CN106635156A - Method for deeply desulfurizing catalytically cracked gasoline - Google Patents
Method for deeply desulfurizing catalytically cracked gasoline Download PDFInfo
- Publication number
- CN106635156A CN106635156A CN201611221208.1A CN201611221208A CN106635156A CN 106635156 A CN106635156 A CN 106635156A CN 201611221208 A CN201611221208 A CN 201611221208A CN 106635156 A CN106635156 A CN 106635156A
- Authority
- CN
- China
- Prior art keywords
- product
- gasoline
- hydrodesulfurization
- reaction
- light component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a method for deeply desulfurizing catalytically cracked gasoline. The method comprises the steps of enabling the catalytically cracked gasoline to enter a thio etherification reactor and removing mercaptan and alkadiene; enabling a reaction product to enter a fractionating tower and performing fractionation to obtain a light component and a heavy component; mixing the obtained heavy component with unreactive hydrocarbon, enabling the mixture to enter a selective hydrodesulfurization reactor and performing hydrodesulfurization reaction; and directly blending the hydrodesulfurization product and the light component, or fractionating the hydrodesulfurization product to obtain a hydrogenation heavy component and unreactive hydrocarbon, and blending the hydrogenation heavy component and the light component to obtain a clean gasoline product. By the method provided by the invention, desulfurization depth and selectivity are improved, mercaptan produced by combination of H2S and olefin in the reaction process is reduced, the octane value loss of the produced gasoline is small, and the product quality meets the national V gasoline quality requirement that the sulfur content is less than 10 ug/g.
Description
Technical field
It, with regard to a kind of method of Deep Desulfurization of FCC Gasoline, is with regard to a kind of reduction more specifically that the present invention is
The generation of secondary mercaptan and the loss of octane number, the method to produce clean gasoline of the sulfur content less than 10 μ g/g.
Background technology
With pay attention to day by day of the people to motor vehicle exhaust emission nuisance, countries in the world propose to the quality of fuel oil for vehicles
Strict requirements.China will implement sulfur content and be less than 10 μ gg in January, 2017-1State V motor petrol standards.It is new to reach
Standard, domestic each oil plant is faced with task of transformation and upgrade are carried out to clean gasoline producing process.China motor petrol master
If being made up of catalytically cracked gasoline, the 80% of gasoline product is accounted for.But, its sulfur content but account for gasoline product 90～
95%.Therefore, the removing of catalytically cracked gasoline sulfide is just into the key of gasoline cleaning.
At present, in desulfurization of FCC gasoline, selective hydrodesulfurization technology is kept away while sulfide is removed
The supersaturation of alkene is exempted from, has reduced the loss of octane number, be that domestic and international oil plant uses wider technology.But,
The H that hydrodesulfurization is generated during catalytic gasoline selective hydrodesulfurizationmodification2Alkene in S and raw material recombines generation
Mercaptan, especially when the high raw material of sulfur content is processed, the secondary mercaptan of generation it is serious have impact on desulfurization depth and product matter
Amount.
CN104479738A discloses a kind of Deep Desulfurization of FCC Gasoline group technology.Catalytically cracked gasoline enters sulphur
Etherification reaction tower removes mercaptan and alkadienes；Effluent fractionates out light component and heavy constituent, light component and methyl alcohol into rectifying column
Etherification reaction tower is entered after mixing, heavy constituent enters the selection for being filled with catalyst for selectively hydrodesulfurizing and isomerization catalyst
Property hydrodesulfurization tower；The secondary mercaptan hydrogenation and removing tower of restructuring lease making after hydrodesulfurization and branched chain isomer is removed after secondary mercaptan
Clean gasoline product is mixed to get with the effluent of etherificate tower.Sulfur content can be less than the catalytic cracking vapour of 700 μ g/g for the invention
Oil is reduced to below 10 μ g/g, and octane number can improve 1～2 unit.
CN103468313A discloses a kind of production method of low-sulphur oil.Gasoline stocks carry out successively hydrodesulfurization reaction
React with secondary desulfuration, product is isolated to low-sulphur oil；Wherein, secondary desulfuration reaction mainly removing hydrodesulfurization reaction
The secondary mercaptan of middle generation.The invention can be reduced to total sulfur content below 20 μ g/g less than the full distillation gasolines of 700 μ g/g, while
Alkene saturation factor is little.
CN103695035A discloses a kind of combined method for producing super low-sulfur oil.Gasoline stocks be fractionated into light fraction and
Heavy distillat, light fraction Jing alkali density removal of mercaptans, heavy distillat sequentially enters the first and second hydrogenation reactors and carries out desulphurization reaction；Take out
Light fraction after carrying obtains super low-sulfur oil with the heavy distillat mediation after desulfurization.Sulfur content can be less than 1000 μ by the inventive method
The gasoline stocks of g/g are reduced to below 10 μ g/g, within 1.5 units of loss of octane number.
CN104650975A discloses a kind of method of deep desulfurization of gasoline.The method includes：Gasoline stocks enter first
Hydrogenation reactor removes alkadienes, while mercaptan is converted into heavy thioether；Effluent is fractionated into weight component into fractionating column, weight
Component enters the second hydrogenation reactor and removes partial vulcanization thing, subsequently enters the 3rd hydrogenation reactor deep desulfuration；Weight after desulfurization
Component is mixed to get gasoline products with light component.The invention is down to 10 μ g/g in the gasoline stocks by sulfur content less than 200 μ g/g
When following, 1～2 unit of loss of octane number.
CN103059967A discloses a kind of catalytically cracked gasoline and coker gas oil mixed hydrogenation method.Catalytically cracked gasoline
Fractionating column fractionation is entered after alkali-free sweetening for light petrol and heavy petrol；It is de- hydrogenation to be carried out after heavy petrol and coker gas oil mixing
Sulphur, separation product obtains desulfurization heavy petrol and the coker gas oil after hydrogenation；Desulfurization heavy petrol and light petrol reconcile and obtain cleaning vapour
Oil product.Nitride competitive Adsorption in the invention contained by coker gas oil in catalyst active center, in causing hydrogenation activity
In the heart poison reduces the hydrogenation saturation of alkene, reduces the loss of octane number.In 300 DEG C of reaction temperature, air speed 2.5h-1Condition
Under, when the FCC gasoline raw material of the μ g/g of sulfur content 700 is reduced into 8 μ g/g, RON only loses 1.7 unit values.But due to nitrogen
The reduction of the catalyst hydrogenation activity that compound is caused, makes the hydrodesulfurization reaction in high reaction temperatures could be by sulphur in product
Near below the 10 μ g/g of content, energy consumption is larger.
CN102465017A discloses a kind of gasoline, kerosene combined hydrogenation technique.Catalytically cracked gasoline fractionation obtains light group
Divide and heavy constituent, after the kerosene mixing after heavy constituent and heating hydrodesulfurization is carried out；Hydrogenation products are carried out after mixing with light component
Fractionation obtains gasoline products and kerosene fuel product.The method can simultaneously produce sulfur content less than the state IV gasoline of 50 μ g/g and qualified
Civilian boat coal, while octane number loss is little.
CN102399587A discloses a kind of method for selective hydrodesulfurizationof of gasoline.Gasoline stocks and heavy distillate mix
After carry out selective hydrodesulfurization, low-sulphur oil product is obtained after product is separated.The loss of octane number is the method reduced, is carried
High desulfurization degree and selectivity.When the catalytically cracked gasoline raw material of the μ g/g of sulfur content 300 or so is processed, sulfur content can be down to
Below 20 μ g/g, alkene saturation factor 19% or so.
The generation of secondary mercaptan during in order to solve selective hydrodesulfurization causes sulfur content excessive problem.Domestic refinery
Generally both increase a reactor after selective hydrodesulfurization reactor to be mainly used in removing selective hydrodesulfurization process
The secondary mercaptan of middle generation, which in turns increases the loss of octane number, and improve investment and the operating cost of device.
The content of the invention
Present invention is primarily targeted at providing a kind of method of improved Deep Desulfurization of FCC Gasoline, desulfurization is improved
Depth and selectivity, reduce the generation of secondary mercaptan and the loss of octane number, and production meets cleaning of the sulfur content less than 10 μ g/g
Gasoline.
It is up to above-mentioned purpose, the invention provides a kind of method of Deep Desulfurization of FCC Gasoline, the main root of the method
According to the content and distribution of sulphur in catalytically cracked gasoline and alkene, the heavy constituent and unreactive hydrocarbons that thioetherification reaction product fractionation is gone out is mixed
Selective hydrodesulfurization is carried out after conjunction, desulfurization depth and selectivity is improve, the generation of secondary mercaptan is reduced, can produce full
Clean gasoline of the sufficient sulfur content less than 10 μ g/g.
Specifically, Deep Desulfurization of FCC Gasoline method of the invention includes step：
(1) catalytically cracked gasoline enters thioetherification reaction device, removing mercaptan and alkadienes；
(2) product that step (1) is obtained enters fractionating column, is fractionated as light component and heavy constituent；
(3) after step (2) gained heavy constituent mixes with unreactive hydrocarbons, into selective hydrodesulfurization reactor, it is hydrogenated with
Desulphurization reaction；
(4) the hydrodesulfurization product that step (3) is obtained obtains being hydrogenated with heavy constituent and unreactive hydrocarbons after being fractionated into, and is hydrogenated with heavy constituent
The light component obtained with step (2) reconciles, and obtains clean gasoline product；Or
The light component that the hydrodesulfurization product that step (3) is obtained directly is obtained with step (2) reconciles, and obtains clean gasoline product
Product.
Specific embodiment of the invention, wherein the Deep Desulfurization of FCC Gasoline method of the present invention, step (1)
Described in thioetherification reaction device in can use thioetherification catalyst in the art conventional, for example can be NiMo/Al2O3Sulphur
Catalyst for etherification.In the present invention, it is preferable that NiMo/Al by weight percentage2O3Thioetherification catalyst contains NiO 8～20%,
MoO35.0～12.0%, balance of Al2O3Carrier.
Specific embodiment of the invention, the Deep Desulfurization of FCC Gasoline method of the present invention, sulphur in step (1)
The operating condition of methyltertiarvbutyl ether reactor is：Reaction temperature is 60～160 DEG C, preferably 80～150 DEG C；1.0～4.0MPa of reaction pressure,
It is preferred that 2.0～3.5MPa；1～7h of volume space velocity-1, preferably 2～5h-1；Hydrogen to oil volume ratio 0.5～30, preferably 1～20.
Specific embodiment of the invention, the Deep Desulfurization of FCC Gasoline method of the present invention is light in step (2)
The cutting temperature of component and heavy constituent is 45～75 DEG C, preferably 50～70 DEG C.Concrete cutting temperature can be according to thioetherification reaction
As a result suitably adjust in scope of the present invention.
Specific embodiment of the invention, the Deep Desulfurization of FCC Gasoline method of the present invention, in step (3)
Unreactive hydrocarbons are selected from one or more of low boiling alkane, such as normal butane, iso-butane, pentane, isopentane, 2,2- dimethyl propylenes
Alkane, 2- methylpentanes, 2,2- dimethylbutanes, 2,3- dimethylbutanes etc..Or, unreactive hydrocarbons can also be reformate, alkyl
One or more of carburetion and isomerized oil.In terms of the percentage by weight of oil product after mixing, unreactive hydrocarbons are 10～70%, preferably 15
～60%, concrete addition can suitably be adjusted with sulphur in apparent weight component and olefin(e) centent in scope of the present invention.
Specific embodiment of the invention, the Deep Desulfurization of FCC Gasoline method of the present invention, in step (3)
The optional conventional catalyst for selectively hydrodesulfurizing of catalyst for selectively hydrodesulfurizing, for example, can be CoMo/Al2O3Catalyst.
In the present invention, it is preferable that CoMo/Al by weight percentage2O3Catalyst contains MoO35.0～18.0%, CoO 1.0～
6.0%, balance of Al2O3Carrier.
Specific embodiment of the invention, the Deep Desulfurization of FCC Gasoline method of the present invention, choosing in step (3)
The operating condition of selecting property hydrodesulphurisatioreactors reactors is：200～320 DEG C of reaction temperature, preferably 210～300 DEG C；Reaction pressure 0.8
～3.0MPa, preferably 1.0～2.5MPa；Volume space velocity 1h～7h-1, preferably 2～5h-1；Hydrogen to oil volume ratio 100～500, preferably
200～400.
Specific embodiment of the invention, the Deep Desulfurization of FCC Gasoline method of the present invention, when the step
(3) when the unreactive hydrocarbons in are selected from low boiling alkane, typically obtain step (3) in step (4) hydrodesulfurization product Jing point
Obtain being hydrogenated with heavy constituent and unreactive hydrocarbons after evaporating, be hydrogenated with the light component mediation that heavy constituent is obtained with step (2), the inertia being fractionated
Hydrocarbon can be recycled.When the unreactive hydrocarbons in the step (3) are selected from reformate, alkylate oil, isomerized oil, in step (4)
The light component that product after the hydrodesulfurization that typically step (3) is obtained can be obtained directly with step (2) reconciles.
Specific embodiment of the invention, the Deep Desulfurization of FCC Gasoline method of the present invention, step (4) is described
Light component may also pass through to be reconciled with heavy constituent hydrodesulfurization product or the hydrogenation heavy constituent again after etherificate and obtain clean gasoline
Product.
Compared with prior art, Deep Desulfurization of FCC Gasoline method of the invention has the characteristics that：
1. catalytically cracked gasoline is during selective hydrodesulfurization, the H that desulfurization is generated2Alkene in S and oil product is again
With reference to generation mercaptan so that mercaptans content is higher in product.Therefore, in regular price gasoline hydrogenation technique, hydrogasoline product is also needed
Through removal of mercaptans process.In the inventive method, being mixed with heavy constituent using unreactive hydrocarbons carries out selective hydrodesulfurization, improves de-
Sulphur depth and selectivity, reduce the generation of secondary mercaptan in course of reaction.Gained hydrogenation products directly can reconcile with light component,
Removal of mercaptans process need not again be carried out.
2. the inventive method can be directed to the catalytically cracked gasoline of different sulphur and olefin(e) centent, realize the same of deep desulfuration
When, reduce the generation of secondary mercaptan and the loss of octane number.Can be used to produce the quality of gasoline requirement (sulphur that sulfur content meets state V
Content<10μg/g).
Specific embodiment
In order to be more clearly understood to the technical characteristic of the present invention, purpose and beneficial effect, in conjunction with being embodied as
Example carries out described further below to technical scheme, it should be understood that these examples are merely to illustrate the present invention rather than limit
The scope of the present invention processed.In embodiment, each Starting reagents material is commercially available, and the experimental technique of unreceipted actual conditions is
Conventional method known to art and normal condition.
Embodiment 1
Catalytic gasoline of whole fraction raw material enters thioetherification reaction device after mixing with hydrogen, and reaction condition is：Temperature 80
～150 DEG C, 2.0～3.5MPa of pressure, 2～5h of volume space velocity-1, hydrogen to oil volume ratio 1～20.Thioetherification product will into rectifying column
Full distillation gasoline is cut into weight two parts, and cutting temperature is 50～70 DEG C, and tower top is light petrol component.Bottom of towe heavy petrol group
Divide and pentane in mass ratio 1:After 2 mixing, then be mixed into selective hydrodesulfurization reactor with hydrogen, temperature 210～
300 DEG C, 1.0～2.5MPa of pressure, 2～5h of volume space velocity-1, selective hydrogenation is carried out under conditions of hydrogen to oil volume ratio 200～400
Desulphurization reaction.Gasoline fractionates out hydrodesulfurization heavy gasoline components and pentane into fractionating column after hydrodesulfurization.Pentane is circulated
Use, hydrodesulfurization heavy constituent gasoline reconciles with light component gasoline and obtains clean gasoline product.
Thioetherification catalyst and catalyst for selectively hydrodesulfurizing are respectively adopted NiMo/Al2O3Catalyst and CoMo/Al2O3
Catalyst, wherein NiMo/Al2O3Thioetherification catalyst contains NiO 8～20%, MoO35.0～12.0%, balance of Al2O3Carry
Body；CoMo/Al2O3Catalyst contains MoO35.0～18.0%, CoO 1.0～6.0%, balance of Al2O3Carrier.
Embodiment 2～5 is reacted using catalytically cracked gasoline raw material C.
Embodiment 2
With embodiment 1, difference is the bottom of towe heavy gasoline components and pentane in mass ratio 5 to step:1 mixing.
Embodiment 3
With embodiment 1, difference is the Fractionator Bottom heavy petrol and reformate in mass ratio 3 to step:1 mixing,
And selective hydrodesulfurization reaction after directly with light petrol reconcile obtain clean gasoline product.
Embodiment 4
With embodiment 1, difference is the Fractionator Bottom heavy petrol and alkylate oil in mass ratio 3 to step:1 mixes
Directly reconcile with light petrol after conjunction, and selective hydrodesulfurization reaction and obtain clean gasoline product.
Embodiment 5
With embodiment 1, difference is the Fractionator Bottom heavy petrol and isomerized oil in mass ratio 3 to step:1 mixes
Directly reconcile with light petrol after conjunction, and selective hydrodesulfurization reaction and obtain clean gasoline product.
Comparative example 1
Step is with embodiment 1, and it is de- that difference is that the bottom of towe heavy gasoline components are directly mixed into hydrogenation with hydrogen
Reaction of Salmon-Saxl device, desulfurization product directly reconciles with light petrol component.
Comparative example 2～4 is reacted using catalytically cracked gasoline raw material C.
Comparative example 2
Step with embodiment 3, difference be Fractionator Bottom heavy petrol carry out after selective hydrodesulfurization again with light vapour
Oil and reformate reconcile.
Comparative example 3
Step with embodiment 4, difference be Fractionator Bottom heavy petrol carry out after selective hydrodesulfurization again with light vapour
Oil and alkylate oil reconcile.
Comparative example 4
Step with embodiment 3, difference be Fractionator Bottom heavy petrol carry out after selective hydrodesulfurization again with light vapour
Oil and isomerized oil reconcile.
Catalytically cracked gasoline property is shown in Table 1.
The raw material oil nature of table 1
Catalyst components content is shown in Table 2.
The catalyst components content of table 2
Thioetherification reaction operating condition is shown in Table 3.
The thioetherification reaction operating condition of table 3
The cutting temperature of different catalytically cracked gasoline raw materials is shown in Table 4.
The cutting temperature of the different catalytically cracked gasoline raw materials of table 4
| Feedstock oil | Catalytically cracked gasoline A | Catalytically cracked gasoline B | Catalytically cracked gasoline C |
| Cutting temperature, DEG C | 65 | 60 | 55 |
The selective hydrogenation desulfurization process condition of different sulfur content feedstock oils is shown in Table 5, and product property is shown in Table 6.
The selective hydrogenation desulfurization process condition of the different catalytically cracked stock of table 5
Blended gasoline product property after the different material desulfurization of table 6
By table 6, the Deep Desulfurization of FCC Gasoline production sulfur content of different sulfur contents is met into the gasoline of state V
During the product of quality requirement, the inventive method feedstock oil loss of octane number high for sulfur content is substantially reduced, and sulphur in product
Alcohol content is low.
During different lighter hydrocarbons additions, the selective hydrogenation desulfurization process condition of catalytically cracked gasoline C is shown in Table 7, product property
It is shown in Table 8.
The selective hydrogenation desulfurization process condition of the different lighter hydrocarbons additions of table 7
| Project | Embodiment 1 | Embodiment 2 | Comparative example 1 |
| Pentane/heavy constituent | 1:2 | 1:5 | 0 |
| Reaction temperature, DEG C | 270 | 285 | 290 |
| Reaction pressure, MPa | 1.6 | 1.6 | 1.6 |
| Volume space velocity, h-1 | 4 | 3.2 | 3 |
| Hydrogen to oil volume ratio | 300 | 300 | 300 |
The different lighter hydrocarbons addition desulfurization product properties of table 8
| Project | Embodiment 1 | Embodiment 2 | Comparative example 1 |
| Density (20 DEG C), g ﹒ cm-3 | 0.7331 | 0.7323 | 0.7324 |
| Sulfur content, μ g ﹒ g-1 | 9.2 | 9.7 | 9.8 |
| Mercaptans content, μ g ﹒ g-1 | 3.3 | 5.7 | 6.2 |
| RON | 89.6 | 88.5 | 88.2 |
| ΔRON | 2.2 | 3.3 | 3.6 |
By table 8, using catalytically cracked gasoline raw material C sulfur content is produced<The clean gasoline product of 10 μ g/g, positive penta
Alkane and heavy petrol in mass ratio 1:During 2 mixing, octane number only loses 2.2 units.
When the lighter hydrocarbons for adding are reformate, alkylate oil or isomerized oil, the selective hydrogenation of catalytically cracked gasoline C takes off
Sulphur process conditions are shown in Table 9, and product property is shown in Table 10.
The selective hydrogenation desulfurization process condition of the embodiment 3～5 of table 9 and comparative example 2～4
The product property of the embodiment 3～5 of table 10 and comparative example 2～4
It can be seen that the inventive method cost of investment is low, and it is easy to operate, meet state V quality of gasoline requirements in production sulfur content
During product, loss of octane number is little.
What is finally illustrated is：Above example is merely to illustrate the implementation process and feature of the present invention, and unrestricted is sent out
Bright technical scheme, although being described in detail to the present invention with reference to above-described embodiment, one of ordinary skill in the art should
Work as understanding：Still the present invention can be modified or equivalent, without departing from the spirit and scope of the present invention any
Modification or local are replaced, and all should be covered in the middle of protection scope of the present invention.
Claims (10)
1. a kind of method of Deep Desulfurization of FCC Gasoline, the method comprising the steps of：
(1) catalytically cracked gasoline enters thioetherification reaction device, removing mercaptan and alkadienes；
(2) product that step (1) is obtained enters fractionating column, is fractionated as light component and heavy constituent；
(3) after step (2) gained heavy constituent mixes with unreactive hydrocarbons, into selective hydrodesulfurization reactor, hydrodesulfurization is carried out
Reaction；
(4) the hydrodesulfurization product that step (3) is obtained obtains being hydrogenated with heavy constituent and unreactive hydrocarbons, hydrogenation heavy constituent and step after being fractionated into
Suddenly the light component that (2) obtain reconciles, and obtains clean gasoline product；Or
The light component that the hydrodesulfurization product that step (3) is obtained directly is obtained with step (2) reconciles, and obtains clean gasoline product.
2. method according to claim 1, wherein, the cutting temperature of the weight component described in step (2) is 45-75 DEG C.
3. method according to claim 1, wherein, the unreactive hydrocarbons described in step (3) selected from low boiling alkane one kind or
It is various, or, one or more in reformate, alkylate oil and isomerized oil；
Preferably, the low boiling alkane is selected from normal butane, iso-butane, pentane, isopentane, 2,2- dimethylpropanes, 2- first
One or more in base pentane, 2,2- dimethylbutanes, 2,3- dimethylbutanes.
4. method according to claim 1, wherein, the unreactive hydrocarbons described in step (3) are selected from reformate, alkylate oil and different
One or more in structure carburetion；
In step (4), the light component that the hydrodesulfurization product that step (3) is obtained directly is obtained with step (2) reconciles.
5. method according to claim 1, wherein, in the mixture of step (3) heavy constituent and unreactive hydrocarbons, unreactive hydrocarbons
Mass fraction be 10～70%.
6. method according to claim 1, wherein, the reaction condition of step (3) selective hydrodesulfurization is：Temperature
200～320 DEG C, 0.8～3.0MPa of pressure, volume space velocity 1h～7h-1, hydrogen to oil volume ratio 100～500.
7. the method according to claim 1 or 6, wherein, the catalyst for selectively hydrodesulfurizing in step (3) is CoMo/
Al2O3Catalyst；Preferably, CoMo/Al by weight percentage2O3Catalyst contains MoO35.0～18.0%, CoO 1.0～
6.0%, balance of Al2O3Carrier.
8. method according to claim 1, wherein, the light component described in step (4) adds with heavy constituent again after etherificate
Hydrogen desulfurization product or the hydrogenation heavy constituent reconcile.
9. method according to claim 1, wherein, NiMo/Al used in the thioetherification reaction device described in step (1)2O3
Thioetherification catalyst；Preferably, NiMo/Al by weight percentage2O3Thioetherification catalyst contains NiO 8～20%, MoO3 5.0
～12.0%, balance of Al2O3Carrier.
10. the method according to claim 1 or 9, wherein, the operating condition of thioetherification reaction device is in step (1)：Reaction
Temperature is 60～160 DEG C, preferably 80～150 DEG C；1.0～4.0MPa of reaction pressure, preferably 2.0～3.5MPa；Volume space velocity 1～
7h-1, preferably 2～5h-1；Hydrogen to oil volume ratio 0.5～30, preferably 1～20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611221208.1A CN106635156B (en) | 2016-12-26 | 2016-12-26 | A kind of method of Deep Desulfurization of FCC Gasoline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611221208.1A CN106635156B (en) | 2016-12-26 | 2016-12-26 | A kind of method of Deep Desulfurization of FCC Gasoline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106635156A true CN106635156A (en) | 2017-05-10 |
| CN106635156B CN106635156B (en) | 2018-07-13 |
Family
ID=58831313
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611221208.1A Active CN106635156B (en) | 2016-12-26 | 2016-12-26 | A kind of method of Deep Desulfurization of FCC Gasoline |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106635156B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108949229A (en) * | 2017-05-19 | 2018-12-07 | 中国石油化工股份有限公司 | Produce the method and system of clean gasoline |
| CN108949226A (en) * | 2017-05-19 | 2018-12-07 | 中国石油化工股份有限公司 | Produce the method and system of clean gasoline |
| CN115368936A (en) * | 2021-05-17 | 2022-11-22 | 中国石油天然气股份有限公司 | Catalytic cracking gasoline modification method and product |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453533A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Method for producing low sulfur gasoline by using by inferior gasoline fractions |
| CN104479738A (en) * | 2014-12-16 | 2015-04-01 | 西安石油大学 | Catalytically cracked gasoline deep desulfurization combined technique |
| US20150175910A1 (en) * | 2012-07-17 | 2015-06-25 | IFP Energies Nouvelles | Process for the production of a light gasoline with a low sulphur content |
-
2016
- 2016-12-26 CN CN201611221208.1A patent/CN106635156B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453533A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Method for producing low sulfur gasoline by using by inferior gasoline fractions |
| US20150175910A1 (en) * | 2012-07-17 | 2015-06-25 | IFP Energies Nouvelles | Process for the production of a light gasoline with a low sulphur content |
| CN104479738A (en) * | 2014-12-16 | 2015-04-01 | 西安石油大学 | Catalytically cracked gasoline deep desulfurization combined technique |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108949229A (en) * | 2017-05-19 | 2018-12-07 | 中国石油化工股份有限公司 | Produce the method and system of clean gasoline |
| CN108949226A (en) * | 2017-05-19 | 2018-12-07 | 中国石油化工股份有限公司 | Produce the method and system of clean gasoline |
| CN108949226B (en) * | 2017-05-19 | 2020-10-27 | 中国石油化工股份有限公司 | Method and system for producing clean gasoline |
| CN108949229B (en) * | 2017-05-19 | 2020-10-27 | 中国石油化工股份有限公司 | Method and system for producing clean gasoline |
| CN115368936A (en) * | 2021-05-17 | 2022-11-22 | 中国石油天然气股份有限公司 | Catalytic cracking gasoline modification method and product |
| CN115368936B (en) * | 2021-05-17 | 2024-03-26 | 中国石油天然气股份有限公司 | Catalytic cracking gasoline modification method and product |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106635156B (en) | 2018-07-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102311795B (en) | Hydrogenation method for producing high-octane gasoline components by diesel oil raw material | |
| CN101845322B (en) | Production method for reducing sulfur and olefin content in gasoline | |
| CN101724457B (en) | Hydrogenation combined method for diesel oil | |
| CN101987971A (en) | Method for producing high-octane petrol by inferior diesel | |
| CN102757818A (en) | Sulfur-free gasoline production method | |
| CN106635156B (en) | A kind of method of Deep Desulfurization of FCC Gasoline | |
| CN105754646B (en) | A kind of catalytic diesel oil hydro-conversion and gasoline hydrogenation integrated processes | |
| CN105623725B (en) | A kind of group technology of heavy/Residual cracking | |
| CN102399585B (en) | Method for producing sweet gasoline | |
| CN104711022B (en) | A kind of yield of gasoline that increases produces the two-stage catalytic gasoline modifying method of super low-sulfur oil | |
| CN102634368B (en) | Method for modifying inferior gasoline | |
| CN109988650A (en) | Hydro-upgrading of inferior diesel and hydrofinishing combined method | |
| CN106929099A (en) | Method for hydro-upgrading inferior gasoline | |
| CN106883872B (en) | Deep desulfurization device and method for gasoline | |
| CN102994148B (en) | Deep desulfurization method for gasoline | |
| CN103059955B (en) | Method for producing clean gasoline from catalytic cracking gasoline | |
| CN106590739B (en) | A kind of method of Deep Desulfurization of FCC Gasoline | |
| CN102634371A (en) | Gasoline modification method | |
| CA2543953C (en) | Unleaded gasoline composition and method for producing the same | |
| CN106479566B (en) | A kind of method for hydrogen cracking producing premium and diesel oil | |
| CN102634370B (en) | Gasoline hydro-upgrading method | |
| CN102443429A (en) | Hydro-processing method for producing ultra-low sulfur diesel | |
| CN103059949A (en) | Catalytic cracking gasoline desulfurization method | |
| CN110184089B (en) | Low-sulfur catalytic cracking gasoline treatment method | |
| CN109722308A (en) | A method of producing low-sulfur, low-alkene gasoline |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |