CN105670688B - A kind of method for producing sweet gasoline - Google Patents
A kind of method for producing sweet gasoline Download PDFInfo
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- CN105670688B CN105670688B CN201410663737.1A CN201410663737A CN105670688B CN 105670688 B CN105670688 B CN 105670688B CN 201410663737 A CN201410663737 A CN 201410663737A CN 105670688 B CN105670688 B CN 105670688B
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Abstract
The invention provides a kind of method for producing sweet gasoline, the method includes：(1) in presence of hydrogen, contacted with selective hydrocatalyst in selective hydrogenation reactor carries out selective hydrogenation to bad gasoline；(2) contacted as the product obtained by step (1) in first choice hydrodesulphurisatioreactors reactors with first choice Hydrobon catalyst, carry out first choice hydrodesulfurization reaction；(3) product as obtained by step (2) enters H2S strippers, obtain containing H from tower top2The gas phase of S, bottom of towe obtains removing H2S liquid phase；(4) liquid phase as obtained by step (3) is contacted in the second selective hydrodesulfurization reactor with the second catalyst for selectively hydrodesulfurizing；(5) entered as the product obtained by step (4) and contacted in hydrofining reactor with Hydrobon catalyst.The method of the present invention can produce and obtain sulfur content and be not more than 5 μ g/g, the less sweet gasoline of loss of octane number, and product high income.
Description
Technical field
The present invention relates to a kind of method for producing sweet gasoline, relate more specifically to a kind of super to high sulfur content and mercaptan sulfur
The method that target gasoline carries out selective hydrogenation process for producing sweet gasoline (sulfur content is not more than 5 μ g/g), more particularly to entirely
The method that the catalytically cracked gasoline (abbreviation FCC gasoline) of cut carries out selective hydrodesulfurization, removal of mercaptans.
Background technology
With the raising of the further strict and automobile engine technology of environmental requirement, the quality to motor petrol is proposed
Requirement higher, current whole nation executed content of sulfur in gasoline index is not more than the standard of state III of 150 μ g/g.Shanghai and Guangzhou are first
Local IV standard that content of sulfur in gasoline index is not more than 50 μ g/g is performed afterwards, and executed content of sulfur in gasoline index in Beijing is not more than 10
μ g/g local V standard.And the standard of state IV and content of sulfur in gasoline index that content of sulfur in gasoline index is not more than 50 μ g/g are not more than
The National V emission standard of 10 μ g/g is expected to be released in the whole nation in recent years.Therefore production super-low sulfur clean gasoline is urgently solved as each oil plant
Problem.
At present, the sulphur in gasoline more than 90% comes from catalytically cracked gasoline.Therefore, the sulfur content of catalytically cracked gasoline is reduced
It is to produce low-sulphur oil, meet the key of current and following specification gasoline with mercaptans content.
Traditional hydrodesulfurization (HDS) technique can effectively reduce the sulphur and mercaptans content in catalytically cracked gasoline.But,
Because while gasoline hydrodesulfurizationmethod, alkene is significantly hydrogenated with saturation, damage octane number (RON values) in this way
Lose larger.
In order to reduce the loss of sulfur-free gasoline octane number, many catalytic gasoline selective hydrogenation are developed both at home and abroad de-
Sulphur (SHDS) process, its method is based on following principle：Hydrodesulfurization optionally is carried out to gasoline, by sulfur compound
Change into H2S, while limiting olefins hydrogenation reaction, can receive so as to reach the octane number damage control
Level.
At present, the catalytic gasoline selective hydrodesulfurizationmodification technique of domestic industry application mainly has CDTECH companies of the U.S.
CDHydr/CDHDS techniques, the Prime-G of France AXNES+, Fushun Petrochemical Research Institute OCT-MD techniques, Bei Jinghai
The CDOS-HCN techniques of Shuande titanium catalyst Co., Ltd.The characteristics of these techniques is to be cut into catalytically cracked gasoline fractionation
Gently, weigh two cuts or it is light, in, weigh three cuts, and characteristic for different fractions is respectively processed, wherein heavy distillat vapour
Oil is to carry out selective hydrodesulfurization using special catalyst, and each cut after processing then is obtained by mixing into low-sulfur vapour again
Oil.These techniques are both needed to set special fractionating device, all different degrees of compared to technique of the present invention to there is investment
Larger, flow is more complicated and the problems such as larger energy consumption.
CN102041086A discloses a kind of high-sulfur, the selective hydrodesulfurization method of olefin catalytic gasoline high, and it is first
Full cut catalytic gasoline is carried out into weighted BMO spaces, after being hydrogenated with pre- desulfurization, feedstock oil is then carried out into fractionation again and is cut into light, weight
Cut is respectively processed, and the sulfur content of products obtained therefrom is not more than 50 μ g/g, and mercaptan sulfur content is not more than 10 μ g/g, and octane number is damaged
Lose 1.5 units.
The method that EP1031622 discloses full cut FCC gasoline hydrodesulfurization, but mercaptan sulfur content exceedes in low sulfur product
10μg/g。
CN101173184A discloses a kind of method of selectively hydrogenating and desulfurizing inferior gasoline, has been described in detail in selectivity
Removing H is added during hydrodesulfurization reaction, in raw material2The depriving hydrogen sulphide agent (such as ammonia, alcamine compound) of S.Although can be with
Full distillation gasoline raw material is handled, and the sulfur content of product is not more than 50 μ g/g, and mercaptan sulfur content is not more than 10 μ g/g, but to disappear
Consume a large amount of depriving hydrogen sulphide agent.
USP6692635 discloses one hydrofining reaction area of supplement behind hydrodesulfurizationreaction reaction zone, is urged in 20%NiO
Further it is hydrogenated with agent, saturation sulfide (including mercaptan) is converted into H2S.In the case of equal desulfurization degree 92%, compare
The example of single hydrodesulfurization reaction, the anti-knock index (RON+MON)/2 of octane number drops to 2 units by losing 5 units.The party
Method needs to carry out raw material fractionation cutting, and heavy distillat gasoline carries out hydrodesulfurization treatment, and product sulfur content only reaches 96~240 μ
g/g。
EP1346144 discloses a kind of gasoline hydrodesulfurizationmethod and the method for limiting mercaptans content, and this method includes a part
Sulfur-free gasoline is recycled to the entrance of desulfurization reactor, and recirculation volume is 0.1-3 times of pending feedstock amount.
CN1294240C discloses a kind of full cut FCC gasoline in presence of hydrogen by the processing of two hydrogenation reactors
Technique, i.e., alkadienes first in chosen property hydrogenation reactor removing gasoline；Urged subsequently into hydro-upgrading reactor and modification
Agent is contacted, and modified including aromatisation, isomerization etc. and is reacted, and improves the octane number of gasoline；Then with reforming reactor bottom
The Hydrobon catalyst contact in portion, removes organic sulfur compound therein and some olefin.Although product sulfur content can be down to not
More than 50 μ g/g, anti-knock index (RON+MON)/2 loss of octane number is not more than 1.8, but product yield 97.5m% is relatively relatively low
A bit.
CN102041086A discloses a kind of high-sulfur, the selective hydrodesulfurization method of olefin catalytic gasoline high, it be by
Full cut catalytic cracking first carries out selective hydrogenation, and then the gasoline after selective hydrogenation carried out by pre- hydrogenation desulfurization process
Fractionation cuts into light, heavy naphtha, heavy distillat gasoline then is carried out into deep hydrodesulfurizationof and obtains low-sulfur content heavy distillat
Hydrogasoline, the clean gasoline of state IV is obtained after finally light fraction gasoline is reconciled by heavy fractioning hydrogenation gasoline.This technical process is deposited
Investing that larger, flow is more complicated and the problems such as larger energy consumption, and oil product after treatment can only achieve the clean gasoline mark of state IV
It is accurate.
In the prior art, inferior patrol production low sulfur clean gasoline has deep desulfuration and octane number excessive loss
The contradiction that mercaptan is regenerated in contradiction, and hydrodesulfurization so that prior art can not be under conditions of relatively relaxing
Obtain that sulfur content is low, loss of octane number is small, while the qualified clean gasoline of mercaptan.
The content of the invention
For above prior art, the technical problem to be solved in the present invention is to provide one kind and can obtain sulfur content and is not more than
5 μ g/g, the less sweet gasoline of loss of octane number, and desulfurization degree is high and side of production sweet gasoline of high income of product
Method.
To realize object defined above, the invention provides a kind of method for producing sweet gasoline, this method includes：(1) it is inferior
Gasoline stocks in presence of hydrogen, contact progress selective hydrogenation in selective hydrogenation reactor with selective hydrocatalyst
Reaction；Wherein, reaction temperature is 80-250 DEG C, and reaction pressure is 1-5MPa, and liquid hourly space velocity (LHSV) is 1-20h-1, hydrogen to oil volume ratio is 5-
100v/v；
(2) product as obtained by step (1) is de- with first choice hydrogenation in first choice hydrodesulphurisatioreactors reactors
Sulfur catalyst is contacted, and carries out first choice hydrodesulfurization reaction；Wherein, reaction temperature is 200-400 DEG C, and reaction pressure is 1-
5MPa, liquid hourly space velocity (LHSV) is 1-20h-1, hydrogen to oil volume ratio is 100-1000v/v；
(3) product as obtained by step (2) enters H2S strippers, obtain containing H from tower top2The gas phase of S, bottom of towe is removed
H2The liquid phase of S；
(4) liquid phase as obtained by step (3) is de- with the second selective hydrogenation in the second selective hydrodesulfurization reactor
Sulfur catalyst is contacted, and carries out second selective hydrodesulfurization reaction；Wherein, reaction temperature is 200-400 DEG C, and reaction pressure is
1-5MPa, liquid hourly space velocity (LHSV) is 1-20h-1, hydrogen to oil volume ratio is 100-1000v/v；
(5) product as obtained by step (4) is added into being contacted with Hydrobon catalyst in hydrofining reactor
Hydrogen refining reaction；Wherein, reaction temperature is 250-450 DEG C, and reaction pressure is 1-5MPa, and liquid hourly space velocity (LHSV) is 1-30h-1, hydrogen oil body
Product is than being 100-1000v/v；The bad gasoline comes from cracking unit.
The method of the present invention, which can be produced, to be obtained sulfur content and is not more than 5 μ g/g, the less sweet gasoline of loss of octane number, and
And the high income of product.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute a part for specification, with following tool
Body implementation method is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the method according to a kind of production sweet gasoline preferred embodiment of the invention.
Embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that described herein specific
Implementation method is merely to illustrate and explain the present invention, and is not intended to limit the invention.
As it was previously stated, the invention provides a kind of method for producing sweet gasoline, this method includes：(1) inferior patrol is former
In presence of hydrogen, contacted with selective hydrocatalyst in selective hydrogenation reactor carries out selective hydrogenation to material；
Wherein, reaction temperature is 80-250 DEG C, preferably 100-220 DEG C；Reaction pressure is 1-5MPa, preferably 1-3MPa；Liquid hourly space velocity (LHSV) is
1-20h-1, preferably 2-6h-1；Hydrogen to oil volume ratio is 5-100v/v, preferably 10-50v/v；
(2) product as obtained by step (1) is de- with first choice hydrogenation in first choice hydrodesulphurisatioreactors reactors
Sulfur catalyst is contacted, and carries out first choice hydrodesulfurization reaction；Wherein, reaction temperature is 200-400 DEG C, preferably 220-350
℃；Reaction pressure is 1-5MPa, preferably 1-3MPa；Liquid hourly space velocity (LHSV) is 1-20h-1, preferably 2-6h-1；Hydrogen to oil volume ratio is 100-
1000v/v, preferably 300-800v/v；
(3) product as obtained by step (2) enters H2S strippers, obtain containing H from tower top2S gas phase, bottom of towe is removed
H2S liquid phase；
(4) taken off as the liquid phase obtained by step (3) in the second selective hydrodesulfurization reactor with the second selective hydrogenation
Sulfur catalyst is contacted, and carries out second selective hydrodesulfurization reaction；Wherein, reaction temperature is 200-400 DEG C, preferably 255-
270℃；Reaction pressure is 1-5MPa, preferably 1-3MPa；Liquid hourly space velocity (LHSV) is 1-20h-1, preferably 2-6h-1；Hydrogen to oil volume ratio is
100-1000v/v, preferably 300-800v/v；
(5) entered as the product obtained by step (4) and contacted in hydrofining reactor with Hydrobon catalyst, added
Hydrogen refining reaction；Wherein, reaction temperature is 250-450 DEG C, preferably 290-310 DEG C；Reaction pressure is 1-5MPa, preferably 1-
3MPa；Liquid hourly space velocity (LHSV) is 1-30h-1, preferably 2-10h-1；Hydrogen to oil volume ratio is 100-1000v/v, preferably 300-800v/v；It is described
Bad gasoline comes from cracking unit.
, according to the invention it is preferred to the temperature of the hydrofining reaction is reacted and/or than the second selective hydrodesulfurization
The temperature of one selective hydrodesulfurization reaction is high 10-50 DEG C, preferably 30-40 DEG C, can so reduce the sulphur in sweet gasoline
Content, and the yield of sweet gasoline can be increased.
A kind of preferred implementation method of the invention, the temperature of the hydrofining reaction adds than the second selectivity
The temperature of hydrogen desulphurization reaction is high 30-40 DEG C, so can further reduce the sulfur content in sweet gasoline, and can increase without sulphur
The yield of gasoline.
According to one kind of the present invention preferred embodiment, the temperature of the hydrofining reaction is 290-310 DEG C, second
The temperature of selective hydrodesulfurization reaction is 255-270 DEG C.
, according to the invention it is preferred to H in step (3)2The operating condition of S strippers causes the removing H that bottom of towe is obtained2The liquid phase of S
Middle hydrogen sulfide content is no more than 50wppm, preferably preferably more than 20wppm, 15-20wppm.
According to invention, optional wider range of the species of the selective hydrocatalyst, in specific implementation of the invention
It is exemplary in example that to illustrate to use selective hydrocatalyst be commercial grades HDDO-100 (according to patent CN101869839A
Method prepare) selective hydrocatalyst result.
According to invention, optional wider range of the species of the catalyst for selectively hydrodesulfurizing, the first choice
Hydrobon catalyst and/or the second catalyst for selectively hydrodesulfurizing can be prepared according to the method disclosed in CN1218021C
Obtain, can also be commercially available, it is exemplary in a particular embodiment of the present invention to illustrate to urge using selective hydrodesulfurization
Agent is the catalyst for selectively hydrodesulfurizing of commercial grades HDOS-200 (industrialization product of patent of invention CN1218021C)
Result.
According to invention, optional wider range of the species of the Hydrobon catalyst, in specific embodiment of the invention
In exemplary illustrate that it is the result of the Hydrobon catalyst of commercial grades HDMS-100 to use Hydrobon catalyst.
, according to the invention it is preferred to which this method also includes：The product laggard promoting the circulation of qi liquid of cooling obtained by step (5) is isolated
Gas and liquid phase substance containing hydrogen sulfide, carry out the liquid phase substance air lift and obtain sweet gasoline.
, according to the invention it is preferred to the method also includes：The sweet gasoline is recycled back into step (1) and/or step (2)
And/or step (4) and/or step (5), wherein, the amount in return to step (1) is the poor quality of the raw material as step (1)
The 0.1-4 times of weight of gasoline stocks, preferably 0.2-3 times of weight；Amount in return to step (2) is the raw material as step (2)
The 0.1-4 times of weight of product obtained by the step (1), preferably 0.2-3 times of weight；Amount in return to step (4) is as step
Suddenly the 0.1-4 times of weight of the liquid phase obtained by the step (3) of the raw material of (4), preferably 0.2-3 times of weight；In return to step (5)
Amount to be used as the 0.1-4 times of weight of the product obtained by the step (4) of the raw material of step (5), preferably 0.2-3 times of weight.
, according to the invention it is preferred to the method also includes：By the step (3) containing H2The gas phase of S and described contain vulcanization
The gas sweetening hydrogen Posterior circle return to step (1) and/or step (2) and/or step (4) and/or step (5) of hydrogen are used as circulation
Hydrogen is used.
The step (3) is contained into H2The gas phase of S and/or the gas sweetening hydrogen containing hydrogen sulfide are industrially usual
The de- H for using2S methods are hydramine method, according to the present invention preferably as the H in the gas of the recycle hydrogen2The control of S concentration is little
In 100 μ l/l, preferably no greater than 50 μ l/l.
The method according to the invention, the μ g/g of the sulfur content of the obtained sweet gasoline≤5, the μ of mercaptans content≤5 g/g are pungent
The loss of alkane value is no more than 2.0 units, and yield is more than 98m%.
The method according to the invention, sulfur content is not more than 1300 μ g/g, preferably 780- in the bad gasoline
1080μg/g；Olefin(e) centent present in the bad gasoline is not more than 50v%, preferably 35-45v%；More preferably institute
State bad gasoline boiling range and do no more than 250 DEG C, especially preferably no more than preferably no greater than 220 DEG C, 205 DEG C.
The method according to the invention, the bad gasoline includes catalytically cracked gasoline, coker gasoline, catalytic pyrolysis vapour
Oil, pressure gasoline, one or more be pyrolyzed in full distillation gasoline and pyrolysis narrow fraction gasoline.
With the method for the invention it is preferred to the bad gasoline is catalytically cracked gasoline, more preferably full cut
Catalytically cracked gasoline (FCC).
Method of the present invention technological process is simple, and is obtained in that with ultra-low sulfur, low-sulfur alcohol content, octane number damage
Lose less sweet gasoline product, and product high income, be very suitable for commercial Application.
The method of production sweet gasoline of the invention is described with reference to Fig. 1.
(1) bad gasoline 1 is introduced by the road, is mixed with the hydrogen from pipeline 2, is then carried out in heat exchanger 17
Heating, is heated to through pipeline 3 entering after the temperature and pressure required for hydrogenation reaction and is selected in selective hydrogenation reactor 18
Selecting property hydrogenation reaction；
(2) product of step (1) 4 outflow from hydrogenation reactor 18 by the road, after then being mixed with hydrogen, through heat exchanger
After 19 heating, into first choice hydrodesulphurisatioreactors reactors 20 carrying out first choice hydrodesulfurization reaction obtains the first choosing
Selecting property hydrodesulfurization reaction product；
(3) first choice hydrodesulfurization reaction product (i.e. the product of step (2)) 5 is hydrogenated with from first choice by the road
H is exited into desulfurization reactor 202The top of S stripping towers 21, carries out the de- H of liquid phase air lift2S, the gas-phase product of the tower top of stripping tower 21
15 enter knockout drum 27 by the road, and the gaseous substance after gas-liquid separation enters de- H through gas discharge pipeline 102S towers 28, take off
H2Hydrogen after S is recycled through circulating hydrogen compressor 30 through gas discharge pipeline 14；
(4) H is taken off2Liquid product after S enters heat exchanger 22 from the second selective hydrodesulfurization reactor through bottom conduit 6
23 top contacts with the second catalyst for selectively hydrodesulfurizing into the second selective hydrodesulfurization reactor 23 and carries out second
Selective hydrodesulfurization is reacted；
(5) by the product (product of step (4)) obtained by the second selective hydrodesulfurization reactor by the second selectivity
The bottom of hydrodesulphurisatioreactors reactors 23 7 enters heat exchangers 24 and enters hydrogenation essence from the top of hydrofining reactor 25 by the road
Reactor 25 processed contacts progress hydrofining reaction with Hydrobon catalyst；
(6) products therefrom of hydrofining reactor 25 8 enters heat exchanger by the road by the bottom of hydrofining reactor 25
26 and enter from one end of knockout drum 27, carry out the gaseous substance after gas-liquid separation and enter de- through gas discharge pipeline 10
H2S towers 28, take off H2Hydrogen after S is recycled through circulation line 16 again through circulating hydrogen compressor 30, and the liquid phase substance of gained is through liquid
Discharging pipeline 9 enters stripping stabilizer 29, sweet gasoline is obtained after air lift and is discharged through product discharge pipeline 12, stripping unit
29 top gas are discharged from pipeline 11；
The stripping gained sweet gasoline of stabilizer 29 is optionally recycled to selective hydrogenation respectively through liquid circulation line 13
Device 18, first choice hydrodesulphurisatioreactors reactors 20, the second selective hydrodesulfurization reactor 23, hydrofining reactor 25
The entrance of entrance and/or knockout drum 27.
The method of the present invention, each described reactor can be realized wrapping simultaneously in a reactor by dispensing catalyst
Include selective hydrogenation reactor, first choice hydrodesulphurisatioreactors reactors, the second selective hydrodesulfurization reactor and hydrogenation
The reactor of finishing reactor, naturally it is also possible to realized in 4 different reactors, the present invention is to this without particular/special requirement.
The method of the present invention is applied to bad gasoline such as catalytic gasoline of whole fraction selective hydrodesulfurization and given birth to
Production, without carrying out cutting fractionation processing to feedstock oil, simplifies operating process, finally obtains sweet gasoline without sulphur clean gasoline,
And mercaptans content is ultralow, loss of octane number is small, and product yield is high.
Below by specific embodiment, the present invention will be described in detail, but the present invention is not limited to this.
The selective hydrocatalyst that the embodiment of the present invention is used is commercial grades HDDO-100 catalyst (by Bei Jinghai
Shuande titanium catalyst Co., Ltd produces)；First choice Hydrobon catalyst and the second catalyst for selectively hydrodesulfurizing
For commercial grades HDOS-200 catalyst (being produced by Beijing Haishunde Titanium Catalyst Co., Ltd.)；Hydrobon catalyst is business
Industry trade mark HDMS-100 catalyst (is produced) by Beijing Haishunde Titanium Catalyst Co., Ltd..
Embodiment of the present invention used catalyst with pending raw material before contacting, it is necessary to carry out vulcanisation step.It is described
Vulcanisation step can be carried out outside system or in system, such as vulcanized inside or outside reactor.
In the present invention, boiling range is measured according to the regulation of GB/T 6536 (ASTM D86), sulfur content (or sulphur
Content) it is measured according to the regulation of SH/T0689 (ASTM D5453), mercaptan sulfur content is according to (the ASTM of GB/T 1792
D3227 regulation) is measured.
In the present invention, FIA (alkene, aromatic hydrocarbons and saturated alkane) is carried out according to the regulation of GB/T11132 (ASTM D1319)
Determine.
In the present invention, diene content enters according to the regulation of QJ/FSH.YX.128-97 (UOP-326-82) Maleic Anhydride Method
Row is determined.
In the present invention, methyl isophthalic acid-butylene and methyl-2-butene are measured using Agilent 6890N type chromatographs, its
In, with N2It is carrier, is measured using HP-PONA chromatographic columns.
In the present invention, research octane number (RON) (RON), motor octane number (MON) are respectively according to the (ASTM of GB/T 5487
D2669), GB/T 503 (ASTM D2700) regulation is measured.
Embodiment 1
Sweet gasoline is produced according to flow shown in Fig. 1, in the small-sized hydrogenation evaluations of 200ml for there are four serial hydrogenation reactors
Selective hydrocatalyst HDDO-100, first choice Hydrobon catalyst HDOS-200, second are respectively charged into device
Catalyst for selectively hydrodesulfurizing HDOS-200 and Hydrobon catalyst HDMS-100, is carried out to feedstock oil A (property is shown in Table 1)
To produce sweet gasoline, property is shown in Table 1 for selective hydrodesulfrization treatment, and in adding equipped with first choice Hydrobon catalyst
H is provided between hydrogen reactor and the hydrogenation reactor equipped with the second catalyst for selectively hydrodesulfurizing2S strippers.
Selective hydrogenation condition for HDDO-100 catalyst is as follows：
Temperature=135 DEG C
Pressure=2.2MPa
Liquid hourly space velocity (LHSV)=3h-1
Hydrogen to oil volume ratio=10v/v
First choice hydrodesulfurization reaction condition for first choice hydrodesulphurisatioreactors reactors HDOS-200 catalyst
It is as follows：
Temperature=240 DEG C
Pressure=2.0MPa
Liquid hourly space velocity (LHSV)=3h-1
Hydrogen to oil volume ratio=400v/v
The H that product after foregoing first choice hydrodesulfurization is wherein dissolved by hydrogen stripped2S, makes bottom of towe after stripping
Liquid product in H2S contents are down to 20wppm；
The second selective hydrodesulfrization reaction condition for the second selective hydrodesulfurization reactor HDOS-200 catalyst
It is as follows：
Temperature=255 DEG C
Pressure=2.0MPa
Liquid hourly space velocity (LHSV)=3h-1
Hydrogen to oil volume ratio=400v/v
The condition of depriving hydrogen sulphide stripping tower includes：
Hydrofining reaction condition for HDMS-100 catalyst is as follows：
Temperature=300 DEG C
Pressure=2.0MPa
Liquid hourly space velocity (LHSV)=3h-1
Hydrogen to oil volume ratio=400v/v.
Table 1
* desulfurization degree %=100% × (feedstock oil sulfur content-content of sulfur in gasoline)/feedstock oil sulfur content
* RON values of △ RON=gasoline products RON values-feedstock oil
Can be seen that the method for the present invention to the desulfurization degree of bad gasoline by the data of table 1 is 99.5%；Gained nothing
Sulfur oil contains the sulphur of 4 μ g/g, wherein, mercaptan sulfur is 2 μ g/g, and it is 1.8 units to be lost compared to the RON of raw material A.
Embodiment 2
Selective hydrogenation catalysis is respectively charged into the small-sized hydrogenation evaluating apparatus of 200ml for there are four serial hydrogenation reactors
Agent HDDO-100, first choice Hydrobon catalyst HDOS-200, the second catalyst for selectively hydrodesulfurizing HDOS-200
And Hydrobon catalyst HDMS-100, selective hydrodesulfrization processing is carried out to feedstock oil B, and equipped with first choice hydrogenation
H is provided between the hydrogenation reactor of desulphurization catalyst and the hydrogenation reactor equipped with the second catalyst for selectively hydrodesulfurizing2S
Stripper.
Wherein, the reaction temperature in selective hydrogenation reactor is 150 DEG C, in the second selective hydrodesulfurization reactor
Reaction temperature is 270 DEG C, and the reaction temperature in hydrofining reactor is 340 DEG C, and remaining condition is same as Example 1, wherein,
Feedstock oil B and sweet gasoline property are listed in table 2.
Table 2
Can be seen that the method for the present invention to the desulfurization degree of bad gasoline by the result of table 2 is 99.5%；Gained nothing
Sulfur oil contains the sulphur of 5 μ g/g, wherein, mercaptan sulfur is 4 μ g/g, and it is 2.0 units to be lost compared to the RON of raw material A.
Embodiment 3
Under the same conditions as in practical example 2, sweet gasoline is recycled to the charging aperture of device, recirculation volume is to wait to locate
0.3-2 times of reason material quantity, and suitably adjustment first choice Hydrobon catalyst and the second selective hydrodesulfurization catalysis
The reaction temperature of agent, so as to get sweet gasoline sulfur content be less than 5 μ g/g, other reaction condition be the same as Examples 2.
Under conditions of different recycling are than (recirculation volume/pending material quantity), to gained after feedstock oil B hydrotreatings
Gasoline products property is shown in Table 3.
Table 3
| Recycling ratio | 0.3 | 0.5 | 1 | 2 |
| Desulfurization reactor entrance olefin(e) centent v% | 39.3 | 37.8 | 35.3 | 33.5 |
| First hydrodesulfurization reaction temperature, DEG C | 240 | 242 | 245 | 250 |
| Second hydrodesulfurization reaction temperature, DEG C | 255 | 257 | 262 | 270 |
| Sulphur, μ g/g | 5.0 | 5.0 | 5.0 | 5.0 |
| Mercaptan sulfur, μ g/g | 3 | 3 | 2 | 3 |
| RON | 90.3 | 90.4 | 90.6 | 90.6 |
| Alkene, v% | 29.5 | 30 | 31.5 | 31.5 |
| △RON* | -2.0 | -1.9 | -1.7 | -1.7 |
Be can be seen that under the conditions of the μ g/g of control product sulfur content 5 by the data of table 3, to recycle a part without sulphur vapour
The mode of oil operates hydrogenation reactor, can obtain product olefin(e) centent gasoline higher, so that product loss of octane number becomes
Small, compared to embodiment 2, RON losses can at most reduce by 0.4 unit.
Embodiment 4
According to the method for embodiment 2, unlike, the reaction temperature in the second selective hydrodesulfurization reactor is 270
DEG C, the reaction temperature in hydrofining reactor is 310 DEG C, and gained sweet gasoline contains the sulphur of 3 μ g/g, wherein, mercaptan sulfur is 2
μ g/g, and it is 1.6 units to be lost compared to the RON of raw material A.
Embodiment 5
According to the method for embodiment 2, unlike, the reaction temperature in the second selective hydrodesulfurization reactor is 270
DEG C, the reaction temperature in hydrofining reactor is 300 DEG C, and gained sweet gasoline contains the sulphur of 3 μ g/g, wherein, mercaptan sulfur is
2.2 μ g/g, and it is 1.7 units to be lost compared to the RON of raw material A.
Embodiment 6
According to the method for embodiment 1, unlike, the reaction temperature in hydrofining reactor is 290 DEG C, and gained is without sulphur
Gasoline contains the sulphur of 2 μ g/g, wherein, mercaptan sulfur is 1.8 μ g/g, and it is 1.6 units to be lost compared to the RON of raw material A.
Comparative example 1
According to traditional CDOS-HCN processes, first by catalytically cracked gasoline raw material B through a selective hydrogenation
Device (using HDDO-100 catalyst) carries out selective hydrogenation, then according to weight quality of gasoline ratio 4:6 fractionation cuttings
Into light petrol (LCN) and heavy petrol (HCN)；LCN is high, it is necessary to which alkali cleaning processing is less than 10 to mercaptan sulfur content due to mercaptan sulfur content
μ g/g, HCN carry out selective hydrodesulfurization by a selective hydrodesulfurization reactor (using HDOS-200 catalyst) again
Reaction, then again by hydrofining reactor (using HDMS-100 catalyst), HCN after refinement treatment again with treatment after
Low-sulphur oil product is obtained after LCN mixing.
Selective hydrogenation condition for HDDO-100 catalyst is as follows：
Temperature=150 DEG C
Pressure=2.2MPa
Liquid hourly space velocity (LHSV)=3h-1
Hydrogen to oil volume ratio=10v/v
Selective hydrodesulfurization reaction condition for HDOS-200 catalyst is as follows：
Temperature=280 DEG C
Pressure=2.0MPa
Liquid hourly space velocity (LHSV)=3h-1
Hydrogen to oil volume ratio=400v/v
Hydrofining reaction condition for HDMS-100 catalyst is as follows：
Temperature=340 DEG C
Pressure=2.0MPa
Liquid hourly space velocity (LHSV)=3h-1
Hydrogen to oil volume ratio=400v/v
The main character of feedstock oil B and gasoline products is listed in table 4.
Table 4
| Project | Feedstock oil B | Product * |
| Ratio, wt% | 100 | 100 |
| Density, gcm-3 | 0.7177 | 0.7180 |
| Sulphur, μ g/g | 1080 | 48 |
| Mercaptan sulfur, μ g/g | 52 | 8 |
| RON | 92.3 | 90.5 |
| Alkene, v% | 42.6 | 31.2 |
| Desulfurization degree, % | \ | 95.6 |
| Alkene saturation factor, % | \ | 25.8 |
| △RON | \ | -1.8 |
Gained gasoline products contain the sulphur of 48 μ g/g, wherein, mercaptan sulfur is 8 μ g/g, and the RON losses compared to raw material B are 1.8
Unit.
Comparative example 2
According to traditional CDOS-HCN processes, except cutting weight quality of gasoline ratio 2:8 and selective hydrodesulfurization
Reaction temperature is 290 DEG C outer, and other conditions are with comparative example 1.
The main character of feedstock oil B and low-sulphur oil product is listed in table 5.
Gained gasoline products contain the sulphur of 10 μ g/g, wherein, mercaptan sulfur is 6 μ g/g, and the RON losses compared to feedstock oil B are
2.4 units.
Table 5
| Project | Feedstock oil B | Product * |
| Ratio, wt% | 100 | 100 |
| Density, gcm-3 | 0.7177 | 0.7150 |
| Sulphur, μ g/g | 1080 | 10 |
| Mercaptan sulfur, μ g/g | 52 | 6 |
| RON | 92.3 | 89.9 |
| Alkene, v% | 42.6 | 27.6 |
| Desulfurization degree, % | \ | 99.1 |
| Alkene saturation factor, % | \ | 35.2 |
| △RON | \ | -2.4 |
* HCN after gasoline products=LCN+ desulfurization, the RON values of △ RON=products RON values-feedstock oil B
According to the method for the comparative example 1 and comparative example 2 of conventional conventional art, when the sulfur content of catalytically cracked gasoline is from 1080
When μ g/g are reduced to 48 μ g/g and 10 μ g/g, its octane number RON losses are respectively 1.8 units and 2.4 units.
According to the method for the present invention, it is all up for the sweet gasoline sulfur content after all raw material oil processings in embodiment
5 μ g/g, while octane number RON losses are no more than 2.0 units, the yield of product is more than 99m%.
Claims (13)
1. a kind of method for producing sweet gasoline, the method includes：
(1) bad gasoline in presence of hydrogen, contacted with selective hydrocatalyst in selective hydrogenation reactor into
Row selective hydrogenation；Wherein, reaction temperature is 80-250 DEG C, and reaction pressure is 1-5MPa, and liquid hourly space velocity (LHSV) is 1-20h-1, hydrogen
Oil volume ratio is 5-100v/v；
(2) product as obtained by step (1) is urged in first choice hydrodesulphurisatioreactors reactors with first choice hydrodesulfurization
Agent is contacted, and carries out first choice hydrodesulfurization reaction；Wherein, reaction temperature is 200-400 DEG C, and reaction pressure is 1-
5MPa, liquid hourly space velocity (LHSV) is 1-20h-1, hydrogen to oil volume ratio is 100-1000v/v；
(3) product as obtained by step (2) enters H2S strippers, obtain containing H from tower top2The gas phase of S, bottom of towe obtains removing H2S
Liquid phase；
(4) urged as the liquid phase obtained by step (3) in the second selective hydrodesulfurization reactor with the second selective hydrodesulfurization
Agent is contacted, and carries out second selective hydrodesulfurization reaction；Wherein, reaction temperature is 200-400 DEG C, and reaction pressure is 1-
5MPa, liquid hourly space velocity (LHSV) is 1-20h-1, hydrogen to oil volume ratio is 100-1000v/v；
(5) product as obtained by step (4) carries out hydrogenation essence into being contacted with Hydrobon catalyst in hydrofining reactor
System reaction；Wherein, reaction temperature is 250-450 DEG C, and reaction pressure is 1-5MPa, and liquid hourly space velocity (LHSV) is 1-30h-1, hydrogen to oil volume ratio
It is 100-1000v/v；
The bad gasoline comes from cracking unit,
Wherein, the temperature of the hydrofining reaction is more de- than the second selective hydrodesulfurization reaction and/or first choice hydrogenation
The temperature of reaction of Salmon-Saxl is high 10-50 DEG C.
2. method according to claim 1, wherein, the temperature of the hydrofining reaction is than the second selective hydrodesulfurization
The temperature of reaction and/or first choice hydrodesulfurization reaction is high 30-40 DEG C.
3. method according to claim 1, wherein, the temperature of the hydrofining reaction is 290-310 DEG C, the second selection
Property hydrodesulfurization reaction temperature be 255-270 DEG C.
4. method according to claim 2, wherein, the temperature of the hydrofining reaction is 290-310 DEG C, the second selection
Property hydrodesulfurization reaction temperature be 255-270 DEG C.
5. the method according to any one in claim 1-4, wherein, the selective hydrocatalyst is HDDO-
100, the first choice Hydrobon catalyst and the second catalyst for selectively hydrodesulfurizing are HDOS-200, the hydrogenation
Catalyst for refining is HDMS-100.
6. the method according to any one in claim 1-4, wherein, this method also includes：By the product obtained by step (5)
Thing cooling laggard promoting the circulation of qi liquid isolated gas and liquid phase substance containing hydrogen sulfide, carry out the liquid phase substance air lift and obtain
Sweet gasoline.
7. method according to claim 6, wherein, the method also includes：The sweet gasoline is recycled back into step (1)
And/or step (2) and/or step (4) and/or step (5), wherein, the amount in return to step (1) is the original as step (1)
The 0.1-4 times of weight of the bad gasoline of material, the amount in return to step (2) is as the described of the raw material of step (2)
The 0.1-4 times of weight of the product obtained by step (1), the amount in return to step (4) is the step of the raw material as step (4)
(3) the 0.1-4 times of weight of the liquid phase obtained by, the amount in return to step (5) is as the step (4) of the raw material of step (5)
The 0.1-4 times of weight of the product of gained.
8. method according to claim 6, wherein, by the step (3) containing H2S gas phase and described contain hydrogen sulfide
Gas sweetening hydrogen Posterior circle return to step (1) and/or step (2) and/or step (4) and/or step (5) as recycle hydrogen
Use.
9. method according to claim 6, wherein, the sulfur content≤5 μ g/g of the sweet gasoline, mercaptans content≤5 μ g/
G, loss of octane number is no more than 2.0 units, and yield is more than 98m%.
10. the method according to any one in claim 1-4, wherein, sulfur content is little in the bad gasoline
In 1300 μ g/g；Olefin(e) centent is not more than 50v%.
11. methods according to claim 10, wherein, sulfur content is 780-1080 μ g/g in the bad gasoline.
12. methods according to claim 10, wherein, olefin(e) centent is 35-45v%.
13. the method according to any one in claim 1-4, wherein, the bad gasoline includes catalytic cracking
One kind in gasoline, coker gasoline, catalytic cracking gasoline, pressure gasoline, the full distillation gasoline of pyrolysis and pyrolysis narrow fraction gasoline
Or it is a variety of.
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| CN103834439A (en) * | 2012-11-23 | 2014-06-04 | 中国海洋石油总公司 | Deep hydrodesulfurization method |
| CN103834438A (en) * | 2012-11-23 | 2014-06-04 | 中国海洋石油总公司 | Hydrodesulfurization process method |
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| CN101089129A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Process of selectively hydrogenating and desulfurizing inferior gasoline |
| CN101619234A (en) * | 2008-07-04 | 2010-01-06 | 中国石油化工股份有限公司 | Method for producing low sulfur gasoline by using light weight gasoline |
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