H2S concentration controls
System<1000ppm.Second segment controls desulfurization degree 60~90%, process conditions：200~300 DEG C of temperature, 5~15kg/cm of pressure2,
2~10h of liquid hourly space velocity (LHSV)-1, hydrogen-oil ratio 178~534v/v, H2S concentration controls<500ppm.If second segment desulfurization still reach to less than
Two sections of desulfurization are exported effluent and continue desulfurization by expected purpose, and process conditions are identical with two sections of desulfurization process conditions.But from it
From the point of view of implementation result, when total desulfurization degree is up to 95%, alkene saturation factor is 25%, and sweet gasoline, production are produced according to this technology
Product loss of octane number can be larger.
Under high desulfurization rate, higher reaction temperature is more advantageous to olefins hydrogenation reaction, if only anti-by improving
A large amount of alkene saturation will be led to, and excessively high reaction temperature can reduce catalyst to further improve desulfurization degree by answering temperature
Operation cycle.Be conducive to improve the selectivity of desulphurization reaction if using relatively low reaction temperature.But in relatively low reaction
At a temperature of, the H of desulphurization reaction generation2Alkene in S and raw material is easier to reaction generation mercaptan.Especially production sulfur content is less than
During state's V gasoline of 10 μ g/g, H2The reaction of S and alkene generation mercaptan is under the conditions of process for selective hydrogenation even close to balance.
This reaction results even in some cases can not produce state's V gasoline that sulfur content is less than 10 μ g/g.Break this reaction
Balance, be allowed to what is moved to desulfurization direction, theoretically analyze there is several methods that：First, it is that alkene in raw material largely adds hydrogen saturation, drops
Low concentration of olefin, reaction can then be moved to desulfurization direction, but a large amount of saturations of alkene cause significantly loss of octane number be exactly me
To be avoided；2nd, the H of desulphurization reaction generation is removed2S, due to H2S is to be continuously generated during the reaction, anti-in fixed bed
It answers in device, is difficult directly to remove H under operation condition2S, it is necessary to which, using two-stage method, first segment removes a large amount of sulphur, Ran Houzhong
Between set high pressure gas tower, cooling carry out gas-liquid separation, by H2S is removed, and deep desulfuration is carried out subsequently into second stage.But
It is that this method will certainly cause very big energy consumption.
Invention content
The technical problems to be solved by the invention are, while gasoline stocks deep hydrodesulfurizationof, how further to subtract
Miscellaneous goods loss of octane number, it is that raw material produces sulfur content less than 10 μ g/g super low-sulfur oils that the present invention, which provides one kind using high sulfur oil,
Method.
Method provided by the invention is to include the following steps：
(1) gasoline stocks are fractionated into light fraction gasoline and heavy distillat gasoline, wherein light fraction gasoline and heavy distillat gasoline
Cut point is 45 DEG C~75 DEG C,
(2) light fraction gasoline enters alkali density unit, refines removing mercaptan sulfur therein through alkali cleaning, obtains refined light fraction
Gasoline；
(3) heavy distillat gasoline and hydrogen together, into the first hydroconversion reaction zone, contacted with the de- diene catalyst of selectivity into
Row reaction, the reaction effluent of the first hydroconversion reaction zone are directly entered the second hydroconversion reaction zone and have passed through catalyst without isolation
The catalyst for selectively hydrodesulfurizing I contacts of selective regulation processing, carry out selective hydrodesulfurization reaction, the second hydrogenation reaction
The reaction effluent in area fully enters third hydroconversion reaction zone without gas-liquid separation, with have passed through catalyst choice regulation and control processing
Catalyst for selectively hydrodesulfurizing II contact reacted, the reaction effluent of third hydroconversion reaction zone is cooled down, is detached,
The liquid phase stream isolated enters stripper, and stripping tower bottom effluent is to add hydrogen heavy distillat gasoline, in the third reaction zone,
It is reacted under the latter stage operation temperature of catalyst for selectively hydrodesulfurizing II, meanwhile, by adjusting the reaction of second reaction zone
Temperature, to compensate the loss of activity of catalyst for selectively hydrodesulfurizing II,
(4) obtained by the refined light fraction gasoline obtained by step (2) and step (3) plus hydrogen heavy distillat gasoline mix, obtain
Gasoline products.
The boiling range of the gasoline stocks is 30-205 DEG C, and the volume fraction of alkene is 5%-60%, sulfur content 50-
5000μg/g.The gasoline stocks are selected from catalytically cracked gasoline, catalytic cracking gasoline, coker gasoline, pressure gasoline, straight run
Gasoline any of which or several miscellas, preferably catalytically cracked gasoline.
The reaction condition of first hydroconversion reaction zone is：It is 1.0~4.0MPa of hydrogen partial pressure, preferably 1.0~3.0MPa, anti-
Answer 80~300 DEG C of temperature, preferably 120~270 DEG C, 2~10h of volume space velocity-1, preferably 6~10h-1, hydrogen to oil volume ratio 200~
1000Nm3/m3, preferably 300~800Nm3/m3。
The reaction condition of second hydroconversion reaction zone is：It is 1.0~3.0MPa of hydrogen partial pressure, preferably 1.0~2.0MPa, anti-
Answer 200~350 DEG C of temperature, preferably 220~300 DEG C, 2.0~8.0h of volume space velocity-1, preferably 3.0~6.0h-1, hydrogen to oil volume ratio
200~1000Nm3/m3；The reaction condition of the third hydroconversion reaction zone is：1.0~3.0MPa of hydrogen partial pressure, reaction temperature 340
~420 DEG C, preferably 350~390 DEG C, 10.0~40.0h of volume space velocity-1, preferably 12.0~30.0h-1, hydrogen to oil volume ratio 200~
1000Nm3/m3。
In the present invention, reaction stream is selected in the second hydrogenation reactor under lower temperature, relatively low air speed
Property hydrodesulfurization reaction, remove raw material in most sulphur, and as possible reduce alkene saturation factor.Control second reactor outlet object
The desulfurization degree of stream is 60~99%, and it is 0.2~2.0, preferably 0.2~1.0 that preferably 80~98%, RON losses, which are not more than).
Second hydrogenation reactor outlet material fully enters third hydrogenation reactor without gas-liquid separation after heating,
Since sulphur most of in raw material removes in the second hydrogenation reactor, sulfur content in the liquid phase of the second hydrogenation reactor outlet material
It is very low, but H in gas phase2S concentration is higher.Sulphur is generated in order to avoid it reacts in third hydrogenation reactor and alkene
The operating condition of third reactor reaction is maintained at catalyst latter stage operation temperature and carried out by alcohol, the present invention.The catalyst
Latter stage operation temperature refers to that catalyst has the maximum operation (service) temperature of catalytic activity.At the same time, third hydrogenation reactor uses
The catalyst for selectively hydrodesulfurizing II that selectivity is preferable but activity is relatively low, then carried out by selective regulation processing step
After processing, reaction stream can carry out further desulphurization reaction, effectively prevent simultaneously at high temperature in third hydrogenation reactor
Mercaptan generates, so as to obtain the heavy distillat gasoline that sulfur content is less than 10 μ g/g.The present invention is by adjusting the second hydrogenation reactor
Reaction temperature compensate the loss of activity of catalyst for selectively hydrodesulfurizing II.
It is preferred that the second hydroconversion reaction zone reaction temperature is 60~150 DEG C lower than third hydroconversion reaction zone reaction temperature.
It is preferred that the second hydroconversion reaction zone volume space velocity is higher 2~38h than third hydroconversion reaction zone volume space velocity-1。
It is the Section VI B being supported in alumina support and/or silica-alumina supports that the selective hydrogenation, which takes off diene catalyst,
Race's metal and/or group VIII metallic catalyst, wherein vib metals are selected from molybdenum and/or tungsten, and 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 components and
Vib metals component and in alcohol, organic acid and organic amine one or more of organic matters catalyst, wherein Section VIII
Race's base metal is selected from cobalt and/or nickel, and vib metals are selected from molybdenum and/or tungsten.
It is preferred that the catalyst for selectively hydrodesulfurizing I, is counted by oxide and on the basis of catalyst, the group VIII
The mass fraction of metal component is 0.1~6%, and the mass fraction of vib metals component is 1~25%, the organic matter with
The molar ratio of group VIII metal component is 0.5~2.5, and the carrier is a kind of bimodal porous aluminum oxide, is characterized with mercury injection method, institute
0.9~1.2 ml/g of the Kong Rongwei of carrier is stated, specific surface area is 50~300 meters2/ gram, the hole body in a diameter of 10~30nm holes
Product accounts for the 55~80% of total pore volume, and the pore volume in a diameter of 300~500nm holes accounts for the 10~35% of total pore volume.
The catalyst for selectively hydrodesulfurizing II is to be supported on silica support your non-gold of group VIII contained
Belong to component and vib metals component and in alcohol, organic acid and organic amine one or more of organic matters catalyst,
Middle group VIII base metal is selected from cobalt and/or nickel, and vib metals are selected from molybdenum and/or tungsten.
It is preferred that the catalyst for selectively hydrodesulfurizing II, is counted by oxide and on the basis of catalyst, the Section VIII
The mass fraction of race's metal component is 0.1~3%, and the mass fraction of vib metals component is 1~15%, the organic matter
It is 0.5~2.5 with the molar ratio of group VIII metal component, the carrier is a kind of silica, 0.5~1.0 milliliter of Kong Rongwei/
Gram, specific surface area is 20~200 meters2/ gram.
The preparation method of preferred catalyst for selectively hydrodesulfurizing I and catalyst for selectively hydrodesulfurizing II is as follows.
In the present invention, at least one non-noble metal metal component selected from VIII group and at least of being introduced on carrier
A kind of method of metal component selected from group vib and one or more of organic matters in alcohol, organic acid and organic amine is excellent
The method of dipping is selected as, the dipping method is conventional method, such as hole saturation dipping, excessive liquid impregnate and spray dipping
Deng.Wherein, the group VIII, group VIB and one or more of organic matters in alcohol, organic acid and organic amine can be single
It solely introduces, two two or three kinds of can also simultaneously introduce.When being introduced using infusion process, including preparing dipping solution, for example, by containing
The chemical combination of the compound of the metal component selected from least one group VIB, the metal component containing at least one group VIII
Object or one or more of organic matters in alcohol, organic acid and organic amine prepare dipping solution respectively, and molten with these dippings
Liquid distinguishes impregnated carrier；Either by containing the metal component selected from least one group VIB, containing at least one group VIII
Metal component compound and one or more of organic matters in alcohol, organic acid and organic amine in match for two or three
System is mixed with dipping solution, and the method for impregnated carrier is distinguished with these dipping solutions.When the dipping is step impregnation, to institute
State the sequence of dipping solution impregnated carrier there is no limit.Although being not required, dry step is preferably included after dipping every time.
The drying condition includes：100~210 DEG C of drying temperature, preferably 120~190 DEG C, 1~6 hour drying time, preferably 2
~4 hours.
The activity of catalyst is weighed to reach the reaction temperature of identical desulfurization degree, catalyst for selectively hydrodesulfurizing I's
Activity than catalyst for selectively hydrodesulfurizing II activity it is 5 DEG C high~60 DEG C.
The 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；Sp- product sulfur content；Sf- feed sulphur content；Op- product alkene quality contains
Amount；Of- raw material olefin mass content.The selectivity of catalyst for selectively hydrodesulfurizing II is than catalyst for selectively hydrodesulfurizing I
2~10 units of high selectivity.
The catalyst for selectively hydrodesulfurizing I and catalyst for selectively hydrodesulfurizing II is carried out after vulcanization
Catalyst choice regulation and control are handled, and reach corresponding activity and selectivity requirement.Catalyst for selectively hydrodesulfurizing passes through
After vulcanization, there are desulphurizing activated centers and olefins hydrogenation activated centre Liang Zhong activated centres.The present invention in sulfidation and
Increase catalyst choice regulation process between normal productive process, one of which activated centre can be significantly shielded, so as to carry
The selectivity of high-selective and hydrogenating desulphurization catalyst.The catalyst choice regulation process is that raw material living will be urged to urge lively atmosphere
It is contacted in the atmosphere of body, in the case where urging reaction condition living with catalyst for selectively hydrodesulfurizing.The process can be effectively so that coking
Charcoal is covered in catalyst olefins hydrogenation activated centre, makes catalyst for selectively hydrodesulfurizing olefins hydrogenation activity significantly
Reduce, and desulphurizing activated center is valid protected, make catalyst for selectively hydrodesulfurizing it is desulphurizing activated it is basic without loss or
Lose very little.
The catalyst choice regulation and control of the catalyst for selectively hydrodesulfurizing I and catalyst for selectively hydrodesulfurizing II
Processing, includes the following steps：
(a) after sulfidation, it is to urge lively atmosphere body to adjust gas in reaction system；
(b) raw material living will be urged to introduce reaction system, and contacted in the case where urging reaction condition living with catalyst 24~96 hours；
(c) it urges and living after reaction, adjusting process condition is normal reaction conditions, and switching reaction feed is full distillation gasoline
Or heavy distillat gasoline；
(d) it is hydrogen-rich gas to adjust gas in reaction system, carries out normal reaction.
It is described that lively atmosphere body is urged to include hydrogen, hydrogen sulfide and carbon monoxide, on the basis of to urge lively atmosphere body entirety, wherein hydrogen
For volume fraction not less than 70%, the sum of volume fraction of hydrogen sulfide and carbon monoxide is 0.05%~5%；Hydrogen preferably wherein
For volume fraction not less than 80%, the sum of volume fraction of hydrogen sulfide and carbon monoxide is 0.3%~2%.
It is described to urge the reaction condition living to be：0.6~2.0MPa of hydrogen partial pressure, 200~350 DEG C of reaction temperature, volume space velocity 1~
10h-1, 50~400Nm of hydrogen to oil volume ratio3/m3.It is preferred that it is small that raw material living is urged to contact 48~80 with catalyst in the case where urging reaction condition living
When.
In one preferred embodiment, the reaction temperature for urging reaction living is higher than the reaction temperature of normal reaction
30~100 DEG C.
In one preferred embodiment, the volume space velocity for urging reaction living is lower than the volume space velocity of normal reaction
2~4h-1。
The boiling range for urging raw material living is 30~350 DEG C, wherein, the volume fraction of alkene is 5%~60%.
It is preferred that described urging also contains aromatic hydrocarbons in raw material living, the volume fraction of aromatic hydrocarbons is 5%~60%.
Step (d) hydrogen-rich gas, on the basis of hydrogen-rich gas entirety, the volume fraction of hydrogen is at least 70%, sulphur
Change the sum of volume fraction of hydrogen and carbon monoxide and be less than 0.05%.It is preferred that the volume fraction of hydrogen is at least 80%, hydrogen sulfide and
The sum of volume fraction of carbon monoxide is less than 0.02%.
In a kind of currently preferred embodiment, in step (b), hydrogen sulfide gas in gas reactor is first reduced
Concentration, be further added by the concentration of CO gas in gas reactor, finally adjust in reactor gas to urge lively atmosphere body.
In a kind of currently preferred embodiment, in step (d), carbon monoxide gas in gas reactor is first reduced
The concentration of body, then the concentration of hydrogen sulfide gas in gas reactor is reduced, it is hydrogen-rich gas finally to adjust gas in reactor.
Using method provided by the invention, the catalytically cracked gasoline of the high alkene of high-sulfur can be handled, product sulfur content is less than
10 μ g/g, loss of octane number is small, and yield of gasoline is up to more than 99%.Compared with prior art, the same of sulfur content is further reduced
When, keep the smaller loss of octane number of product.It is damaged simultaneously by second reactor to compensate the activity of third reactor catalyst
It loses, maintains the service life of catalyst, improve the selectivity of reaction to greatest extent and extend the device operation cycle.
Description of the drawings
Attached drawing is the flow diagram provided by the invention for reducing content of sulfur in gasoline method.
Specific embodiment
Method provided by the present invention is further detailed below in conjunction with the accompanying drawings, but does not therefore limit this hair
It is bright.
As shown in drawings, the method provided by the invention for reducing content of sulfur in gasoline is described in detail as follows：From the complete of pipeline 1
Distillation gasoline raw material enters fractionating column 2, and the light fraction gasoline obtained after shunting enters alkali density removal of mercaptans unit through pipeline 3
4 carry out removal of mercaptans processing, and the light fraction gasoline after removal of mercaptans comes out is mixed to get through pipeline 5 and the logistics from pipeline 34
Full fraction product.The heavy distillat gasoline obtained from fractionating column 2 is flowed out from pipeline 6, after 7 boosting of raw material pump and from pipeline 31
Enter after hydrogen mixing after heat exchanger 8, with the material-heat-exchanging from pipeline 22 and enter the first hydrogenation reactor 10 through pipeline 9, into
De- two alkene reactions of row selectivity.First hydrogenation reactor effluent through pipeline 11 enter heating furnace 12 heat after, through pipeline 13 into
Enter the second hydrogenation reactor 14, carry out selective hydrodesulfurization reaction.Second hydrogenation reactor effluent is through pipeline 15 with coming from
The material of pipeline 21 is after the heat exchange of heat exchanger 16, after pipeline 17 enters the heating of heating furnace 18, adds hydrogen into third through pipeline 19
Reactor 20, third reactor effluent is after pipeline 21 enters heat exchanger 16 and the material-heat-exchanging from pipeline 15 through pipeline 22
Into heat exchanger 8, enter after the cooling of air-cooled 24, water cooling 25 through pipeline 23 after being exchanged heat with the material from pipeline 7 and enter
High-pressure separator 26.After high-pressure separator 26 carries out gas-liquid separation, the hydrogen-rich gas at top enters desulfurizing tower 28 through pipeline 27
Remove H in hydrogen2It boosts after S through pipeline 29 into circulating hydrogen compressor 30, the H after boosting27 are pumped through pipeline 31 and raw material
Outlet material mixes.The stream passes via line 32 obtained from 26 bottom of high-pressure separator enters stabilizer 33, the light hydrocarbon gas of tower top
It is extracted out by pipeline 35, tower bottom product is mixed to get full distillation gasoline product through pipeline 34 with the logistics from pipeline 5.
The following examples will be further described method provided by the invention, but therefore not limit this hair
It is bright.
The trade names of hydrotreating catalyst C, D, E used in comparative example be respectively RGO-3, RSDS-21,
RSDS-22 is produced by Sinopec catalyst Chang Ling branch company.
The trade names that selective hydrogenation used in embodiment takes off diene catalyst are RGO-3, by Sinopec catalyst
Chang Ling branch company produces.
Catalyst for selectively hydrodesulfurizing I used in embodiment is catalyst A, and catalyst for selectively hydrodesulfurizing II is urges
Agent B.The carrier of catalyst A is aluminium oxide, and active metal composition is：13.5 heavy % of molybdenum oxide, 4.0 heavy % of cobalt oxide.Catalysis
The carrier of agent B is silica, and active metal composition is：8.5 heavy % of molybdenum oxide, 3.0 heavy % of cobalt oxide.
The activity of catalyst is weighed to reach the reaction temperature of identical desulfurization degree, the activity of catalyst A is than catalyst B's
Activity is 5~60 DEG C high.
Weigh the selectivity of catalyst with selectivity factor, high selectivity 2 of the selectivity than catalyst B of catalyst A~
10 units.
Selectivity factor uses following definition：S=log (Sp/Sf)/log(Op/Of).In formula：S-selectivity factor；
Sp- product sulfur content；Sf- feed sulphur content；Op- product alkene mass content；Of- raw material olefin mass content.
To give full play to the hydrodesulfurization performance of catalyst, above-mentioned catalyst is required to carry out before formal raw material is contacted pre-
Vulcanizing treatment.In comparative example and embodiment set forth below, the method for pre-sulphuration of each catalyst is identical.
In embodiment, selective regulation processing has all been carried out to catalyst A and catalyst B, process is：Vulcanization terminates
Afterwards, gas in reaction system is adjusted, to urge lively atmosphere body, to urge in lively atmosphere body, the volume fraction of hydrogen is 90%, hydrogen sulfide and an oxygen
The sum of the volume fraction for changing carbon is 1.8%, and raw material living will be urged to introduce reaction system, and urge condition living for hydrogen partial pressure 1.6MPa,
Hydrogen-oil ratio 100Nm3/m3, volume space velocity 4.0h-1, make raw material living is urged to contact 72h with catalyst under conditions of 350 DEG C of reaction temperature,
Selective regulation processing is carried out to catalyst.The boiling range for urging raw material living is 30~350 DEG C, wherein, the volume fraction of alkene is
28%, the volume fraction of aromatic hydrocarbons is 20%.Catalyst carries out selective regulation after treatment, is adjusted to normal reaction conditions,
Switch reaction feed and be the heavy distillat of feedstock oil, and it is hydrogen-rich gas to switch gas in reactor, with hydrogen-rich gas generally base
Standard, the volume fraction of hydrogen is 90%, and the sum of volume fraction of hydrogen sulfide and carbon monoxide is 0.005%.
Comparative example 1
A kind of catalytically cracked gasoline feedstock oil F (its raw material oil nature is shown in Table 1) is first segmented into light fraction in fractionating column inscribe
Gasoline (boiling range C5~65 DEG C) and heavy distillat gasoline (65 DEG C~190 DEG C of boiling range).Wherein light fraction quality of gasoline ratio is 25%,
Heavy distillat quality of gasoline ratio is 75%.Light fraction gasoline alkali density removal of mercaptans；Heavy distillat gasoline uses the choosing of two reactors
Selecting property hydrodesulfurizationprocess process carries out hydrodesulfurization processing, and loading catalyst C, is loaded in the second reactor in the first reactor
Catalyst D and E, the two admission space ratio are D:E=85:15.Light fraction gasoline after alkali density adds hydrogen to take off with passing through
Heavy distillat gasoline after sulphur is mixed to get full distillation gasoline product.Product property and reaction process condition are as shown in table 2, by table 2
It can be seen that the sulfur content of product is 8 μ g/g, alkene volume saturation factor loses 3.2 for 43.8%, RON, and product quality yield is
99.8%.
Comparative example 2
A kind of catalytically cracked gasoline feedstock oil F is first segmented into light fraction gasoline (boiling range C in fractionating column inscribe5~65 DEG C) and
Heavy distillat gasoline (65 DEG C~190 DEG C of boiling range).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；The method that heavy distillat gasoline carries out subregion reaction using three reactors.First is anti-
Answer device loading catalyst C, second reactor and the equal loading catalyst E of third reactor.Specific reaction condition and full fraction vapour
Oil 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 saturation factor is 31.5%, RON
It is 1.6 to lose, and product yield is 99.7 heavy %.
But since the activity of catalyst E is relatively low, second reactor employs higher reaction temperature desulfurization to be kept to live
Property, after running 3000 hours, catalyst E activity is decreased obviously, and the work of catalyst E is maintained using continuing to improve reaction temperature
Property, the operation temperature of the second hydrogenation reactor is carried by 310 temperature to 320 temperature, since temperature raising space is limited, is urged quickly reaching
Agent latter stage operation temperature, therefore the whole device cycle of operation is short.
Embodiment 1
Using a kind of catalytically cracked gasoline as feedstock oil F, raw material oil nature is as shown in table 1.Feedstock oil F is first in fractionating column
It is cut into light fraction gasoline (boiling range C5~65 DEG C) and heavy distillat gasoline (65 DEG C~190 DEG C of boiling range).Wherein light fraction gasoline matter
Amount ratio is 25%, and heavy distillat quality of gasoline ratio is 75%.Light fraction gasoline alkali density removal of mercaptans；Heavy distillat gasoline is using this
Technological process carries out hydrodesulfurization processing in invention attached drawing.Light fraction gasoline after alkali density with after hydrodesulfurization
Heavy distillat gasoline is mixed to get full distillation gasoline product.
First reactor, second reactor and the specific reaction condition of third reactor and full distillation gasoline product property are such as
Shown in table 3, the sulfur content of product is 9 μ g/g as can be seen from Table 3, and olefin(e) centent only loses 1.5 for 30.6 volume %, RON, production
Product yield is 99.8 heavy %.
The operating condition of third reactor reaction is maintained at catalyst latter stage operation temperature and carried out, and pass through tune by the present invention
The reaction temperature of whole second hydrogenation reactor compensates the loss of activity of catalyst for selectively hydrodesulfurizing II.Due to the second reaction
The higher catalyst A of device filling activity, equally, after running 3000 hours, the operation temperature of the second hydrogenation reactor of the invention needs
It to be carried by 260 temperature to 270 temperature, still, since the temperature raising space of the second hydrogenation reactor of the invention is big, it is entire to fill
It is long to put the operation cycle.
Embodiment 2
Using a kind of catalytically cracked gasoline as feedstock oil G, raw material oil nature is as shown in table 1.Feedstock oil G is first in fractionating column
It is cut into light fraction gasoline (boiling range C5~58 DEG C) and heavy distillat gasoline (58 DEG C~205 DEG C of boiling range).Wherein light fraction steam oil ratio (SOR)
Example is 25 heavy %, and heavy distillat gasoline proportionality is 75 heavy %.Light fraction gasoline alkali density removal of mercaptans；Heavy distillat gasoline is using the present invention
Technological process carries out hydrodesulfurization processing in attached drawing.Light fraction gasoline after alkali density and the double distilled after hydrodesulfurization
Gasoline is divided to be mixed to get full distillation gasoline product in products pot.
First reactor, second reactor and the specific reaction condition of third reactor and full distillation gasoline product property are such as
Shown in table 3, the sulfur content of product is 8 μ g/g as can be seen from Table 3, and olefin(e) centent only loses 1.1 for 24.1 volume %, RON, production
Product yield is 99.7 heavy %.
Embodiment 3
Using a kind of catalytically cracked gasoline as feedstock oil I, raw material oil nature is as shown in table 1.Feedstock oil I is first in fractionating column
It is cut into light fraction gasoline (boiling range C5~60 DEG C) and heavy distillat gasoline (60 DEG C~205 DEG C of boiling range).Wherein light fraction steam oil ratio (SOR)
Example is 24 heavy %, and heavy distillat gasoline proportionality is 76 heavy %.Light fraction gasoline alkali density removal of mercaptans；Heavy distillat gasoline is using the present invention
Technological process carries out hydrodesulfurization processing in attached drawing.Light fraction gasoline after alkali density and the double distilled after hydrodesulfurization
Gasoline is divided to be mixed to get full distillation gasoline product in products pot.
First reactor, second reactor and the specific reaction condition of third reactor and full distillation gasoline product property are such as
Shown in table 3, the sulfur content of product is 8 μ g/g as can be seen from Table 3, and olefin(e) centent only loses 1.0 for 22.6 volume %, RON, production
Product yield is 99.6 heavy %.
Table 1
| Material name | F | G | I |
| Density (20 DEG C), g/cm3 | 0.7234 | 0.7321 | 0.7311 |
| Sulphur, 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 | |
| Feedstock oil | F | F |
| Reaction condition | ||
| First reactor | ||
| Catalyst | C | C |
| Reaction temperature, DEG C | 180 | 180 |
| Hydrogen partial pressure, 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 partial pressure, MPa | 1.6 | 1.6 |
| Hydrogen to oil volume ratio, Nm3/m3 | 400 | 400 |
| Volume space velocity, h-1 | 4.0 | 4.0 |
| Third reactor | Nothing | |
| Catalyst | - | E |
| Reaction temperature, DEG C | - | 360 |
| Hydrogen partial pressure, 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 | |
| Feedstock oil | F | G | I |
| Reaction condition | |||
| First hydrotreating reactor | |||
| Catalyst | C | C | C |
| Reaction temperature, DEG C | 180 | 180 | 180 |
| Hydrogen partial pressure, 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 partial pressure, 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 |
| Third hydrotreating reactor | |||
| Catalyst | B | B | B |
| Reaction temperature, DEG C | 360 | 380 | 390 |
| Hydrogen partial pressure, 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 (19)
1. a kind of method for reducing content of sulfur in gasoline, includes the following steps：
(1) gasoline stocks are fractionated into the cutting of light fraction gasoline and heavy distillat gasoline, wherein light fraction gasoline and heavy distillat gasoline
Point is 45 DEG C~75 DEG C；
(2) light fraction gasoline enters alkali density unit, refines removing mercaptan sulfur therein through alkali cleaning, obtains refined light fraction vapour
Oil；
(3) heavy distillat gasoline and hydrogen together, into the first hydroconversion reaction zone, it is anti-to contact progress with the de- diene catalyst of selectivity
Should, the reaction effluent of the first hydroconversion reaction zone is directly entered the second hydroconversion reaction zone and have passed through catalyst choice without isolation
Property regulation and control processing catalyst for selectively hydrodesulfurizing I contact, carry out selective hydrodesulfurization reaction, the second hydroconversion reaction zone
Reaction effluent fully enters third hydroconversion reaction zone without gas-liquid separation, the choosing with have passed through catalyst choice regulation and control processing
Selecting property Hydrobon catalyst II contacts are reacted, and the reaction effluent of third hydroconversion reaction zone is cooled down, detached, separation
The liquid phase stream gone out enters stripper, and stripping tower bottom effluent is to add hydrogen heavy distillat gasoline, in the third hydroconversion reaction zone,
It is reacted under the latter stage operation temperature of catalyst for selectively hydrodesulfurizing II, meanwhile, by adjusting the second hydroconversion reaction zone
Reaction temperature, to compensate the loss of activity of catalyst for selectively hydrodesulfurizing II, the second hydroconversion reaction zone reaction temperature
60~150 DEG C lower than third hydroconversion reaction zone reaction temperature, the second hydroconversion reaction zone volume space velocity adds hydrogen anti-than third
Answer the low 2~38h of area's volume space velocity-1,
(4) obtained by the refined light fraction gasoline obtained by step (2) and step (3) plus hydrogen heavy distillat gasoline mix, obtain gasoline
Product.
2. according to the method described in claim 1, which is characterized in that the boiling range of the gasoline stocks is 30-205 DEG C, alkene
Volume fraction for 5%-60%, sulfur content is 50-5000 μ g/g.
3. according to the method for claim 1, which is characterized in that the reaction condition of first hydroconversion reaction zone is：Hydrogen
Divide 1.0~4.0MPa, 80~300 DEG C of reaction temperature, 2~10h of volume space velocity-1, 200~1000Nm of hydrogen to oil volume ratio3/m3。
4. according to the method for claim 1, which is characterized in that the reaction condition of second hydroconversion reaction zone is：Hydrogen
Divide 1.0~3.0MPa, 200~350 DEG C of reaction temperature, 2.0~8.0h of volume space velocity-1, 200~1000Nm of hydrogen to oil volume ratio3/
m3；The reaction condition of the third hydroconversion reaction zone is：1.0~3.0MPa of hydrogen partial pressure, 340~420 DEG C of reaction temperature, volume
10.0~40.0h of air speed-1, 200~1000Nm of hydrogen to oil volume ratio3/m3。
5. according to the method for claim 1, it is characterised in that the catalyst for selectively hydrodesulfurizing I and selectivity adds
The selective regulation processing of hydrogen desulphurization catalyst II includes the following steps：
(a) after sulfidation, it is to urge lively atmosphere body to adjust gas in reaction system；
(b) raw material living will be urged to introduce reaction system, and contacted in the case where urging reaction condition living with catalyst 24~96 hours；
(c) it urges and living after reaction, adjusting process condition is normal reaction conditions, and switching reaction feed is for full distillation gasoline or again
Distillation gasoline；
(d) it is hydrogen-rich gas to adjust gas in reaction system, carries out normal reaction.
6. according to the method for claim 5, it is characterised in that described that lively atmosphere body is urged to include hydrogen, hydrogen sulfide and an oxidation
Carbon, on the basis of urging lively atmosphere body entirety, the wherein volume fraction of hydrogen is not less than 70%, the volume point of hydrogen sulfide and carbon monoxide
The sum of number is 0.05%~5%.
7. according to the method for claim 6, it is characterised in that it is described to urge in lively atmosphere body, on the basis of urging lively atmosphere body entirety,
For the wherein volume fraction of hydrogen not less than 80%, the sum of volume fraction of hydrogen sulfide and carbon monoxide is 0.3%~2%.
8. according to the method for claim 5, it is characterised in that urge the reaction condition living to be：0.6~2.0MPa of hydrogen partial pressure, reaction
200~350 DEG C of temperature, 1~10h of volume space velocity-1, 50~400Nm of hydrogen to oil volume ratio3/m3。
9. according to the method for claim 5, it is characterised in that raw material living is urged to be contacted in the case where urging reaction condition living with catalyst
48~80 hours.
10. according to the method for claim 5, it is characterised in that the boiling range for urging raw material living is 30~350 DEG C,
In, the volume fraction of alkene is 5%~60%.
11. according to the method for claim 10, it is characterised in that described urging also contains aromatic hydrocarbons, the body of aromatic hydrocarbons in raw material living
Fraction is 5%~60%.
12. according to the method for claim 5, it is characterised in that the hydrogen-rich gas of the step (d), with hydrogen-rich gas entirety
On the basis of, the volume fraction of hydrogen is at least 70%, and the sum of volume fraction of hydrogen sulfide and carbon monoxide is less than 0.05%.
13. according to the method for claim 1, which is characterized in that the selective hydrogenation takes off diene catalyst for load
Vib metals and/or group VIII metallic catalyst on alumina support and/or silica-alumina supports, wherein group VIB gold
Belong to selected from molybdenum and/or tungsten, group VIII metal is selected from cobalt and/or nickel.
14. according to the method for claim 1, it is characterised in that the catalyst for selectively hydrodesulfurizing I is is supported on
On alumina support containing group VIII non-noble metal components and vib metals component and selected from alcohol, organic acid and have
The catalyst of one or more of organic matters in machine amine, wherein group VIII base metal are selected from cobalt and/or nickel, vib metals
Selected from molybdenum and/or tungsten.
15. according to the method for claim 14, it is characterised in that the catalyst for selectively hydrodesulfurizing I, with oxide
It counts and on the basis of catalyst, the mass fraction of the group VIII metal component is 0.1~6%, vib metals component
Mass fraction is 1~25%, and the molar ratio of the organic matter and group VIII metal component is 0.5~2.5, and the carrier is one
The bimodal porous aluminum oxide of kind, is characterized, 0.9~1.2 ml/g of the Kong Rongwei of the carrier with mercury injection method, and specific surface area is 50~300
Rice2/ gram, the pore volume in a diameter of 10~30nm holes accounts for the 55~80% of total pore volume, the pore volume in a diameter of 300~500nm holes
Account for the 10~35% of total pore volume.
16. according to the method for claim 1, it is characterised in that the catalyst for selectively hydrodesulfurizing II is is supported on
On silica support containing group VIII non-noble metal components and vib metals component and selected from alcohol, organic acid and have
The catalyst of one or more of organic matters in machine amine, wherein group VIII base metal are selected from cobalt and/or nickel, vib metals
Selected from molybdenum and/or tungsten.
17. according to the method for claim 16, it is characterised in that the catalyst for selectively hydrodesulfurizing II, with oxide
It counts and on the basis of catalyst, the mass fraction of the group VIII metal component is 0.1~3%, vib metals component
Mass fraction is 1~15%, and the molar ratio of the organic matter and group VIII metal component is 0.5~2.5, and the carrier is one
Kind silica, 0.5~1.0 ml/g of Kong Rongwei, specific surface area are 20~200 meters2/ gram.
18. according to the method any in claim 1,14,15,16,17, which is characterized in that reach identical desulfurization degree
Reaction temperature weigh the activity of catalyst, the activity of catalyst for selectively hydrodesulfurizing I is catalyzed than selective hydrodesulfurization
Agent II activity it is 5 DEG C high~60 DEG C.
19. according to the method any in claim 1,14,15,16,17, which is characterized in that weighed with selectivity factor
The selectivity of catalyst, selectivity of the selectivity than catalyst for selectively hydrodesulfurizing I of catalyst for selectively hydrodesulfurizing II
High 2~10 units.
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| FR3103822B1 (en) * | 2019-12-02 | 2022-07-01 | Ifp Energies Now | METHOD FOR TREATMENT OF PYROLYSIS OILS FROM PLASTICS WITH A VIEW TO RECYCLING THEM IN A STEAM CRACKING UNIT |
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