CN104277874B - A kind of method of cracking gasoline absorption desulfurization - Google Patents
A kind of method of cracking gasoline absorption desulfurization Download PDFInfo
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- CN104277874B CN104277874B CN201310292325.7A CN201310292325A CN104277874B CN 104277874 B CN104277874 B CN 104277874B CN 201310292325 A CN201310292325 A CN 201310292325A CN 104277874 B CN104277874 B CN 104277874B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
The present invention discloses a kind of method of adsorbing and desulfurizing catalytic cracking gasoline, with the catalytic gasoline after selective hydrodesulfurization as raw material (sulfur content ＜ 150 μ g/g), first passes through fractionating column and carries out cutting fractionation, be fractionated as light petrol and heavy petrol.Light petrol enters fixed bed reactors and carries out non-hydrogen physical absorption desulfurization, and physical absorption desulfurization does not reduce olefin(e) centent, it is ensured that the octane number of product does not loses；Heavy petrol enters fixed bed reactors to carry out facing hydrogen absorption desulfurization, and product can reach the clean gasoline product of Europe V sulphur index request with the mediation of light petrol physical absorption desulfurization product.The inventive method can be connected mutually with existing selective hydrogenation desulfurization process, produces the clean gasoline meeting Europe V sulphur index request, and equipment investment is few, and absorbent filling is convenient, and simple to operate, loss of octane number is few.
Description
Technical field
A kind of method that the present invention relates to adsorbing and desulfurizing catalytic cracking gasoline, belongs to Petroleum Processing Technology field.
Background technology
The subject matter of China's quality of gasoline is sulfur content and olefin(e) centent height, and reason is owing to catalytically cracked gasoline accounts for vapour
Ratio in oil sump is too high.In China, catalytically cracked gasoline is the main blend component of gasoline, accounts for more than 75%.Use catalysis is split
Change olefine lowering catalyst, auxiliary agent and new catalytic cracking technology, the olefin(e) centent in catalytic gasoline can be made to be down toAfter traditional selective hydrogenation desulfurization process, olefin(e) centent can reduce further, then by allotment
Oil refinery gasoline can be made to reach olefin(e) centent be less thanTarget.But sulfur content is less than 50 μ g/g or further less than 10 μ g/g
Requirement just ratio be relatively inaccessible to, when deep hydrodesulfurizationof, the hydrogenation reaction of unsaturated hydrocarbons is violent, and hydrogen consumption increases considerably, and
The loss of octane number of gasoline is bigger.Oil refining enterprise and scientific research institution carry out the research of Novel desulphurization technology one after another, and gasoline adsorption takes off
Sulphur technique is gradually paid attention to.Absorption desulfurization can be divided into chemisorbed and physical absorption two class, and chemisorbed is typically facing hydrogen
Under the conditions of carry out, have that alkene is saturated, loss of octane number, physical absorption is typically carried out under conditions of non-hydrogen, there is not octane
Value loss.
Patent WO03/084656(S-zorb technique) disclose a kind of use in fluid-bed sweetening reactor renewable solid
The hydrocarbon desulfurization system of body desulfuration adsorbent particle.This technique use fluidized-bed reactor, make desulfuration adsorbent particle reactor,
Regenerative system and reductor circulate, it is achieved that the continuous desulfurization of catalytically cracked gasoline and the cyclic regeneration of desulfuration adsorbent, be
The Typical Representative of chemisorbed desulfurization.
Patent US5730860(IRVAD technique) use a kind of solid aluminum based selective modified through inorganic accelerator to inhale
Attached dose, in multi-stage absorption tower, adsorbent and gasoline counter current contacting (moving bed process), adsorbing and removing sulfur-bearing therein chemical combination
Thing, desulfurization degree reaches more than 90%.The adsorbent of inactivation regenerates in the activator of atmosphere of hydrogen, is recycled to adsorption tower and is continuing with,
It it is the Typical Representative of physical absorption desulfurization.
The LADS technique of patent CN200410010353.6(Sinopec Luoyang Petrochemical engineering company exploitation, belongs to physics
Absorption) inferior patrol is heated to 20～220 DEG C, it is 0.1～10h at volume space velocity-1, pressure is the condition of normal pressure～0.5MPa
Contacting with desulfuration adsorbent down, the gasoline after desulfurization goes out device, after desulfuration adsorbent absorption is saturated, utilizes desorbing agent to inhale desulfurization
Attached dose carries out desorption process, after carrying out absorption and desorption process 1～1000 times the most again, uses regenerative agent to enter desulfuration adsorbent
Row regeneration, the sorbent circulation after regeneration uses.Described desorbing agent is steam, purify dry gas, nitrogen or the one of air or
Above mixture, described regenerative agent is C1～C5Little molecular fat alcohols, C2～C8Ethers, C3～C5Ketone or C6~
C8Arene compounds in one or more mixture.This technique can be the sulfur content in gasoline from 1290 μ
G/g is down to 800～400 μ g/g.
Patent CN1289639 discloses a kind of desulfurization being made up of nano zine oxide, silica, aluminum oxide and reduced state nickel
Adsorbent, utilizes this adsorbent can take off the raw gasoline of sulphur sulfur-bearing 2000 μ g/g to 5 below μ g/g in fixed bed reactors, and
And the octane number of gasoline does not reduces.In same reactor, the desulfuration adsorbent of reaction inactivation can be passed through O2And N2Carry out again
Raw, reusable after hydrogen reducing the most under certain condition.
Patent CN101845322 discloses a kind of method reducing sulfur in gasoline and olefin(e) centent, raw material catalytic cracking vapour
Oil first passes through pre-hydrogenator removing alkadienes, is fractionated into light, heavy petrol subsequently into fractionating column cutting, and light petrol faces
Hydrogen absorption desulfurization, heavy petrol enters selective hydrogenation reactor hydrodesulfurization, and reaction effluent enters back into hydro-upgrading reactor
Carrying out hydro-upgrading, reduce olefin(e) centent, the heavy petrol after modification is in harmonious proportion with light petrol absorption desulfurization product and is met standard
The clean gasoline required.
Although absorbing desulfurization catalyst has good removal effect for the sulfide in gasoline, but absorption desulfurization is urged
The sulfur capacity of agent is limited, and in sweetening process, the activated centre in catalyst surface and duct gradually can be occupied generation by sulphur atom
Adsorb saturated and lose activity, so being only generally used for the catalyst single trip use cycle of adsorbing and desulfurizing catalytic cracking gasoline
20-200 hour.Use fluid bed and moving-burden bed reactor that the design of catalyst is had higher requirement, additionally both
Technique, the reaction of absorbing desulfurization catalyst, regenerates and reduces and carry out in different reactors, and investment is big, and energy consumption is high.And use
Fixed bed reactors, the reaction of catalyst, regenerate and reduce and can carry out in same reactor, due to the sulfur capacity of catalyst
Limited, need frequently to switch over, it is more difficult to realize commercial Application.It addition, absorption desulfurization runs under conditions of facing hydrogen, also can satisfy
Carrying out adsorbing desulfurization with the alkene in catalytically cracked gasoline, especially light petrol, the olefin component octane number in light petrol is higher,
The octane number that can cause gasoline loses in a large number.
Summary of the invention
The present invention is (sulfur content ＜ 150 μ g/g) with the catalytic gasoline after selective hydrodesulfurization as raw material, it is therefore an objective to
One is provided to use fixed-bed process, absorption desulfurization to produce the side meeting Europe V sulphur index request (＜ 10 μ g/g) clean gasoline
Method, reduces the loss of octane number simultaneously.
The present invention is achieved by the following technical solutions: raw material enters fractionating column and carries out cutting fractionation, is fractionated as light vapour
Oil and heavy petrol, light petrol enters non-hydrogen physical absorption desulfurization fixed bed reactors and carries out physical absorption desulfurization, physical absorption
Desulfurization does not reduce olefin(e) centent, it is ensured that the octane number of product does not loses；Heavy petrol mixes with hydrogen, enters and faces hydrogen absorption desulfurization admittedly
Fixed bed reactor carries out facing hydrogen absorption desulfurization, belongs to chemisorbed desulfurization.
The operation pressure of fractionating column is 0.1～1.0MPa, and the sulfur content of light petrol is less than 40 μ g/g.
Light petrol non-hydrogen physical absorption desulfurization through the following steps that realize:
1. light petrol is heated to 20～400 DEG C, at volume space velocity 0.2～10h-1, under conditions of operation pressure 0.1～3MPa
Entering fixed bed reactors to contact with desulfuration adsorbent, the light petrol after absorption desulfurization goes out fixed bed reactors.Preferably work
Skill condition is that light petrol is heated to 100～350 DEG C, and volume space velocity is 0.5～5h-1, operation pressure is 0.5～2MPa.
2. stopping entering light petrol after desulfuration adsorbent absorption is saturated, in temperature higher than adsorption temp 0～50 DEG C, volume is empty
Speed is 10～2000h-1, under conditions of operation pressure 0.1～3MPa, make hydrogen pass through desulfuration adsorbent bed, desulfurization adsorbed
Agent carries out facing hydrogen and processes.Preferably process conditions are that temperature is higher than adsorption temp 30～50 DEG C, and volume space velocity is 500～1000h-1, operate pressure 0.5～2MPa.
3., after carrying out step 1 and the absorption of step 2, facing hydrogen processing procedure 5-20 time, desulfuration adsorbent needs regeneration and also
Former.Regeneration condition is: regeneration temperature 300～600 DEG C, and regeneration pressure 0.1～2.0MPa, regeneration gas comprises oxygen, such as may be used
Be oxygen volume content be the mixed gas of oxygen and the inert gas of 0.1%～21.0%, can be more specifically oxygen and
The mixed gas of nitrogen.Desulfuration adsorbent after regeneration and reducing gas react and realize desulfuration adsorbent reduction, and reducing condition is:
Reduction temperature 260～600 DEG C, reduce pressure 0.1～2.0MPa, and reducing gas is the gas that hydrogen volume content is at least 40%,
The mixed gas of such as hydrogen and nitrogen or hydrogen and the mixed gas of other gas.Desulfuration adsorbent after reduction continues cycling through
Use.
The desulfuration adsorbent of light petrol non-hydrogen physical absorption desulfurization of the present invention, can with nickel, zinc as active component
With commodity in use desulfuration adsorbent, or the desulfuration adsorbent prepared by prior art, as can be according to ZL03139159.1 right
Require that described in 1, method prepares.
Desulfuration adsorbent of the present invention is mainly made up of zinc oxide and reduced state nickel, wherein zinc oxide account for 15%～
90%, reduced state nickel accounts for 2%～85%.Not specified " % " of the present invention refers both to mass percent.In described desulfuration adsorbent
Also comprise silica, aluminum oxide etc..
Present invention also offers preferably constituting of described desulfuration adsorbent, its weight percent consists of: particle diameter 100～500 μ
The nano zine oxide 30%～85% of m, silica 5%～60%, aluminum oxide 5%～30%, reduced state nickel 3%～60%.
By the non-hydrogen physical adsorption process of step 1, make the sulfur-containing compound in catalytic gasoline be attracted to desulfurization and inhale
The surface of attached dose, sees Fig. 1-a, and owing to being non-hydrogen physical adsorption process, the alkene in catalytic gasoline will not be hydrogenated saturated, pungent
Alkane value also will not be lost.When the sulfur-containing compound of non-hydrogen physical absorption reach a certain amount of after, desulfurization degree can decline to a great extent, stop
Add catalytic gasoline raw material, make hydrogen pass through desulfuration adsorbent bed, desulfuration adsorbent is faced hydrogen and processes.This faces hydrogen and processes
Principle of Process is as follows: in hydrogen with desulfuration adsorbent under the effect of nickel, the sulphur atom in the sulfur-containing compound of adsorbent surface
Zinc oxide in adsorbent is combined generation zinc sulphide and transfers to absorbent interior, and loses the hydrocarbon compound desorption of sulphur atom
Diffuse out adsorbent, see Fig. 1-b.The room of adsorbent surface is released the non-hydrogen physics that can repeat step 1
Absorption.After repeating step 1 and many times of step 2, the solid sulphur component zinc oxide major part in adsorbent is occupied, and sees Fig. 1-c.To de-
After sulfur absorbent carries out regenerating and reducing, adsorbent can recycle, and sees Fig. 1-d.Use the present invention desulfuration adsorbent and
Non-hydrogen physical absorption sweetening process, light petrol desulfurization degree is up to more than 80%.
Heavy petrol face hydrogen absorption desulfurization fixed bed reactors filling its weight percent of adsorbent consist of: particle diameter 100～
The nano zine oxide 10%～85% of 500 μm, silica 5%～80%, aluminum oxide 5%～30%, reduced state nickel 4%～45%.Adsorbent
Can be with commodity in use adsorbent, or the catalyst (patent: described in claim 4 in ZL03139159.1 prepared as prior art
Method is carried out).
It is heavy petrol volume space velocity 0.2～10h that heavy petrol faces the operating condition of hydrogen absorption desulfurization fixed bed reactors-1, instead
Answer temperature 180～420 DEG C, hydrogen to oil volume ratio 20～100v/v, operate pressure 0.5～3.0MPa.
Heavy petrol face hydrogen absorption desulfurization fixed bed reactors filling adsorbent reach work Sulfur capacity after, carry out regenerating and going back
Former.Regeneration condition is: regeneration temperature 300～600 DEG C, and regeneration pressure 0.1～2.0MPa, regeneration gas comprises oxygen, such as may be used
Be oxygen volume content be the mixed gas of oxygen and the inert gas of 0.1%～21.0%, can be more specifically oxygen and
The mixed gas of nitrogen.
Desulfuration adsorbent after regeneration and reducing gas react and realize adsorbent reduction, and reducing condition is: reduction temperature 260
～600 DEG C, reduce pressure 0.1～2.0MPa, reducing gas be the gas that hydrogen volume content is at least 40%, such as hydrogen and
The mixed gas of nitrogen or hydrogen and the mixed gas of other gas.
It can be one that heavy petrol faces hydrogen absorption fixed bed reactors used by desulfurization, it is also possible to be multiple fixed bed reactions
Device is used in series.
Heavy petrol face hydrogen absorption desulfurization fixed bed reactors in adsorbent reach work Sulfur capacity after, need to be switched to the most also
Another fixed bed reactors of connection or the fixed bed reactors of multiple series connection.
The present invention is (sulfur content ＜ 150 μ g/g) with the catalytic gasoline after selective hydrodesulfurization as raw material, first passes through
Fractionating column carries out cutting fractionation, is fractionated as light petrol and heavy petrol.It is anti-that light petrol enters non-hydrogen physical absorption desulfurization fixed bed
Answering device to carry out physical absorption desulfurization, physical absorption desulfurization does not reduce olefin(e) centent, it is ensured that the octane number of product does not loses；Heavy petrol
Entering to face hydrogen absorption desulfurization fixed bed reactors to carry out facing hydrogen absorption desulfurization, product is adjusted with light petrol physical absorption desulfurization product
With the clean gasoline product that can reach Europe V sulphur index request.Owing to light petrol is rich in alkene, and the alkene octane number of this part
The highest, physical absorption desulfurization can not be lost alkene and i.e. be ensured that octane number does not loses.Only heavy petrol is faced hydrogen absorption desulfurization, reduces
The treating capacity of fixed bed reactors, and heavy petrol olefin(e) centent is low, and the alkene octane number of this part is low, is keeping higher
Under conditions of desulfurization degree, loss of octane number is few；By optimization of process conditions, the one way facing hydrogen absorption desulfurization can be run the time
Bring up to more than 1800 hours, it is easy to commercial Application.
The inventive method can be connected mutually with existing selective hydrogenation desulfurization process, produces and meets Europe V sulphur index request
Clean gasoline, equipment investment is few, and absorbent filling is convenient, and simple to operate, loss of octane number is few.
Accompanying drawing explanation
Fig. 1-a is non-hydrogen physical absorption schematic diagram.
Fig. 1-b processes schematic diagram for facing hydrogen.
Fig. 1-c is that repeatedly non-hydrogen physical absorption-face hydrogen processes schematic diagram.
Fig. 1-d is schematic diagram after non-hydrogen physical absorption schematic diagram regeneration-reduction.
In figureRepresent ZnO；Represent Ni；Represent ZnS；Represent sulfide；Represent hydrocarbon.
Fig. 2 and Fig. 3 is present invention process schematic flow sheet.
Catalytic gasoline after 1-selective hydrodesulfurization in figure, 2-fractionating column, 3-light petrol, 4-heavy petrol, 5-hydrogen, 6-
Heating furnace, 7-enters first and faces hydrogen absorption desulfurization fixed bed reactors raw material, and it is anti-that 8-first faces hydrogen absorption desulfurization fixed bed
Answering device, 9-first to face hydrogen absorption desulfurization fixed bed reactors product, 10-high-pressure separator, 11-tail gas, after 12-separates
Liquid-phase product, 13-regeneration gas, 14-valve, 15-hydrogen, 16-preheater, 17-entrance second is faced hydrogen absorption desulfurization and is fixed
Bed reactor feedstocks, 18-second faces hydrogen absorption desulfurization fixed bed reactors, and it is anti-that 19-second faces hydrogen absorption desulfurization fixed bed
Answering product, 20-high-pressure separator, 21-tail gas, liquid-phase product after 22-separation, 23-regeneration gas, 24-preheater, 25-enters
Physical absorption desulfurization fixed bed raw material, 26-physical absorption desulfurization fixed bed reactors, 27-physical absorption desulfurization product, 28-is high
Pressure separator, 29-tail gas, liquid-phase product after 30-separation, 31-hydrogen, 32-regeneration gas.
Detailed description of the invention
Catalytic gasoline 1 after selective hydrodesulfurization is fractionated into tower 2 fractionation and obtains light petrol 3 and heavy petrol 4.
Light petrol non-hydrogen physical absorption sweetening process:
Enter fixed bed reactors 26 after the preheated device of light petrol 3 24 and carry out non-hydrogen physical absorption desulfurization, product 27 with
Product 22 obtains reaching the clean gasoline product of Europe V sulphur index request after being in harmonious proportion.
Face hydrogen processing procedure:
After the desulfurization degree of light petrol declines to a great extent, light petrol 3 stops charging, and hydrogen 31 enters fixed bed reactors 26,
The sulfide on desulfuration adsorbent surface is desorbed from adsorbent surface, through high-pressure separator after removing sulphur atom under the effect of hydrogen
After 28 separate, the main hydrogen of logistics 29, logistics 30 is also super-low sulfur catalytic gasoline product.
Regeneration-reduction process:
Light petrol 3 stops charging, and regeneration gas 32 enters fixed bed reactors 26, when the sulfur content in regeneration tail gas 29 is low
After 20 μ g/g, stopping entering regeneration gas 32, hydrogen 31 enters fixed bed reactors 26 and realizes desulfuration adsorbent reduction reaction.
Heavy petrol face hydrogen absorption sweetening process:
Entering fixed bed reactors 8 after heavy petrol 4 and the heating of hydrogen heated stove 6, product 9 is through high-pressure separator 10
After separation, the main hydrogen of tail gas 11, can recycle.Enter after liquid-phase product 12 and the heated stove of hydrogen 15 16 after separation
Fixed bed reactors 18, product 19 through high-pressure separator 20 separate after, the main hydrogen of tail gas 21, can recycle.
Face hydrogen desulfuration adsorbent regeneration-reduction process:
Close valve 14, enter fixed bed reactors 8 after regeneration gas 13 and 23 is heated and 18 pairs of desulfuration adsorbents enter
Row regeneration, after the sulfur content in regeneration tail gas 11 and 21 is less than 20 μ g/g, hydrogen 5 and 15 enters fixed bed reactors 8 and 18
Realize catalyst reduction reaction.
The method providing the present invention is further described by the following examples, but is the most therefore limited to this
Bright, those skilled in the art can be according to raw material of different nature and the product of different index, the condition needed for concrete optimization.
Comparative example 1
With the catalytic gasoline A of chosen property hydrodesulfurization for raw material (see Table 1), with hydrogen by 1 fixed bed reactors
In carry out adsorb desulphurization reaction, process for adsorption desulfuration condition and product property are as shown in table 2, table 3.Although from table 3 it can be seen that
The sulfur content of product is 9.7 μ g/g, and RON loss of octane number reaches 1.3 units, but the one way of adsorbent only runs the time
394h。
Embodiment 1:
Compared with comparative example 1, in the case of raw material is identical, light petrol non-hydrogen physical absorption desulfurization and heavy petrol face hydrogen
The adsorbent of chemisorbed desulfurization is all prepared by ZL03139159.1 embodiment 3, and the method using the present invention, by selectivity
The catalytic gasoline A fractionation of hydrodesulfurization is that light petrol and heavy petrol (see Table 1), heavy petrol and hydrogen pass through 1 fixed bed reaction
Device carries out facing hydrogen absorption desulphurization reaction, and product and light petrol non-hydrogen physical absorption desulfurization product are in harmonious proportion and are finally modified
Gasoline products.Heavy petrol faces hydrogen absorption desulfurization and light petrol non-hydrogen physical absorption desulfurization process conditions is shown in Table 2, and product property is such as
Shown in table 3.From table 3 it can be seen that the sulfur content of product is 8.7 μ g/g, only 0.3 unit of RON loss of octane number, adsorbent
The one way operation time reaches 2194h.
Embodiment 2:
Compared with comparative example 1, in the case of raw material is identical, light petrol non-hydrogen physical absorption desulfurization and heavy petrol face hydrogen
The adsorbent of chemisorbed desulfurization is all prepared by ZL03139159.1 embodiment 3, and the method using the present invention, by selectivity
The catalytic gasoline A fractionation of hydrodesulfurization is light petrol and heavy petrol (see Table 1), and it is anti-that heavy petrol, hydrogen pass sequentially through 2 fixed beds
Answering device to carry out facing hydrogen absorption desulphurization reaction, product and light petrol non-hydrogen physical absorption desulfurization product are in harmonious proportion and are finally changed
Matter gasoline products.Heavy petrol faces hydrogen absorption desulfurization and light petrol non-hydrogen physical absorption desulfurization process conditions is shown in Table 2, product property
As shown in table 3.From table 3 it can be seen that the sulfur content of product is 9.0 μ g/g, only 0.5 unit of RON loss of octane number, adsorbent
One way run the time reach 2616h.
The raw material that table 1 comparative example 1, embodiment 1 and embodiment 2 use
| Project | Raw material A | Light petrol | Heavy petrol |
| Density (20 DEG C)/g/cm3 | 0.718 | 0.689 | 0.783 |
| Total sulfur/μ g/g | 49.1 | 12.1 | 86.9 |
| Alkene/w% | 27.2 | 43.5 | 15.4 |
| Boiling range/DEG C | |||
| Initial boiling point | 36.0 | - | 75.7 |
| 10% | 50.0 | 39.2 | 100.1 |
| 30% | 66.2 | 41.7 | 116.5 |
| 50% | 88.9 | 45.5 | 128.4 |
| 70% | 119.9 | 49.8 | 149.3 |
| 90% | 165.2 | 59.6 | 175.4 |
| The end point of distillation | 188.0 | 76.5 | 197.2 |
| RON | 90.6 | - | - |
Table 2 comparative example 1, embodiment 1 and embodiment 2 process conditions
Table 3 comparative example 1, embodiment 1 and embodiment 2 product property
| Comparative example 1 | Embodiment 1 | Embodiment 2 | |
| Density (20 DEG C)/g/cm3 | 0.722 | 0.728 | 0.739 |
| Total sulfur/μ g/g | 9.7 | 8.7 | 9.0 |
| Alkene/w% | 19.7 | 25.1 | 24.3 |
| RON | 89.3 | 90.3 | 90.1 |
| One way operation/time/h | 394 | 2194 | 2616 |
Comparative example 2
With the catalytic gasoline B of chosen property hydrodesulfurization for raw material (see Table 4), with hydrogen by 1 fixed bed reactors
In carry out adsorb desulphurization reaction, process for adsorption desulfuration condition and product property are as shown in table 5, table 6.As can be seen from Table 6, although
The sulfur content of product is 9.6 μ g/g, and RON loss of octane number reaches 1.4 units, but the one way of adsorbent only runs the time
310h。
Embodiment 3:
Compared with comparative example 2, in the case of raw material is identical, light petrol non-hydrogen physical absorption desulfurization and heavy petrol face hydrogen
The adsorbent of chemisorbed desulfurization is all prepared by ZL03139159.1 embodiment 5, and the method using the present invention, by selectivity
The catalytic gasoline B fractionation of hydrodesulfurization is that light petrol and heavy petrol (see Table 4), heavy petrol and hydrogen pass through 1 fixed bed reaction
Device carries out facing hydrogen absorption desulphurization reaction, and product and light petrol non-hydrogen physical absorption desulfurization product are in harmonious proportion and are finally modified
Gasoline products.Heavy petrol faces hydrogen absorption desulfurization and light petrol non-hydrogen physical absorption desulfurization process conditions is shown in Table 5, and product property is such as
Shown in table 6.As can be seen from Table 6, the sulfur content of product is 9.4 μ g/g, only 0.4 unit of RON loss of octane number, adsorbent
The one way operation time reaches 1854h.
Embodiment 4:
Compared with comparative example 2, in the case of raw material is identical, light petrol non-hydrogen physical absorption desulfurization and heavy petrol face hydrogen
The adsorbent of chemisorbed desulfurization is all prepared by by ZL03139159.1 embodiment 5, the method using the present invention, will select
Property hydrodesulfurization catalytic gasoline B fractionation for light petrol and heavy petrol (see Table 4), heavy petrol, hydrogen pass sequentially through 2 fixed beds
Reactor carries out facing hydrogen absorption desulphurization reaction, and product and light petrol non-hydrogen physical absorption desulfurization product are in harmonious proportion and obtain finally
Reformulated gasoline product.Heavy petrol faces hydrogen absorption desulfurization and light petrol non-hydrogen physical absorption desulfurization process conditions is shown in Table 5, product
Matter is shown in Table 6.As can be seen from Table 6, the sulfur content of product is 9.5 μ g/g, only 0.6 unit of RON loss of octane number, adsorbent
The one way operation time reaches 2076h.
The raw material that table 4 comparative example 2, embodiment 3 and embodiment 4 use
| Project | Raw material B | Light petrol | Heavy petrol |
| Density (20 DEG C)/g/cm3 | 0.720 | 0.662 | 0.763 |
| Total sulfur/μ g/g | 108.3 | 25.2 | 148.2 |
| Alkene/w% | 28.3 | 41.4 | 22.7 |
| Boiling range/DEG C | |||
| Initial boiling point | 37.2 | - | 63.1 |
| 10% | 50.9 | 36.4 | 93.9 |
| 30% | 65.2 | 37.1 | 106.2 |
| 50% | 89.7 | 39.9 | 118.6 |
| 70% | 121.3 | 44.5 | 146.1 |
| 90% | 171.2 | 52.6 | 174.8 |
| The end point of distillation | 193.2 | 66.0 | 198.2 |
| RON | 91.2 | - | - |
Table 5 comparative example 2, embodiment 3 and embodiment 4 process conditions
Table 6 comparative example 2, embodiment 3 and embodiment 4 product property
| Comparative example 2 | Embodiment 3 | Embodiment 4 | |
| Density (20 DEG C)/g/cm3 | 0.723 | 0.730 | 0.738 |
| Total sulfur/μ g/g | 9.6 | 9.4 | 9.5 |
| Alkene/w% | 20.3 | 25.2 | 24.1 |
| RON | 89.8 | 90.8 | 90.6 |
| One way operation/time/h | 310 | 1854 | 2076 |
Claims (19)
1. the method for an adsorbing and desulfurizing catalytic cracking gasoline, it is characterised in that: with the catalysis after selective hydrodesulfurization
Cracking gasoline is raw material, enters fractionating column and carries out cutting fractionation, is fractionated as light petrol and heavy petrol, light petrol entrance physical absorption
Desulfurization fixed bed reactors carry out non-hydrogen physical absorption desulfurization, and heavy petrol mixes with hydrogen, and entrance is faced hydrogen absorption desulfurization and fixed
Bed reactor carries out facing hydrogen absorption desulfurization.
2. the method for claim 1, it is characterised in that the operation pressure of fractionating column is 0.1～1.0MPa, and fractionation obtains
The sulfur content of light petrol less than 40 μ g/g.
3. the method for claim 1, it is characterised in that described light petrol non-hydrogen physical absorption desulfurization includes following
Step:
1) non-hydrogen physical absorption: light petrol raw material is heated to 20～400 DEG C, in volume space velocity 0.2～10h-1, operation pressure
Entering fixed bed reactors under conditions of power 0.1～3MPa to contact with desulfuration adsorbent, the light petrol after absorption desulfurization goes out solid
Fixed bed reactor；
2) face hydrogen and process desulfuration adsorbent: stop after desulfuration adsorbent absorption is saturated entering feedstock oil, in temperature higher than absorption temperature
Spending 0～50 DEG C, volume space velocity is 10～2000h-1, under conditions of operation pressure 0.1～3MPa, makes hydrogen be adsorbed by desulfurization
Agent bed, faces hydrogen and processes desulfuration adsorbent.
4. method as claimed in claim 3, it is characterised in that carry out described step 1) and step 2) process 5-20 time after, right
Desulfuration adsorbent carries out regenerating and reducing.
5. method as claimed in claim 4, it is characterised in that carrying out described regeneration condition is: regeneration temperature 300～600
DEG C, regeneration pressure 0.1～2.0MPa, regeneration gas comprises oxygen.
6. method as claimed in claim 4, it is characterised in that the desulfuration adsorbent after regenerating and reducing gas react real
Existing desulfuration adsorbent reduction, reducing condition is: reduction temperature 260～600 DEG C, and reduction pressure 0.1～2.0MPa, reducing gas is
Hydrogen volume content is at least the gas of 40%.
7. method as claimed in claim 3, it is characterised in that described desulfuration adsorbent is mainly by zinc oxide and reduced state nickel
Composition.
8. method as claimed in claim 3, it is characterised in that described desulfuration adsorbent comprise percentage by weight be 15%～
The zinc oxide of 90% and the reduced state nickel that percentage by weight is 2%～85%.
9. method as claimed in claim 3, it is characterised in that described desulfuration adsorbent comprises silica and aluminum oxide.
10. method as claimed in claim 3, it is characterised in that described desulfuration adsorbent weight percent consists of: particle diameter 100
～500 zinc oxide 30%～85% of μm, silica 5%～60%, aluminum oxide 5%～30%, reduced state nickel 3%～60%.
11. methods as claimed in claim 3, it is characterised in that step 1) in raw material be heated to 100～350 DEG C, volume space velocity
Being 0.5～5h-1, operation pressure is 0.5～2MPa.
12. methods as claimed in claim 3, it is characterised in that step 2) it is higher than adsorption temp 30～50 DEG C, volume in temperature
Air speed is 500～1000h-1, under conditions of operation pressure 0.5～2MPa, makes hydrogen pass through desulfuration adsorbent bed, to desulfurization
Adsorbent carries out facing hydrogen and processes.
13. the method for claim 1, it is characterised in that described heavy petrol faces hydrogen absorption desulfurization fixed bed reactors dress
Its weight percent of the adsorbent filled out consists of: zinc oxide 10%～85%, silica 5%～80%, aluminum oxide 5%～30%,
Reduced state nickel 4%～45%.
14. the method for claim 1, it is characterised in that heavy petrol faces the operation bar of hydrogen absorption desulfurization fixed bed reactors
Part is heavy petrol volume space velocity 0.2～10h-1, reaction temperature 180～420 DEG C, hydrogen to oil volume ratio 20～100v/v, operates pressure
0.5～3.0MPa.
15. the method for claim 1, it is characterised in that heavy petrol faces the suction of hydrogen absorption desulfurization fixed bed reactors filling
After attached dose reaches work Sulfur capacity, carry out regenerating and reducing.
16. methods as claimed in claim 15, it is characterised in that regeneration condition is: regeneration temperature 300～600 DEG C, regeneration pressure
Power 0.1～2.0MPa, regeneration gas comprises oxygen.
17. methods as claimed in claim 15, it is characterised in that the desulfuration adsorbent after regeneration and reducing gas react realization
Adsorbent reduces, and reducing condition is: reduction temperature 260～600 DEG C, and reduction pressure 0.1～2.0MPa, reducing gas is hydrogen
Long-pending content is at least the gas of 40%.
18. the method for claim 1, it is characterised in that heavy petrol faces hydrogen absorption fixed bed reactors used by desulfurization and is
One fixed bed reactors or the series connection of multiple fixed bed reactors.
19. the method for claim 1, it is characterised in that heavy petrol faces the absorption in hydrogen absorption desulfurization fixed bed reactors
After agent reaches work Sulfur capacity, it is switched to another fixed bed reactors in parallel therewith or the fixed bed reaction of multiple series connection
Device.
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| CN104673376B (en) * | 2015-02-04 | 2016-08-31 | 中国石油大学(北京) | A kind of gasoline desulfating method |
| WO2016123859A1 (en) * | 2015-02-04 | 2016-08-11 | 中国石油大学(北京) | Desulfurization adsorbent for petrol and petrol desulfurization method |
| US10011779B2 (en) | 2015-02-04 | 2018-07-03 | China University Of Petroleum-Beijing | Adsorbent for desulfurization of gasoline and method for desulfurization of gasoline |
| US11254880B2 (en) | 2017-02-10 | 2022-02-22 | Advanced Energy Materials, Llc | Desulfurization and sulfur tolerant hydrogenation processes of hydrocarbon feedstocks |
| WO2018148366A1 (en) * | 2017-02-10 | 2018-08-16 | Advanced Energy Materials, Llc | Nanometal oxide adsorbents for desulfurization of hydrocarbon fuels |
| CN108659880B (en) * | 2017-03-28 | 2020-10-27 | 中国石油化工股份有限公司 | Method and system for gasoline desulfurization and aromatization |
| CN108659883B (en) * | 2017-03-28 | 2020-10-27 | 中国石油化工股份有限公司 | Method and system for gasoline desulfurization and aromatization |
| CN110857402B (en) * | 2018-08-22 | 2023-06-06 | 中国石油化工股份有限公司 | Combined processing technology of catalytic cracking gasoline |
| CN111676051A (en) * | 2020-06-17 | 2020-09-18 | 陕西华大骄阳能源环保发展集团有限公司 | Method for desulfurizing light oil in non-hydrogenation or hydrogenation atmosphere |
| CN116064154A (en) * | 2021-11-01 | 2023-05-05 | 中国石油化工股份有限公司 | Deep desulfurization method and system for gasoline |
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