CN105694949B - The method of gasoline absorbing desulfurization - Google Patents
The method of gasoline absorbing desulfurization Download PDFInfo
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- CN105694949B CN105694949B CN201410699821.9A CN201410699821A CN105694949B CN 105694949 B CN105694949 B CN 105694949B CN 201410699821 A CN201410699821 A CN 201410699821A CN 105694949 B CN105694949 B CN 105694949B
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Abstract
The present invention relates to a kind of method of gasoline absorbing desulfurization, this method includes：Absorption desulfurization is carried out to catalytic hydrogenation gasoline using gasoline adsorbing and desulfurizing agent, the condition of the absorption desulfurization includes：Temperature is 300 400 DEG C, and pressure is 0.5 1.0MPa, and volume space velocity is 3 7h‑1, H2/ gasoline-volume ratio is 1:100 120, wherein, the preparation method of the gasoline adsorbing and desulfurizing agent includes：It is molded after active component, carrier and water are well mixed, then dries, is calcined, gasoline adsorbing and desulfurizing agent is obtained, wherein, the active component contains ZnO, NiO, NiCO3、CuO、K2CO3And KNO3, the carrier contains SiO2、Al2O3With SBA 15.Absorption desulfurization is carried out to gasoline using the method for the present invention, the desulfurization degree of gasoline absorbing desulfurization can be improved while octane number is reduced, can make it that desulfurization degree is up to more than 80%.
Description
Technical field
The present invention relates to a kind of method of gasoline absorbing desulfurization.
Background technology
Sulfide in motor petrol causes serious threat to human health and environment, for example, sulphur can make vehicle startup
Catalyst poisoning in machine catalyst converter, the SOx of generation of burning causes serious atmosphere pollution with exhaust emissions, through poisoning
The tail gas that gives off of catalyst changer contain substantial amounts of imperfect combustion hydrocarbon, the nitrogen of generation or the oxide of carbon are through sunlight
Irradiation forms photochemical fog.With the continuous improvement of environmental requirement, in the last few years for motor petrol quality requirement not yet
Disconnected to improve, the total sulfur in gasoline is even more a very important index.EC regulations limit the sulfur content of motor petrol within 2009
In below 10 μ g/g (Europe V standards).Provincial standard is formulated in Beijing and Shanghai of China for 2009 respectively, is limited gasoline sulfure content and is existed
Below 50 μ g/g, implement the standard of state IV.Beijing in 2012 is and suitable by promotion and implementation by further genralrlization low energy consumption automobile
In state's V standards of Euro V emissions, then also necessarily propose tightened up requirement to the sulfur content in gasoline, by 50 former μ
G/g drops to 10 μ g/g, and producing super low-sulfur oil, oneself turns into the general trend that current world's gasoline cleaningization develops.In recent years, one
A little researchers are removed using chemiadsorption to the sulfide of gasoline.But the research to absorption method sulfur removal technology is also compared
It is few, there is desulfuration efficiency defect not high in existing process for adsorption desulfuration.
Therefore, a kind of desulfurizing method by adsorption that can improve desulfuration efficiency is badly in need of now.
The content of the invention
The invention aims to overcome in the prior art the not high defect of desulfuration efficiency there is provided a kind of gasoline adsorption is de-
The method of sulphur.
The present inventor has found that it is de- that absorption is carried out to catalytic hydrogenation gasoline using gasoline adsorbing and desulfurizing agent under study for action
Sulphur, the condition of the absorption desulfurization includes：Temperature is 300-400 DEG C, and pressure is 0.5-1.0MPa, and volume space velocity is 3-7h-1,
H2/ gasoline-volume ratio is 1:100-120, the preparation method of the gasoline adsorbing and desulfurizing agent includes：By active component, carrier and water
Be molded after well mixed, then dried, roasting, gasoline adsorbing and desulfurizing agent is obtained, wherein, the active component contain ZnO,
NiO、NiCO3、CuO、K2CO3And KNO3, the carrier contains SiO2、Al2O3And SBA-15, can be in reduction loss of octane number
The desulfurization degree of gasoline absorbing desulfurization is improved simultaneously.
Therefore, to achieve these goals, the invention provides a kind of method of gasoline absorbing desulfurization, the method includes：
Absorption desulfurization is carried out to catalytic hydrogenation gasoline using gasoline adsorbing and desulfurizing agent, the condition of the absorption desulfurization includes：Temperature is
300-400 DEG C, pressure is 0.5-1.0MPa, and volume space velocity is 3-7h-1, H2/ gasoline-volume ratio is 1:100-120, wherein, it is described
The preparation method of gasoline adsorbing and desulfurizing agent includes：It is molded after active component, carrier and water are well mixed, then dry,
Roasting, is made gasoline adsorbing and desulfurizing agent, wherein, the active component contains ZnO, NiO, NiCO3、CuO、K2CO3And KNO3, institute
State carrier and contain SiO2、Al2O3And SBA-15.
Absorption desulfurization is carried out to gasoline using the method for the present invention, gasoline adsorption can be improved while octane number is reduced
The desulfurization degree of desulfurization, can make it that desulfurization degree is up to more than 80%.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
The embodiment to the present 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.
The invention provides a kind of method of gasoline absorbing desulfurization, the method includes：Using gasoline adsorbing and desulfurizing agent to urging
Change hydrogasoline and carry out absorption desulfurization, the condition of the absorption desulfurization includes：Temperature is 300-400 DEG C, and pressure is 0.5-
1.0MPa, volume space velocity is 3-7h-1, H2/ gasoline-volume ratio is 1:100-120, wherein, the preparation of the gasoline adsorbing and desulfurizing agent
Method includes：It is molded after active component, carrier and water are well mixed, then dries, is calcined, gasoline absorbing desulfurization is obtained
Agent, wherein, the active component contains ZnO, NiO, NiCO3、CuO、K2CO3And KNO3, the carrier contains SiO2、Al2O3With
SBA-15。
In the present invention, above-mentioned absorption desulfurization can be carried out in fixed bed micro-reaction device.
In the present invention, liquid air speed is 1-3h-1The gasoline adsorbing and desulfurizing agent relative to 5g is referred to, volume space velocity is 1-
3h-1.Pressure is that 0.5-0.8MPa refers to that the system pressure in fixed bed micro-reaction device is 0.5-1.0MPa, H2/ gasoline body
Product is than being 1:100-120 refers to adsorb before desulfurization, H in hydrogasoline2With the volume ratio of gasoline.
According to method of the present invention, wherein, as long as carrying out absorption desulfurization using the above method, you can reducing octane
The desulfurization degree of gasoline absorbing desulfurization is improved while value.But, in order to further improve the desulfurization degree of absorption desulfurization and reduce pungent
Alkane value is lost, it is preferable that the method is activated gasoline adsorbing and desulfurizing agent before being additionally included in absorption desulfurization.
According to method of the present invention, wherein, the method for the activation can inhale for the conventional activation gasoline in this area
The method of attached desulfurizing agent, it is preferable that the activation includes：At 50-70 DEG C, process gasoline with 30-50 volume % dust technologies and inhale
Attached desulfurizing agent 10-20h, can further improve the desulfuration efficiency of gasoline absorbing desulfurization and reduce loss of octane number.
According to method of the present invention, wherein it is preferred to, after the method for gasoline absorbing desulfurization is additionally included in absorption desulfurization
Carry out gasoline adsorbing and desulfurizing agent regeneration such that it is able to further reduce the consumption of gasoline adsorbing and desulfurizing agent, further reduces cost.
According to method of the present invention, wherein, gasoline adsorbing and desulfurizing agent regeneration method can be that this area is conventional
Gasoline adsorbing and desulfurizing agent regeneration method, it is preferable that gasoline adsorbing and desulfurizing agent regeneration method includes：At 400-450 DEG C, N2
0.5-0.8h is purged, then passing to air makes O in regeneration reactor2Concentration is 2-5 volume %, then raises regeneration reactor temperature
To 500-550 DEG C, the sulfur content in the tail gas of detection regeneration reactor discharge, when the sulfur content in tail gas is less than 10ppm, vapour
Oily adsorption desulfurizing agent regeneration ending, wherein, total air speed is 2000-2500h-1, can further improve the de- of gasoline absorbing desulfurization
Sulphur efficiency simultaneously reduces loss of octane number.Wherein, the gasoline adsorbing and desulfurizing agent after regeneration can activate or not activate and continue to use
In absorption desulfurization.
In the present invention, the mixed method of active component and carrier and water can be by each component in active component and carrier
Mixed with water again after being first well mixed.
According to method of the present invention, wherein it is preferred to, on the basis of the gross weight of active component, carrier and water,
ZnO content is that 10-15 weight %, NiO content are 5-10 weight %, NiCO3Content containing for 5-10 weight %, CuO
Measure is 2-4 weight %, K2CO3Content be 0.8-1.2 weight %, KNO3Content be 0.4-1 weight %, SiO2Content be
10-25 weight %, Al2O3Content for 5-10 weight %, SBA-15 content be 5-10 weight %, balance of water.
It is highly preferred that on the basis of the gross weight of active component, carrier and water, the content of ZnO is 12-14 weight %, NiO
Content be 6-8 weight %, NiCO3Content be that 6-8 weight %, CuO content is 2.6-3 weight %, K2CO3Content be
1-1.2 weight %, KNO3Content be 0.4-0.5 weight %, SiO2Content be 15-20 weight %, Al2O3Content be 6-8
The content of weight %, SBA-15 is 6-8 weight %, balance of water such that it is able to further improves desulfurization degree and reduces octane number
Loss.
The present inventor has found under study for action, when SBA-15 is donut-like, enable to active component ZnO,
NiO、NiCO3、CuO、K2CO3And KNO3It is better dispersed in mixed carrier SiO2/Al2O3On/SBA-15, so as to more abundant
Ground plays the effect of each active component, and then further improves the desulfurization degree of gasoline absorbing desulfurization and reduce loss of octane number.
The various donut-likes that heretofore described donut-like can be had been generally acknowledged that for this area, for example, can be tool
There are opening or the various circular or classes annular shapes without opening, the SBA-15 carriers of the donut-like can be by various
Mode is obtained, for example, be commercially available, it is also possible to prepared according to various methods of the prior art.
According to method of the present invention, wherein, dry condition can be that the conventional gasoline adsorption for preparing in this area takes off
The drying condition used during sulphur agent, for example, can be 90-150 DEG C for temperature, and the time is 2-6h.
According to method of the present invention, wherein, the condition of roasting can be that the conventional gasoline adsorption for preparing in this area takes off
The condition of the roasting used during sulphur agent, for example, can be 450-550 DEG C for temperature, and the time is 2-6h.
According to method of the present invention, wherein, the technique of the shaping can be the conventional moulding process in this area, example
Such as can be extrusion forming, pressing shaping, preferably extrusion forming, more preferably extrusion forming inhales final obtained gasoline
Attached desulfurizing agent is shaped as strip.
In the present invention, the crushing strength for using the gasoline adsorbing and desulfurizing agent of above-mentioned method for optimizing preparation can be 50-65/
N·cm-1, specific surface area can be 30-50m2·g-1, pore volume can be 0.2-0.5mLg-1。
In the case of more preferably, i.e., active component, carrier and water are in the range of most preferred content or SBA-15 is bagel
During shape SBA-15, the crushing strength of obtained gasoline adsorbing and desulfurizing agent is 58-62/Ncm-1, specific surface area is 40-45m2·g-1, pore volume is 0.25-0.4mLg-1。
Preparation example
Donut-like SBA-15 carriers according to Sun Jinyu, Zhao Dongyuan, the big-pore mesoporous molecule of " bagel " shape high-sequential
Sieve SBA-15 synthesis, SCI, 2000,1 (21):It is prepared by 21~23 preparation method.
The specific preparation method of donut-like SBA-15 is：
With DMF (DMF) as cosolvent, by 2.0 grams of Pluronic F-127 ethers-polycyclic oxypropylene ether-poly-
Oxireme ether triblock copolymer surfactant (Aldrich, average molecular mass Mn=5800, molecular formula EO20PO70EO20)
It is dissolved in 45 grams of distilled water and 30 grams of (4mol/L) hydrochloric acid, 15 grams of DMF is added at 40 DEG C.Stirring adds 4.45 grams after 1 hour
Tetraethyl orthosilicate (TEOS, Shenyang chemical reagent work), in 40 DEG C of stirring reactions 24 hours.It is mesoporous former powder to be obtained after filtering, washing, drying
Material.The former powder mesoporous material of gained is calcined 24 hours for 600 DEG C in Muffle furnace, template agent is removed, obtains donut-like mesoporous
Material SBA-15.
Preparation example 1
By 12g ZnO, 6g NiO, 8g NiCO3、2.6g CuO、1g K2CO3、0.5g KNO3、15gSiO2、6g Al2O3、
6g SBA-15 (donut-like) and 42.9g water are well mixed, then carry out extrusion forming for strip, then dry 3h at 90 DEG C,
Then 4h is dried at 450 DEG C again, gasoline adsorbing and desulfurizing agent A1 is made.
Preparation example 2
By 14g ZnO, 7g NiO, 7g NiCO3、3g CuO、1.1g K2CO3、0.5g KNO3、17gSiO2、7g Al2O3、
8g SBA-15 (donut-like) and 35.4g water are well mixed, and it is strip then to carry out extrusion forming, then is dried at 150 DEG C
2h, then dries 2h at 550 DEG C again, and gasoline adsorbing and desulfurizing agent A2 is made.
Preparation example 3
By 13g ZnO, 8g NiO, 6g NiCO3、2.8g CuO、1.2g K2CO3、0.4g KNO3、20g SiO2、8g
Al2O3, 7g SBA-15 (donut-like) and 33.6g water it is well mixed, then carry out extrusion forming for strip, then at 120 DEG C
6h is dried, then 6h is dried at 500 DEG C again, gasoline adsorbing and desulfurizing agent A3 is obtained.
Preparation example 4
Method according to preparation example 1 prepares gasoline adsorbing and desulfurizing agent, unlike, by 15g ZnO, 10gNiO, 10g
NiCO3、4g CuO、0.8g K2CO3、1g KNO3、10g SiO2、10g Al2O3, 10g SBA-15 (donut-like) and 29.2g
Water is well mixed, and gasoline adsorbing and desulfurizing agent A4 is made.
Preparation example 5
Method according to preparation example 1 prepares gasoline adsorbing and desulfurizing agent, unlike, Changchun (is purchased from using bar-shaped SBA-15
High-tech limited company of Jilin University) donut-like SBA-15 is replaced, gasoline adsorbing and desulfurizing agent A5 is made.
Preparation example 6
Method according to preparation example 1 prepares gasoline adsorbing and desulfurizing agent, unlike, CuO is not contained in active component, is made
Gasoline adsorbing and desulfurizing agent D1.
Preparation example 7
Method according to preparation example 1 prepares gasoline adsorbing and desulfurizing agent, unlike, K is not contained in active component2CO3With
KNO3, gasoline adsorbing and desulfurizing agent D2 is made.
Test case
The crushing strength of gasoline adsorbing and desulfurizing agent A1-A5 and D1-D2 is determined using GB/T 10505.1-1989 methods, is adopted
With GB/T 19587-2004 methods measurement the specific area and pore volume, as a result as shown in table 1.
Embodiment
In the following Examples and Comparative Examples, desulfurization degree=1- (gross masses of the sulfur-containing compound after desulfurization in gasoline/de-
The gross mass of the sulfur-containing compound before sulphur in gasoline) × 100%.
Embodiment 1
The present embodiment is used for the method for illustrating gasoline absorbing desulfurization of the invention.
At 50 DEG C, gasoline adsorbing and desulfurizing agent 10h is processed with 30 volume % dust technologies, then with catalytic hydrogenation gasoline (sulphur
Content is 20.6mg/L, and 90.2) it is reaction raw materials that octane number is, wherein, the H in hydrogasoline2/ gasoline-volume ratio is 1:100,
Using fixed bed micro-reaction device, the loading of gasoline adsorbing and desulfurizing agent A1 is 5g, is 300 DEG C in temperature, and pressure is 0.5MPa,
Volume space velocity is 3h-1Under conditions of, catalytic hydrogenation gasoline is passed through the gasoline absorbing desulfurization filled in fixed bed micro-reaction device
Agent A1 carries out absorption desulfurization, and then the desulfurizing agent adsorbed after desulfurization is put into regeneration reactor, at 400 DEG C, N2Purging
0.5h, then passing to air makes O in regeneration reactor2Concentration is 2 volume %, then raises regeneration reactor temperature to 500 DEG C, is examined
The sulfur content surveyed in the tail gas of regeneration reactor discharge, when the sulfur content in tail gas is less than 10ppm, gasoline adsorbing and desulfurizing agent is again
Life terminates, wherein, total air speed is 2000h-1, the gasoline adsorbing and desulfurizing agent that obtains of regeneration be not required to reactivation just can continue cycling through for
Adsorb in sweetening process, contain in the gasoline through adsorbing desulfurization flowed out using chromatography determination fixed bed micro-reaction device exit
The content of sulphur compound, the results are shown in Table 2, use gasoline octane number tester determine through adsorb desulfurization gasoline octane number for
90.1, loss of octane number is 0.1 unit.
Embodiment 2
The present embodiment is used for the method for illustrating the gasoline absorbing desulfurization of the present invention.
At 60 DEG C, gasoline adsorbing and desulfurizing agent 15h is handled with 40 volume % dust technologies, then with catalytic hydrogenation gasoline (sulphur
Content is 20.6mg/L, and 90.2) it is reaction raw materials that octane number is, wherein, the H in hydrogasoline2/ gasoline-volume ratio is 1:110,
Using fixed bed micro-reaction device, the loading of gasoline adsorbing and desulfurizing agent A2 is 5g, is 350 DEG C in temperature, and pressure is 0.7MPa,
Volume space velocity is 5h-1Adsorption conditionses under, make catalytic hydrogenation gasoline pass through fixed bed micro-reaction device in fill gasoline adsorption
Desulfurizing agent A2 carries out absorption desulfurization, and then the desulfurizing agent adsorbed after desulfurization is put into regeneration reactor, at 420 DEG C, N2Blow
0.7h is swept, then passing to air makes O in regeneration reactor2Concentration is 4 volume %, then raises regeneration reactor temperature to 520 DEG C,
The sulfur content in the tail gas of regeneration reactor discharge is detected, when the sulfur content in tail gas is less than 10ppm, gasoline adsorbing and desulfurizing agent
Regeneration ending, wherein, total air speed is 2300h-1, the gasoline adsorbing and desulfurizing agent that regeneration is obtained is not required to be re-activated just can continue cycling through use
In absorption sweetening process, in the gasoline through adsorbing desulfurization flowed out using chromatography determination fixed bed micro-reaction device exit
The content of sulfur-containing compound, the results are shown in Table 2, use gasoline octane number tester determine through adsorb desulfurization gasoline octane number for
90.1, loss of octane number is 0.1 unit.
Embodiment 3
The present embodiment is used for the method for illustrating gasoline absorbing desulfurization of the invention.
At 70 DEG C, gasoline adsorbing and desulfurizing agent 20h is processed with 50 volume % dust technologies, then with catalytic hydrogenation gasoline (sulphur
Content is 20.6mg/L, and 90.2) it is reaction raw materials that octane number is, wherein, the H in hydrogasoline2/ gasoline-volume ratio is 1:120,
Using fixed bed micro-reaction device, the loading of gasoline adsorbing and desulfurizing agent A3 is 5g, is 400 DEG C in temperature, and pressure is 1.0MPa,
Volume space velocity is 7h-1Adsorption conditionses under, catalytic hydrogenation gasoline is passed through the gasoline adsorption filled in fixed bed micro-reaction device
Desulfurizing agent A3 carries out absorption desulfurization, and then the desulfurizing agent adsorbed after desulfurization is put into regeneration reactor, at 450 DEG C, N2Blow
0.8h is swept, then passing to air makes O in regeneration reactor2Concentration is 5 volume %, then raises regeneration reactor temperature to 550 DEG C,
The sulfur content in the tail gas of regeneration reactor discharge is detected, when the sulfur content in tail gas is less than 10ppm, gasoline adsorbing and desulfurizing agent
Regeneration ending, wherein, total air speed is 2500h-1, the gasoline adsorbing and desulfurizing agent that regeneration is obtained is not required to be re-activated just can continue cycling through use
In sweetening process is adsorbed, using in the gasoline through adsorbing desulfurization that chromatography determination fixed bed micro-reaction device exit is flowed out
The content of sulfur-containing compound, the results are shown in Table 2, use gasoline octane number tester determine through adsorb desulfurization gasoline octane number for
90.1, loss of octane number is 0.1 unit.
Embodiment 4
The present embodiment is used for the method for illustrating gasoline absorbing desulfurization of the invention.
Method according to embodiment 1 carries out absorption desulfurization to catalytic hydrogenation gasoline, the difference is that using gasoline absorbing desulfurization
Agent A4, the Removal of Sulfur Compounds from Gasoline through adsorbing desulfurization flowed out using chromatography determination fixed bed micro-reaction device exit
Content, the results are shown in Table 2, use the octane number of gasoline of the gasoline octane number tester measure through absorption desulfurization for 89.9, octane number
It is 0.3 unit to lose.
Embodiment 5
The present embodiment is used for the method for illustrating gasoline absorbing desulfurization of the invention.
Absorption desulfurization is carried out to catalytic hydrogenation gasoline according to the method for embodiment 1, the difference is that using gasoline absorbing desulfurization
Agent A5, the Removal of Sulfur Compounds from Gasoline through adsorbing desulfurization flowed out using chromatography determination fixed bed micro-reaction device exit
Content, the results are shown in Table 2, use the octane number of gasoline of the gasoline octane number tester measure through absorption desulfurization for 89.9, octane number
Lose as 0.3 unit.
Comparative example 1
Method according to embodiment 1 carries out absorption desulfurization to catalytic hydrogenation gasoline, the difference is that using gasoline absorbing desulfurization
Agent D1, the Removal of Sulfur Compounds from Gasoline through adsorbing desulfurization flowed out using chromatography determination fixed bed micro-reaction device exit
Content, the results are shown in Table 2, and the octane number for using gasoline octane number tester to determine the gasoline through adsorbing desulfurization is 88.2, octane number
It is 2 units to lose.
Comparative example 2
Method according to embodiment 1 carries out absorption desulfurization to catalytic hydrogenation gasoline, the difference is that using gasoline absorbing desulfurization
Agent D2, the Removal of Sulfur Compounds from Gasoline through adsorbing desulfurization flowed out using chromatography determination fixed bed micro-reaction device exit
Content, the results are shown in Table 2, and the octane number for using gasoline octane number tester to determine the gasoline through adsorbing desulfurization is 88.2, octane number
It is 2 units to lose.
Comparative example 3
Use with the constituent identical catalytic hydrogenation gasoline of embodiment 1 that (sulfur content is 20.6mg/L, and octane number is
90.2), continue to carry out the catalytic hydrogenation gasoline hydrodesulfurization, hydrogenation by the way of hydrodesulfurization is without using absorption desulfurization
The specific method of desulfurization is carried out according to patent application CN101787307A.Using containing in the gasoline after chromatography determination hydrodesulfurization
The content of sulphur compound, the results are shown in Table 2, and the octane of the gasoline after continuing hydrodesulfurization is determined using gasoline octane number tester
It is 88.2 to be worth, and loss of octane number is 2 units.
Table 1
| Crushing strength (Ncm-1) | Specific surface area (m2·g-1) | Pore volume (mLg-1) | |
| Preparation example 1 | 58.2 | 41 | 0.26 |
| Preparation example 2 | 63 | 42 | 0.3 |
| Preparation example 3 | 61 | 45 | 0.4 |
| Preparation example 4 | 50 | 30 | 0.2 |
| Preparation example 5 | 65 | 50 | 0.5 |
| Preparation example 6 | 30 | 20 | 0.1 |
| Preparation example 7 | 25 | 20 | 0.1 |
Table 2
The desulfurization degree that can be seen that embodiment 1-5 gasoline absorbing desulfurizations by the data of table 2 is significantly higher than comparative example 1-3
Desulfurization degree.In addition, by the way that embodiment 1-5 and comparative example 1-3 octane number to be compared to the octane as can be seen that embodiment 1-5
Value loss is substantially less than comparative example 1-3.
Embodiment 1 is compared with embodiment 4 to can be seen that and worked as on the basis of the gross weight of active component, carrier and water,
ZnO content is that 12-14 weight %, NiO content are 6-8 weight %, NiCO3Content be 6-8 weight %, CuO content
It is 2.6-3 weight %, K2CO3Content be 1-1.2 weight %, KNO3Content be 0.4-0.5 weight %, SiO2Content be
15-20 weight %, Al2O3Content be that 6-8 weight %, SBA-15 content is 6-8 weight %, when surplus is water, obtained vapour
The crushing strength of oily adsorption desulfurizing agent is 58-62/Ncm-1, specific surface area is 40-45m2·g-1, pore volume is 0.25-0.4mL
g-1Such that it is able to further improve the desulfurization degree of gasoline absorbing desulfurization and reduce loss of octane number.
Embodiment 1 is compared with embodiment 5 and be can be seen that when SBA-15 is donut-like SBA-15, obtained gasoline
The crushing strength of adsorption desulfurizing agent is 58-62/Ncm-1, specific surface area is 40-45m2·g-1, pore volume is 0.25-0.4mLg-1, so as to further improve the desulfurization degree of gasoline absorbing desulfurization and reduce loss of octane number.
Absorption desulfurization is carried out to gasoline using the method for the present invention, gasoline adsorption can be improved while octane number is reduced
The desulfurization degree of desulfurization, can make it that desulfurization degree is up to more than 80%.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy is no longer separately illustrated.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (9)
1. a kind of method of gasoline absorbing desulfurization, it is characterised in that the method includes：Catalysis is added using gasoline adsorbing and desulfurizing agent
Hydrogen gasoline carries out absorption desulfurization, and the condition of the absorption desulfurization includes：Temperature is 300-400 DEG C, and pressure is 0.5-1.0MPa, body
Product air speed is 3-7h-1, H2/ gasoline-volume ratio is 1:100-120, wherein, the preparation method of the gasoline adsorbing and desulfurizing agent includes：
It is molded after active component, carrier and water are well mixed, then dries, is calcined, gasoline adsorbing and desulfurizing agent is obtained, wherein,
The active component contains ZnO, NiO, NiCO3、CuO、K2CO3And KNO3, the carrier contains SiO2、Al2O3And SBA-15；Its
In, on the basis of the gross weight of active component, carrier and water, ZnO content is that 10-15 weight %, NiO content are 5-10 weights
Amount %, NiCO3Content be that 5-10 weight %, CuO content is 2-4 weight %, K2CO3Content be 0.8-1.2 weight %,
KNO3Content be 0.4-1 weight %, SiO2Content be 10-25 weight %, Al2O3Content be 5-10 weight %, SBA-15
Content be 5-10 weight %, balance of water.
2. according to the method described in claim 1, wherein, this method be additionally included in absorption desulfurization before gasoline adsorbing and desulfurizing agent is entered
Row activation.
3. method according to claim 2, wherein, the activation includes：At 50-70 DEG C, with the 30-50 volumes dilute nitre of %
Acid treatment gasoline adsorbing and desulfurizing agent 10-20h.
4. method according to claim 1, wherein, the method carries out gasoline adsorbing and desulfurizing agent after being additionally included in absorption desulfurization
Regeneration.
5. method according to claim 4, wherein, gasoline adsorbing and desulfurizing agent regeneration method includes：At 400-450 DEG C
Under, N20.5-0.8h is purged, then passing to air makes O in regeneration reactor2Concentration is 2-5 volume %, then raises regeneration reactor
To 500-550 DEG C, the sulfur content in the tail gas of detection regeneration reactor discharge treats that the sulfur content in tail gas is less than 10ppm to temperature
When, gasoline adsorbing and desulfurizing agent regeneration ending, wherein, total air speed is 2000-2500h-1。
6. according to the method described in claim 1, wherein, on the basis of the gross weight of active component, carrier and water, ZnO's contains
Measure as the content of 12-14 weight %, NiO is 6-8 weight %, NiCO3Content for 6-8 weight %, CuO content be 2.6-3
Weight %, K2CO3Content be 1-1.2 weight %, KNO3Content be 0.4-0.5 weight %, SiO2Content be 15-20 weight
Amount %, Al2O3Content for 6-8 weight %, SBA-15 content be 6-8 weight %, balance of water.
7. according to the method described in claim 1, wherein, the SBA-15 be donut-like SBA-15.
8. according to the method described in claim 1, wherein, dry condition includes：Temperature is 90-150 DEG C, and the time is 2-6h.
9. method according to claim 1, wherein, the condition of roasting includes：Temperature is 450-550 DEG C, and the time is 2-6h.
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| WO2014030964A1 (en) * | 2012-08-23 | 2014-02-27 | 에스케이이노베이션 주식회사 | Oxidative desulphurisation method for hydrocarbons |
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| WO2014030964A1 (en) * | 2012-08-23 | 2014-02-27 | 에스케이이노베이션 주식회사 | Oxidative desulphurisation method for hydrocarbons |
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| SBA-15分子筛改性及其对噻吩的吸附脱除;鲍磊;《太原理工大学学报》;20140531;第45卷(第3期);第319-323页 * |
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