CN107638885A - A kind of ultra-deep desulfurization catalyst and preparation method thereof - Google Patents
A kind of ultra-deep desulfurization catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of ultra-deep desulfurization catalyst and preparation method thereof.The preparation method, which comprises the following steps (1) molybdate is dissolved in deionized water, obtains molybdic acid saline solution, adjusts pH to 1.0 5.0；Bull quaternary ammonium salt aqueous solution is added, adjusts pH to 1.0 5.0；Centrifugation, washing, dry, obtain Mo base presomas GSMPs；(2) GSMPs is scattered in deionized water, the SiO added after tabletting sieving2‑Al2O3Carrier is reacted, and is washed, is dried to obtain GSMPs/SA, is then calcined, and obtains oxidized catalyst Mo GSHD；(3) Mo GSHD are impregnated with nickel salt solution, then dries, is calcined, obtain oxidized catalyst NiMo GSHD；(4) by NiMo GSHD presulfurizations, ultra-deep desulfurization catalyst is obtained.The catalyst is applied to the modification of poor quality fuel oil, and be particularly suitable for use in high-sulfur fuel oil, and ultra-deep desulfurization of fuel can be achieved.
Description
Technical field
The present invention relates to a kind of ultra-deep desulfurization catalyst and preparation method thereof, belong to catalyst preparation technical field.
Background technology
With rapid economic development, automobile quantity is continuously increased, and refinery, which must produce super-low sulfur clean fuel oil, to expire
The increasingly strict environmental regulation of foot and oil product standard.But for this macromolecular Containing Sulfur of 4,6- dimethyl Dibenzothiophenes
Compound, because the steric hindrance effect of the methyl of 4 and 6 makes it be difficult to deviate from, sternness is proposed to ultra-deep desulfurization of fuel
Test.Hydrodesulfurization technology is a kind of method of sulfide in wide variety of removing fuel oil, and high-performance hydrodesulfurization catalytic
The synthesis of agent is to improve the key of its desulfurized effect.
It is that auxiliary agent has been carried on the catalyst of alumina support synthesis using Mo (W) sulfide as active component, with Ni (Co)
It is widely used in hydrodesulfurization technology.Research finds that Co (Ni)-Mo (W)-S-phase is with I phases and II phases on the alumina support
Two kinds of forms are present：In I phases, Mo is connected with each other with the Al in alumina support by oxygen bridge, and metal component state of cure (vulcanization) is low, urges
Agent hydrodesulfurization activity is low；In II phases, interacted between Co and carrier by weaker Van der Waals force, state of cure (vulcanization) is high, urges
Agent hydrodesulfurization activity is high.When Mo has strong interaction with carrier, Mo decentralization is high, but sulphidity is low；Mo and carrier
Between interaction it is weak when, Mo decentralization is low, but sulphidity is high.
In alumina load Mo catalyst, the interaction between Mo and carrier is by aluminium in Mo oxides and carrier
Caused by the chemical bond that hydroxyl is formed.Klimova et al. (T.Klimova, M.Calder ó n, J.Ram í rez,
Appl.Catal.,A：Gen.240 (2003) 29-40) use Mesoporous silica MCM 41 to weaken for carrier between Mo and carrier
Interaction, but MCM-41 mechanical strength, heat and hydrothermal stability are relatively low, limit its commercial Application.Felipe Sá
Nchez-Minero et al. (F.S á nchez-Minero, J.Ram í rez, A.Guti é rrez-Alejandre, C.Fern á
ndez-Vargas,P.Torres-Mancera,R.Cuevas-Garcia,Catal.Today.133-135(2008)267-
276) by with SiO2Modify γ-Al2O3The mode on surface, the quantity of surfaces of aluminum hydroxyl is significantly reduced, reduces Mo and carrier
Between interaction, improve Mo sulphidity；But due to the declines between Mo and carrier, Mo phases is gathered into bulky grain,
Reduce Mo decentralization.
Balance cake filtration method (F.Y.A.El Kady, M.G.Abd El Wahed, S.Shaban, A.O.Abo El
Naga, Fuel.89 (2010) 3193-3206), precipitation-sedimentation (M.V.Landau, L.Vradman, M.Herskowitz,
Y.Koltypin, A.Gedanken, J.Catal.201 (2001) 22-36), ultrasound and chemical vapour deposition technique (A.Cho,
J.J.Lee, J.H.Koh, A.Wang, S.H.Moon, Green Chem.9 (2007) 620-625) pass through metal component and carrier
Between strong interaction, improve metal dispersity, but be reduction of the stacking degree of metal component, hinder 4,6- dimethyl
The absorption and reaction of dibenzothiophenes.
By using metallo-chelate as metal precursor, the stacking degree of metal component can be significantly improved
(K.A.Leonova,O.V.Klimov,E.Y.Gerasimov,P.P.Dik,V.Y.Pereyma,S.V.Budukva,
A.S.Noskov,Adsorption.19(2013)723-731).But metallo-chelate stability is low, in loading process easily
Decompose, cause metal component scattered uneven, catalytic activity is low.
In summary, coordinate hydrodesulfurization metal component decentralization and stacking degree effectively to eliminate macromolecular Containing Sulfur
The space steric effect of compound, it is still an arduous challenge.
The content of the invention
In order to solve the above technical problems, it is an object of the invention to provide a kind of ultra-deep desulfurization catalyst and its preparation side
Method, the catalyst are applied to the modification of poor quality fuel oil, and be particularly suitable for use in high-sulfur fuel oil, and ultra-deep desulfurization of fuel can be achieved.
In order to achieve the above object, the invention provides a kind of preparation method of ultra-deep desulfurization catalyst, this method bag
Include following steps：
(1) molybdate is dissolved in deionized water and obtains molybdic acid saline solution, adjust pH to 1.0-5.0；Add bull season
Ammonium salt aqueous solution, adjust pH to 1.0-5.0；Centrifugation, washing, dry, obtain Mo base presomas GSMPs；
(2) GSMPs is scattered in deionized water, the SiO added after tabletting sieving2-Al2O3Carrier is reacted, and is washed
Wash, be dried to obtain GSMPs/SA, be then calcined, obtain oxidized catalyst Mo-GSHD；
(3) Mo-GSHD is impregnated with nickel salt solution, then dries, is calcined, obtain oxidized catalyst NiMo-GSHD；
(4) by NiMo-GSHD presulfurizations, ultra-deep desulfurization catalyst is obtained.
In above-mentioned preparation method, it is preferable that in step (1), the molybdate is Ammonium Molybdate Tetrahydrate, seven hydration molybdenums
One or more of combinations in sour ammonium and sodium molybdate.
In above-mentioned preparation method, it is preferable that the concentration of the molybdic acid saline solution is 0.01-0.02mol/L.
In above-mentioned preparation method, it is preferable that the concentration of the quaternary ammonium salt aqueous solution is 0.03-0.10mol/L, is added
Measure as 0.1-1.0 times of molybdate aqueous solution volume.
In above-mentioned preparation method, it is preferable that in step (1), the bull quaternary ammonium salt is double end quaternary ammonium salt, three seasons
One or more in ammonium salt and four-head quaternary ammonium salt；
Preferably, the formula of double end quaternary ammonium salt is：
(CH3(CH2)xN(CH3)2(CH2)yN(CH3)2(CH2)zCH3)Br2
Wherein, x=7-20, y=2-10, z=7-20；
Preferably, the formula of tri-quaternary ammonium is：
(CH3(CH2)mN(CH3)2(CH2)nN(CH3)2(CH2)oN(CH3)2(CH2)pCH3)Br3
Wherein, m=7-20, n=2-10, o=2-10, p=7-20；
Preferably, the formula of four-head quaternary ammonium salt is：
(CH3(CH2)aN(CH3)2(CH2)bN(CH3)2(CH2)cN(CH3)2(CH2)dN(CH3)2(CH2)eCH3)Br4
Wherein, a=7-20, b=2-10, c=2-10, d=2-10, e=7-20.
In above-mentioned preparation method, it is preferable that in step (1), adding the operation of bull quaternary ammonium salt aqueous solution is：In
30-80 DEG C under vigorous stirring, adds bull quaternary ammonium salt aqueous solution, and regulation pH stirs 1h-3h after 30 DEG C of -80 DEG C of constant temperature.
In above-mentioned preparation method, it is preferable that in step (2), the SiO2-Al2O3The quality group of carrier turns into：
Al2O3Account for 70%-98%, SiO2Account for 2%-30%；Preferably, Al2O3Account for 96.4%, SiO2Account for 3.6%.
In above-mentioned preparation method, it is preferable that in step (2), GSMPs：SA：The mass ratio of water is (1-3)：(50-
90)：(2-6).
In above-mentioned preparation method, it is preferable that in step (2), the reaction temperature of the reaction is 100-150 DEG C, instead
It is 12h-48h between seasonable.
In above-mentioned preparation method, it is preferable that the temperature of the roasting is 400 DEG C -600 DEG C, time 3h-6h, gas
Atmosphere is nitrogen.
In above-mentioned preparation method, it is preferable that in step (3), the nickel salt is in nickel nitrate, nickel chloride, nickel acetate
One or more of combinations.
In above-mentioned preparation method, it is preferable that the concentration of the nickel salt solution is 0.1-0.3mol/L, and the nickel salt is molten
The amount ratio of liquid and the Mo-GSHD is (0.5-1.5) ml：1g.
In above-mentioned preparation method, it is preferable that the temperature of the roasting is 400 DEG C -600 DEG C, time 3h-6h, gas
Atmosphere is nitrogen.
In above-mentioned preparation method, it is preferable that be in step (4), the step of the presulfurization：
NiMo-GSHD is fitted into reactor, with 900h-1Volume space velocity be passed through H2, reactor is warming up to 120 DEG C -180
DEG C, to beds with 1-5h-1Volume space velocity injection 2-5wt.% sulfurized oil, make H2：The volume ratio of sulfurized oil is
300：1；
Then, the beds are warming up to 300 DEG C -380 DEG C, after keeping 4h-8h, complete the presulfurization；
Preferably, the sulfurized oil is CS2With the mixed solution of normal heptane.
The present invention also provides a kind of ultra-deep desulfurization catalyst being prepared by above-mentioned preparation method.
Metal active constituent decentralization is high in ultra-deep desulfurization catalyst provided by the present invention, and stacking degree is suitable, pole
The earth reduces the steric hindrance effect of macromolecular sulfur-containing compound, has ultra-deep desulfurization catalytic activity, surpasses available for fuel oil
Deep desulfuration reacts.
Brief description of the drawings
Fig. 1 is the TEM figures of the ultra-deep desulfurization catalyst prepared by embodiment 1.
Fig. 2 is the TEM figures of the ultra-deep desulfurization catalyst prepared by embodiment 4.
Embodiment
In order to which technical characteristic, purpose and the beneficial effect of the present invention is more clearly understood, now to the skill of the present invention
Art scheme carry out it is described further below, but it is not intended that to the present invention can practical range restriction.
Comparative example 1
This comparative example provides a kind of preparation method of desulphurization catalyst, and this method comprises the following steps：
96.4wt.%Al will be contained2O3And 3.6wt.%SiO2SiO2-Al2O3Carrier in 10MPa pressure lower sheeting into
Type, 20-40 mesh sieves are crossed, obtain carrier S A；
4.0g SA are taken, (the NH for being 0.211mol/L with 4ml concentration4)6Mo7O24·4H2The O aqueous solution impregnates, then 120 DEG C
2h is dried, the lower 500 DEG C of roastings 4h of nitrogen atmosphere, obtains oxidation state Mo base catalyst；
By Ni (NO of the above-mentioned oxidation state Mo bases catalyst using 3.4ml concentration as 0.181mol/L3)2·6H2The O aqueous solution soaks
Stain, then 120 DEG C of dry 2h, the lower 500 DEG C of roastings 4h of nitrogen atmosphere, obtain oxidation state NiMo base catalyst；
Above-mentioned oxidation state NiMo base catalyst is fitted into internal diameter 8.0mm reactors, with 900h-1Volume space velocity be passed through
H2, 150 DEG C are warming up to, to beds with 3h-1Volume space velocity injection sulfurized oil (3wt.% CS2With mixing for normal heptane
Close solution), adjust H2Flow, it is 300 to make hydrogen to oil volume ratio：1,360 DEG C, constant temperature 6h are warming up to 15 DEG C/h speed, catalysis
Agent bed is cooled to 330 DEG C, and presulfurization terminates, and obtains a kind of desulphurization catalyst, and catalyst characterization result is as shown in table 1.
The sulfurized oil of injecting catalyst bed is switched into FCC diesel oil (boiling ranges：200-395 DEG C, density：0.861g/cm3,
Sulfur content：3640 μ g/g), regulation volume space velocity to 2.0h-1, regulation hydrogen-oil ratio to 500：1, regulation pressure to 4.0MPa, start
Hydrodesulfurization reaction is carried out, after reacting 24h, device is stable, takes the sample in plant running 24-260h to carry out test sign, ties
Fruit is as shown in table 2.
Embodiment 1
A kind of preparation method of ultra-deep desulfurization catalyst is present embodiments provided, this method comprises the following steps：
By 1.04g (NH4)6Mo7O24·4H2O is dissolved in 50ml deionized waters, then molten as 2.4mol/L HCl using concentration
Liquid adjusts pH to 3.0；(the C that 20ml concentration is 0.074mol/L is added under conditions of strong agitation in 50 DEG C16H33N(CH3)2C6H12N(CH3)2C16H33)Br2Solution, the HCl solution using concentration as 2.4mol/L adjust pH to 3.0, and 50 DEG C of constant temperature stir 2h；
By the solution centrifugal, 100 DEG C of dry 6h, the Mo base presomas being connected with double end quaternary ammonium salt are obtained；
96.4wt.%Al will be contained2O3And 3.6wt.%SiO2SiO2-Al2O3Carrier in 10MPa pressure lower sheeting into
Type, 20-40 mesh sieves are crossed, obtain carrier S A；
Take the above-mentioned Mo bases presomas of 1.791g to be scattered in 70ml deionized waters, 4.0g SA are added, by the solution 120
DEG C 24h is stood, obtain GSMPs/SA, by GSMPs/SA in 120 DEG C of drys 2h, lower 500 DEG C of nitrogen atmosphere is calcined 4h, is aoxidized
State Mo base catalyst；
Ni (the NO that above-mentioned oxidation state Mo bases catalyst is 0.181mol/L with 3.4ml concentration3)2·6H2The O aqueous solution impregnates,
Then 120 DEG C of dry 2h, the lower 500 DEG C of roastings 4h of nitrogen atmosphere, obtain oxidation state NiMo base catalyst；
Above-mentioned oxidation state NiMo base catalyst is fitted into internal diameter 8.0mm reactors, with 900h-1Volume space velocity be passed through
H2, 150 DEG C are warming up to, to beds with 3h-1Volume space velocity injection sulfurized oil (3wt.% CS2With mixing for normal heptane
Close solution), adjust H2Flow, it is 300 to make hydrogen to oil volume ratio：1, it is warming up to 360 DEG C with 15 DEG C/h speed, after constant temperature 6h, urges
Agent bed is cooled to 330 DEG C, and presulfurization terminates, and obtains a kind of ultra-deep desulfurization catalyst, the TEM figure such as Fig. 1 of the catalyst
Shown, catalyst characterization result is as shown in table 1.
The sulfurized oil of injecting catalyst bed is switched into FCC diesel oil (boiling ranges：200-395 DEG C, density：0.861g/cm3,
Sulfur content：3640 μ g/g), regulation volume space velocity to 2.0h-1, regulation hydrogen-oil ratio to 500：1, regulation pressure to 4.0MPa, start
Hydrodesulfurization reaction is carried out, after reacting 24h, device is stable, takes the sample in plant running 24-260h to carry out test sign, ties
Fruit is as shown in table 2.
Embodiment 2
A kind of preparation method of ultra-deep desulfurization catalyst is present embodiments provided, this method comprises the following steps：
By 1.04g (NH4)6Mo7O24·4H2O is dissolved in 50ml deionized waters, then molten as 2.4mol/L HCl using concentration
Liquid adjusts pH to 3.0；(the C that 20ml concentration is 0.074mol/L is added under conditions of strong agitation in 80 DEG C8H17N(CH3)2C6H12N(CH3)2C8H17)Br2Solution, the HCl solution using concentration as 2.4mol/L adjust pH to 3.0, and 80 DEG C of constant temperature stir 3h；
By the solution centrifugal, 100 DEG C of dry 6h, the Mo base presomas being connected with double end quaternary ammonium salt are obtained；
96.4wt.%Al will be contained2O3And 3.6wt.%SiO2SiO2-Al2O3Carrier in 10MPa pressure lower sheeting into
Type, 20-40 mesh sieves are crossed, obtain carrier S A；
Take the above-mentioned Mo bases presomas of 1.791g to be scattered in 70ml deionized waters, 4.0g SA are added, by the solution 150
DEG C 48h is stood, obtain GSMPs/SA, by GSMPs/SA in 120 DEG C of drys 2h, lower 600 DEG C of nitrogen atmosphere is calcined 4h, is aoxidized
State Mo base catalyst；
Ni (the NO that above-mentioned oxidation state Mo bases catalyst is 0.181mol/L with 3.4ml concentration3)2·6H2The O aqueous solution impregnates,
Then 120 DEG C of dry 2h, the lower 600 DEG C of roastings 4h of nitrogen atmosphere, obtain oxidation state NiMo base catalyst；
Above-mentioned oxidation state NiMo base catalyst is fitted into internal diameter 8.0mm reactors, with 900h-1Volume space velocity be passed through
H2, 150 DEG C are warming up to, to beds with 3h-1Volume space velocity injection sulfurized oil (3wt.% CS2With mixing for normal heptane
Close solution), adjust H2Flow, it is 300 to make hydrogen to oil volume ratio：1, it is warming up to 360 DEG C with 15 DEG C/h speed, after constant temperature 6h, urges
Agent bed is cooled to 330 DEG C, and presulfurization terminates, and obtains a kind of ultra-deep desulfurization catalyst, the catalyst characterization result such as institute of table 1
Show.
The sulfurized oil of injecting catalyst bed is switched into FCC diesel oil (boiling ranges：200-395 DEG C, density：0.861g/cm3,
Sulfur content：3640 μ g/g), regulation volume space velocity to 2.0h-1, regulation hydrogen-oil ratio to 500：1, regulation pressure to 4.0MPa, start
Hydrodesulfurization reaction is carried out, after reacting 24h, device is stable, takes the sample in plant running 24-260h to carry out test sign, ties
Fruit is as shown in table 2.
Embodiment 3
A kind of preparation method of ultra-deep desulfurization catalyst is present embodiments provided, this method comprises the following steps：
By 1.04g (NH4)6Mo7O24·4H2O is dissolved in 50ml deionized waters, then molten as 2.4mol/L HCl using concentration
Liquid adjusts pH to 3.0；(the C that 20ml concentration is 0.049mol/L is added under conditions of strong agitation in 30 DEG C16H33N(CH3)2C6H12N(CH3)2C6H12N(CH3)2C16H33)Br2Solution, using concentration as 2.4mol/L HCl solution adjust pH to 2.0,30 DEG C
Constant temperature stirs 2h；By the solution centrifugal, 120 DEG C of dry 6h, the Mo base presomas being connected with double end quaternary ammonium salt are obtained；
96.4wt.%Al will be contained2O3And 3.6wt.%SiO2SiO2-Al2O3Carrier in 10MPa pressure lower sheeting into
Type, 20-40 mesh sieves are crossed, obtain carrier S A；
Take the above-mentioned Mo bases presomas of 1.791g to be scattered in 70ml deionized waters, 4.0g SA are added, by the solution 100
DEG C 12h is stood, obtain GSMPs/SA, by GSMPs/SA in 120 DEG C of drys 2h, lower 400 DEG C of nitrogen atmosphere is calcined 6h, is aoxidized
State Mo base catalyst；
Ni (the NO that above-mentioned oxidation state Mo bases catalyst is 0.181mol/L with 3.4ml concentration3)2·6H2The O aqueous solution impregnates,
Then 120 DEG C of dry 2h, the lower 500 DEG C of roastings 4h of nitrogen atmosphere, obtain oxidation state NiMo base catalyst；
Above-mentioned oxidation state NiMo base catalyst is fitted into internal diameter 8.0mm reactors, with 900h-1Volume space velocity be passed through
H2, 150 DEG C are warming up to, to beds with 3h-1Volume space velocity injection sulfurized oil (3wt.% CS2With mixing for normal heptane
Close solution), adjust H2Flow, it is 300 to make hydrogen to oil volume ratio：1, it is warming up to 360 DEG C with 15 DEG C/h speed, after constant temperature 6h, urges
Agent bed is cooled to 330 DEG C, and presulfurization terminates, and obtains a kind of ultra-deep desulfurization catalyst, the catalyst characterization result such as institute of table 1
Show.
The sulfurized oil of injecting catalyst bed is switched into FCC diesel oil (boiling ranges：200-395 DEG C, density：0.861g/cm3,
Sulfur content：3640 μ g/g), regulation volume space velocity to 2.0h-1, regulation hydrogen-oil ratio to 500：1, regulation pressure to 4.0MPa, start
Hydrodesulfurization reaction is carried out, after reacting 24h, device is stable, takes the sample in plant running 24-260h to carry out test sign, ties
Fruit is as shown in table 2.
A kind of preparation method of ultra-deep desulfurization catalyst is present embodiments provided, this method comprises the following steps：
By 1.04g (NH4)6Mo7O24·4H2O is dissolved in 50ml deionized waters, then molten as 2.4mol/L HCl using concentration
Liquid adjusts pH to 3.0；(the C that 20ml concentration is 0.074mol/L is added under conditions of strong agitation in 50 DEG C16H33N(CH3)2C6H12N(CH3)2C6H12N(CH3)2C6H12N(CH3)2C16H33)Br4Solution, the HCl solution using concentration as 2.4mol/L adjust pH
2h is stirred to 3.0,50 DEG C of constant temperature；By the solution centrifugal, 100 DEG C of dry 6h, the Mo base forerunners being connected with double end quaternary ammonium salt are obtained
Body；
96.4wt.%Al will be contained2O3And 3.6wt.%SiO2SiO2-Al2O3Carrier in 10MPa pressure lower sheeting into
Type, 20-40 mesh sieves are crossed, obtain carrier S A；
Take the above-mentioned Mo bases presomas of 1.791g to be scattered in 70ml deionized waters, 4.0g SA are added, by the solution 120
DEG C 24h is stood, obtain GSMPs/SA, by GSMPs/SA in 120 DEG C of drys 2h, lower 500 DEG C of nitrogen atmosphere is calcined 4h, is aoxidized
State Mo base catalyst；
Ni (the NO that above-mentioned oxidation state Mo bases catalyst is 0.181mol/L with 3.4ml concentration3)2·6H2The O aqueous solution impregnates,
Then 120 DEG C of dry 2h, the lower 500 DEG C of roastings 4h of nitrogen atmosphere, obtain oxidation state NiMo base catalyst；
Above-mentioned oxidation state NiMo base catalyst is fitted into internal diameter 8.0mm reactors, with 900h-1Volume space velocity be passed through
H2, 150 DEG C are warming up to, to beds with 3h-1Volume space velocity injection sulfurized oil (3wt.% CS2With mixing for normal heptane
Close solution), adjust H2Flow, it is 300 to make hydrogen to oil volume ratio：1, it is warming up to 360 DEG C with 15 DEG C/h speed, after constant temperature 6h, urges
Agent bed is cooled to 330 DEG C, and presulfurization terminates, and obtains a kind of ultra-deep desulfurization catalyst, the TEM figure such as Fig. 2 of the catalyst
Shown, catalyst characterization result is as shown in table 1.
The sulfurized oil of injecting catalyst bed is switched into FCC diesel oil (boiling ranges：200-395 DEG C, density：0.861g/cm3,
Sulfur content：3640 μ g/g), regulation volume space velocity to 2.0h-1, regulation hydrogen-oil ratio to 500：1, regulation pressure to 4.0MPa, start
Hydrodesulfurization reaction is carried out, after reacting 24h, device is stable, takes the sample in plant running 24-260h to carry out test sign, ties
Fruit is as shown in table 2.
Embodiment 5
A kind of preparation method of ultra-deep desulfurization catalyst is present embodiments provided, this method comprises the following steps：
By 1.04g (NH4)6Mo7O24·4H2O is dissolved in 50ml deionized waters, then molten as 2.4mol/L HCl using concentration
Liquid adjusts pH to 3.0；(the C that 20ml concentration is 0.074mol/L is added under conditions of strong agitation in 50 DEG C16H33N(CH3)2C6H12N(CH3)2C16H33)Br2Solution, the HCl solution using concentration as 2.4mol/L adjust pH to 3.0, and 50 DEG C of constant temperature stir 2h；
By the solution centrifugal, 100 DEG C of dry 6h, the Mo base presomas being connected with double end quaternary ammonium salt are obtained；
96.4wt.%Al will be contained2O3And 3.6wt.%SiO2SiO2-Al2O3Carrier in 10MPa pressure lower sheeting into
Type, 20-40 mesh sieves are crossed, obtain carrier S A；
Take the above-mentioned Mo bases presomas of 1.791g to be scattered in 70ml deionized waters, 4.0g SA are added, by the solution 120
DEG C 24h is stood, obtain GSMPs/SA, by GSMPs/SA in 120 DEG C of drys 2h, lower 500 DEG C of nitrogen atmosphere is calcined 4h, is aoxidized
State Mo base catalyst；
Ni (the NO that above-mentioned oxidation state Mo bases catalyst is 0.181mol/L with 3.4ml concentration3)2·6H2The O aqueous solution impregnates,
Then 120 DEG C of dry 2h, the lower 500 DEG C of roastings 4h of nitrogen atmosphere, obtain oxidation state NiMo base catalyst；
Above-mentioned oxidation state NiMo base catalyst is fitted into internal diameter 8.0mm reactors, with 900h-1Volume space velocity be passed through
H2, 150 DEG C are warming up to, to beds with 3h-1Volume space velocity injection sulfurized oil (3wt.% CS2With mixing for normal heptane
Close solution), adjust H2Flow, it is 300 to make hydrogen to oil volume ratio：1, it is warming up to 360 DEG C with 15 DEG C/h speed, after constant temperature 6h, urges
Agent bed is cooled to 330 DEG C, and presulfurization terminates, and obtains a kind of ultra-deep desulfurization catalyst, the catalyst characterization result such as institute of table 1
Show.
The sulfurized oil of injecting catalyst bed is switched into FCC gasoline (boiling range：37-198 DEG C, density：0.715g/cm3,
Sulfur content：1320 μ g/g), regulation volume space velocity to 4.0h-1, regulation hydrogen-oil ratio to 500：1, regulation pressure to 3.0MPa, start
Hydrodesulfurization reaction is carried out, after reacting 24h, device is stable, takes the sample in plant running 24-260h to carry out test sign, ties
Fruit is as shown in table 2.As it can be seen from table 1 active component MoS in the ultra-deep desulfurization catalyst being prepared by the method for the present invention2
Average length reduces, the average stacking number of plies and decentralization significantly improve.
MoS in the different catalysts of table 12Average length and average stacked layers number
| Catalyst | MoS2Average length (L)/nm of layer | MoS2The average stacking number of plies | Decentralization (fMo) |
| Comparative example 1 | 4.4 | 1.7 | 0.26 |
| Embodiment 1 | 2.7 | 3.0 | 0.40 |
| Embodiment 2 | 3.0 | 3.1 | 0.38 |
| Embodiment 3 | 2.9 | 2.9 | 0.39 |
| Embodiment 4 | 2.7 | 3.1 | 0.38 |
| Embodiment 5 | 2.7 | 3.0 | 0.40 |
Note：
Wherein, niFor MoS2The number of Mo atoms on layer side, by measuring MoS2The length (L) of layer, by formula L=3.2
(2ni- 1)/10 it is calculated；T is the MoS counted by TEM2The number of layer.
From table 2 it can be seen that the desulfurization degree for the ultra-deep desulfurization catalyst being prepared by the method for the present invention up to 99.6 with
On, it is significantly higher than conventional catalyst.
The hydrodesulfurization reaction performance of the different catalysts of table 2
| Catalyst | Feedstock oil total sulfur (μ g/g) | Product oil mean content of sulfur (μ g/g) | Desulfurization degree (%) |
| Comparative example 1 | 3640 | 138.3 | 96.2 |
| Embodiment 1 | 3640 | 9.5 | 99.7 |
| Embodiment 2 | 3640 | 14.6 | 99.6 |
| Embodiment 3 | 3640 | 9.5 | 99.7 |
| Embodiment 4 | 3640 | 14.6 | 99.6 |
| Embodiment 5 | 1320 | 2.6 | 99.8 |
Above-mentioned two embodiment shows that ultra-deep desulfurization catalyst prepared by the inventive method, its active metal component has
There are the suitable stacking number of plies and high degree of dispersion, make the catalyst that there is excellent ultra-deep desulfurization activity.
Claims (10)
1. a kind of preparation method of ultra-deep desulfurization catalyst, this method comprise the following steps：
(1) molybdate is dissolved in deionized water and obtains molybdic acid saline solution, adjust pH to 1.0-5.0；Add bull quaternary ammonium salt
The aqueous solution, adjust pH to 1.0-5.0；Centrifugation, washing, dry, obtain Mo base presomas GSMPs；
(2) GSMPs is scattered in deionized water, the SiO added after tabletting sieving2-Al2O3Carrier is reacted, and is washed, is done
It is dry to obtain GSMPs/SA, then it is calcined, obtains oxidized catalyst Mo-GSHD；
(3) Mo-GSHD is impregnated with nickel salt solution, then dries, is calcined, obtain oxidized catalyst NiMo-GSHD；
(4) by NiMo-GSHD presulfurizations, ultra-deep desulfurization catalyst is obtained.
2. preparation method as claimed in claim 1, wherein, in step (1), the molybdate is Ammonium Molybdate Tetrahydrate, seven water
Close one or more of combinations in ammonium molybdate and sodium molybdate；
Preferably, the concentration of the molybdic acid saline solution is 0.01-0.02mol/L；
Preferably, the concentration of the bull quaternary ammonium salt aqueous solution is 0.03-0.10mol/L, and addition is molybdate aqueous liquid
Long-pending 0.1-1.0 times.
3. such as the preparation method any one of claim 1-2, wherein, in step (1), the bull quaternary ammonium salt is double end
One or more of combinations in quaternary ammonium salt, tri-quaternary ammonium and four-head quaternary ammonium salt；
Preferably, the formula of double end quaternary ammonium salt is：
(CH3(CH2)xN(CH3)2(CH2)yN(CH3)2(CH2)zCH3)Br2
Wherein, x=7-20, y=2-10, z=7-20；
Preferably, the formula of tri-quaternary ammonium is：
(CH3(CH2)mN(CH3)2(CH2)nN(CH3)2(CH2)oN(CH3)2(CH2)pCH3)Br3
Wherein, m=7-20, n=2-10, o=2-10, p=7-20；
Preferably, the formula of four-head quaternary ammonium salt is：
(CH3(CH2)aN(CH3)2(CH2)bN(CH3)2(CH2)cN(CH3)2(CH2)dN(CH3)2(CH2)eCH3)Br4
Wherein, a=7-20, b=2-10, c=2-10, d=2-10, e=7-20.
4. such as the preparation method any one of claim 1-3, wherein, in step (1), add bull quaternary ammonium salt aqueous solution
Operation be：In 30 DEG C -80 DEG C under vigorous stirring, quaternary ammonium salt aqueous solution is added, regulation pH stirs after 30 DEG C of -80 DEG C of constant temperature
1h-3h。
5. such as the preparation method any one of claim 1-4, wherein, in step (2), the SiO2-Al2O3Carrier
Quality group turns into：Al2O3Account for 70%-98%, SiO2Account for 2%-30%；
Preferably, Al2O3Account for 96.4%, SiO2Account for 3.6%.
6. such as the preparation method any one of claim 1-5, wherein, in step (2), GSMPs：SA：The mass ratio of water
For (1-3)：(50-90)：(2-6).
7. such as the preparation method any one of claim 1-6, wherein, in step (2), the reaction temperature of the reaction is
100 DEG C -150 DEG C, reaction time 12h-48h；
Preferably, the temperature of the roasting is 400 DEG C -600 DEG C, and time 3h-6h, atmosphere is nitrogen.
8. such as the preparation method any one of claim 1-7, wherein, in step (3), the nickel salt is nickel nitrate, chlorine
Change one or more of combinations in nickel, nickel acetate；
Preferably, the concentration of the nickel salt solution is 0.1-0.3mol/L, the nickel salt solution and the Mo-GSHD amount ratio
For (0.5-1.5) ml：1g；
Preferably, the temperature of the roasting is 400 DEG C -600 DEG C, and time 3h-6h, atmosphere is nitrogen.
9. such as the preparation method any one of claim 1-8, wherein, it is in step (4), the step of the presulfurization：
NiMo-GSHD is fitted into reactor, with 900h-1Volume space velocity be passed through H2, reactor is warming up to 120-180 DEG C, to
Beds are with 1-5h-1Volume space velocity injection 2-5wt.% sulfurized oil, make H2：The volume ratio of sulfurized oil is 300：1；
Then, the beds are warming up to 300 DEG C -380 DEG C, after keeping 4h-8h, complete the presulfurization；
Preferably, the sulfurized oil is CS2With the mixed solution of normal heptane.
10. the ultra-deep desulfurization catalyst being prepared with the preparation method any one of claim 1-9.
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| WO2009149923A1 (en) * | 2008-06-11 | 2009-12-17 | Eni S.P.A. | Catalytic system and process for the hydroconversion of heavy oil products |
| CN102423718A (en) * | 2011-10-20 | 2012-04-25 | 中国石油大学(北京) | Preparation method for novel FCC (Fluid Catalytic Cracking) gasoline low-temperature sulfur transfer catalyst |
| CN102941125A (en) * | 2012-09-24 | 2013-02-27 | 中国石油天然气股份有限公司 | Preparation method of gasoline deep hydrodesulfurization catalytic material and catalyst |
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| CN101298047A (en) * | 2007-04-30 | 2008-11-05 | 中国石油天然气集团公司 | Preparation of hydrogenation catalyst |
| WO2009149923A1 (en) * | 2008-06-11 | 2009-12-17 | Eni S.P.A. | Catalytic system and process for the hydroconversion of heavy oil products |
| CN102423718A (en) * | 2011-10-20 | 2012-04-25 | 中国石油大学(北京) | Preparation method for novel FCC (Fluid Catalytic Cracking) gasoline low-temperature sulfur transfer catalyst |
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| CN111359629A (en) * | 2020-03-19 | 2020-07-03 | 昆明理工大学 | Metal single-atom site catalyst and preparation method and application thereof |
| CN111359629B (en) * | 2020-03-19 | 2021-04-23 | 昆明理工大学 | Metal single-atom site catalyst and preparation method and application thereof |
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