CN105694955B - A kind of method of inferior feedstock oil hydrogenation desulfurization and denitrogenation - Google Patents
A kind of method of inferior feedstock oil hydrogenation desulfurization and denitrogenation Download PDFInfo
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Abstract
The invention provides a kind of method of inferior feedstock oil hydrogenation desulfurization and denitrogenation, wherein, the method includes：Under the conditions of hydrogenation desulfurization and denitrogenation, inferior feedstock oil is contacted with hydrogen and catalyst, wherein, the catalyst includes：The hydrogenation active component element of carrier and load on this carrier, wherein, the carrier includes aluminum oxide and donut-like SBA 15.Catalyst HDS denitrification activity of the invention is high, specifically, uses carrier of the invention, only with Ni and W as metal active constituent element, desulfurization degree and denitrification percent higher can be also obtained, it can be seen that, not only activity is high to prepare catalyst using carrier of the invention, and low cost.
Description
Technical field
The present invention relates to a kind of method of inferior feedstock oil hydrogenation desulfurization and denitrogenation.
Background technology
In recent years, as crude oil heaviness is on the rise, coking vapour increasingly strict with clean fuel sulfur content statute of limitation
The quality of oil, coker gas oil, catalytic cracking diesel oil and high-sulfur straight-run diesel oil can not meet the requirement of product oil, it is impossible to directly go out
Factory, it is necessary to which high-quality petrol and diesel oil can just be produced by carrying out hydrofinishing to it.In fact, the core of Hydrofining Technology is to add
Hydrogen catalyst for refining.
Gasoline hydrogenation catalyst disclosed in CN85104438 is using high-purity alpha-alumina as carrier, using tungsten, nickel as active component,
Using fluorine as auxiliary agent.Fluorine in the catalyst is easily lost in industry park plan, and fluorine etching apparatus and pollution environment.
CN1872959A is disclosed with aluminum oxide as carrier, and nickel-loaded, molybdenum, tungsten are clean property component, and it is auxiliary agent to introduce fluorine
Hydrogenation catalyst.Compared with the hydrogenation catalyst of traditional bimetallic component, its three metal component catalyst activity for providing has
Improved, but due to reasons such as carrier properties, it improves limitation, and activity is still relatively low.Meanwhile, the catalyst also faces fluorine and exists
Be easy to run off in industry park plan and fluorine etching apparatus and pollution environment the problems such as.
CN1040610A discloses to contain TiO2γ-A12O3For the Hydrobon catalyst of carrier, its carrier catalysis
Agent γ-A12O3The content of middle titanium oxide is 5-30%, with W, Mo, Ni as active component.With TiO2Modified A12O3For carrier
The performance of hydrogenation catalyst can be improved necessarily, and carrier acid amount is relatively low, and especially middle strong acidity center is less, is unfavorable for azepine
The open loop fracture of ring, denitrification effect is not obvious.
A kind of hydrogenation catalyst with high activity is used in the petroleum hydrocarbon hydrotreating method that USP4880524 is proposed.
The catalyst is Ni-Mo/A12O3Type, specific surface area is more than 300m2/ g, the aperture less than 7nm is more than 70%.The catalyst for
Light fraction oil has the clean property of preferable hydrofinishing, but the active metal of its load is two kinds of components of Ni, Mo, with regard to the country at present
From the point of view of price, molybdenum oxide is higher than tungsten oxide price, therefore for domestic oil refining enterprises, using Ni-Mo/A12O3Type catalyst can increase
Plus production cost.
In face of new clean fuel environmental regulation requirement, traditional Hydrofining Technology is faced with formidable challenges at present.Always
Since, hydrodesulfurization attention, but this situation changes, on the one hand the processing of high nitrogen heavy oil is into trend of the times,
The presence of another aspect nitride suppresses catalyst depth hydrodesulfurization performance.The processing of China's nitrogen Crude oil from CNOOC high is in China
Occupy considerable proportion in petroleum refining industry, it is therefore desirable to develop nitrogen inferior distillate oil deep hydrodesulfurizationof catalyst high.
CN102151582B discloses a kind of high nitrogen gasoline and diesel hydrogenation desulphurization catalyst inferior, with A12O3-TiO2-SiO2Three
First oxide is complex carrier；Catalyst composition includes carrier, auxiliary agent, active metal；Active metal includes the oxygen of nickel, molybdenum and tungsten
Compound；Auxiliary agent is phosphorus；Carrier includes aluminum oxide and titanium oxide, silica；Percentage by weight of each component on the basis of catalyst
Content is：Nickel oxide accounts for 1-15wt%, and molybdenum oxide is 2-12wt%；Tungsten oxide accounts for 12-35wt%, and phosphorus pentoxide accounts for 2-
5wt%；Titanium oxide accounts for 2-15wt%；Silica accounts for 2-20wt%, and remaining is aluminum oxide；Dissolving is prepared using room temperature complexing method
The stable W-Mo-Ni-P co-impregnation liquid of performance, then supports active metal using substep saturation dipping technique on above-mentioned carrier
Component W-Mo-Ni and auxiliary agent P.The catalyst hydrodesulfurization active and hydrodenitrogenationactivity activity can be improved further.
The content of the invention
It is an object of the invention to provide a kind of side of the inferior feedstock oil hydrogenation desulfurization and denitrogenation of hydrogenation desulfurization and denitrogenation efficiency high
Method.
In order to realize object defined above, the invention provides a kind of method of inferior feedstock oil hydrogenation desulfurization and denitrogenation, wherein, should
Method includes：Under the conditions of hydrogenation desulfurization and denitrogenation, inferior feedstock oil is contacted with hydrogen and catalyst, wherein, the catalyst
Including：Carrier and load hydrogenation active component element on this carrier, wherein, the carrier includes aluminum oxide and donut-like
SBA-15。
The catalyst HDS denitrification activity of the present invention is high, specifically, using the carrier of the present invention, even if only with Ni
With W as metal active constituent element, desulfurization degree and denitrification percent higher can be also obtained, it can be seen that, using load of the invention
Body prepares catalyst, and not only activity is high, and low cost.
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.
As it was previously stated, the invention provides a kind of method of inferior feedstock oil hydrogenation desulfurization and denitrogenation, wherein, the method bag
Include：Under the conditions of hydrogenation desulfurization and denitrogenation, inferior feedstock oil is contacted with hydrogen and catalyst, wherein, the catalyst includes：Carry
Body and load hydrogenation active component element on this carrier, wherein, the carrier includes aluminum oxide and donut-like SBA-15.
Wherein, hydrogenation active component element typically exists with oxidation states in catalyst, before use, typically can be by
Catalyst carries out presulfurization, and the method for presulfurization is well known to those skilled in the art, and the present invention is not described here in detail.
Therefore, the present invention preferably catalyst is pre-sulfide catalyst.
, according to the invention it is preferred to aluminum oxide is 0.1-100 with the weight ratio of donut-like SBA-15:1, more preferably 1-
50:1, more preferably 2-10:1.
In the present invention, as long as ensureing that the carrier includes donut-like SBA-15 and the purpose of the present invention can be achieved, for
The present invention, preferably described SBA-15 is donut-like, and the internal diameter of the donut-like SBA-15 is preferably with the ratio of external diameter
0.3-0.9, more preferably 0.5-0.85；Average grain diameter is preferably 3-20 μm, more preferably 3-10 μm；Average thickness is preferably
0.1-2 μm, more preferably 1-2 μm.The various bagels that heretofore described donut-like can be had been generally acknowledged that for this area
Shape, for example, can be that the various circular or classes with opening or without opening are circular, and the internal diameter and external diameter are respectively
Circular radius where circular radius and periphery where referring to the inner circumferential of the bagel；The average thickness refers to multiple faces
The average value of the thickness of bag round SBA-15.Each donut-like SBA-15 thickness refers to each of donut-like SBA-15
The average thickness of position.The most probable pore size of the SBA-15 can be 7-10nm, preferably 8-9nm；Pore volume can be 0.5-3
Ml/g, preferably 1-2 mls/g；Specific surface area can be 600-1000 meters squared per grams, preferably 650-800 square metres/
Gram.
Donut-like SBA-15 of the present invention can be obtained by various modes, for example, be commercially available, can also
Prepared according to various methods of the prior art.
In the present invention, the carrier can be formed body, it is also possible to directly for powdered, specifically can be according to reaction formation
Determine.
Aluminum oxide and donut-like SBA-15 directly can be mixed to get by the aforementioned bearer of the present invention, then according to reaction
Form determines its form, for example, can be directly powdered, can also obtain formed body according to needing progress to be molded.
For the present invention, preferably carrier of the invention is prepared as follows：In the presence of acetic acid, by boehmite with
Donut-like SBA-15 is contacted.
, according to the invention it is preferred to acetic acid is 5-20 with the consumption weight ratio of donut-like SBA-15:100.
, according to the invention it is preferred to which described include boehmite with the donut-like SBA-15 conditions contacted：Temperature is
50-100℃。
, according to the invention it is preferred to described also include the condition that boehmite is contacted with donut-like SBA-15：Time
For 1-5h.
, according to the invention it is preferred to boehmite counts the weight ratio with donut-like SBA-15 as 0.1-100 with aluminum oxide:
1, preferably 1-50:1, more preferably 2-10:1.
The property of the donut-like SBA-15 is described in detail in the foregoing description to carrier, no longer goes to live in the household of one's in-laws on getting married herein
State.
, according to the invention it is preferred to the method for preparing carrier also includes：Material after contact is heat-treated, preferably hot place
The condition of reason includes：Temperature is 300-400 DEG C, and the time being more preferably heat-treated is 3-4h.
According to the present invention, through Overheating Treatment after, can according to need the powder after heat treatment is molded, the present invention it is right
The method of shaping is without particular/special requirement, for the present invention, it is preferable that by the solid powder after heat treatment and aqueous solution of nitric acid kneading, into
It is calcined after type, wherein, preferably the concentration of aqueous solution of nitric acid is 40-50 weight %, and nitric acid is 1 with the weight ratio of solid powder：1-
2。
And the shape of shaping can for example use extruded moulding, the present invention according to needing to carry out selection molding mode
It is not described one by one herein.
According to the present invention, the condition of the roasting can be the conventional selection of this area, and the temperature of such as roasting is preferably
500-600 DEG C, the time is preferably 2-8h, can be more preferably dried before roasting, and dry temperature can be 100-150
DEG C, the time is 1-5h.
Source of the invention to the boehmite is without particular/special requirement, for the present invention, preferably described boehmite
Alumina content be 60-80 weight %.
According to the present invention, the hydrogenation active component element can be the conventional selection of this area, for the present invention, preferably
It is selected from one or more in group VIII metallic element and vib metals element.
, according to the invention it is preferred on the basis of the gross weight of catalyst, in terms of oxide, the content of hydrogenation active component is
10-50 weight %, preferably 30-40 weight %；The content of carrier is 50-90 weight %, preferably 60-70 weight %.
It is of the invention it is a kind of preferred embodiment the hydrogenation active component element is Ni and W, more preferably urging
On the basis of the gross weight of agent, in terms of oxide, the content of Ni is 25-35 weight % for the content of 2-10 weight %, W.
The catalyst of the present invention can be obtained using conventional load dipping method such as saturation impregnation, the present invention
To this without particular/special requirement.
According to the present invention, the condition of the hydrogenation desulfurization and denitrogenation condition can be the conventional selection of this area, for this hair
It is bright, preferably include：Pressure is 5-15MPa, and temperature is 300-450 DEG C, and volume space velocity is 0.5-3h during liquid-1, hydrogen to oil volume ratio is
500-1000。
According to the present invention, the inferior feedstock oil can be the conventional selection of this area, preferably inferior former for the present invention
Nitrogen content is 2000-3000wppm in material oil, and sulfur content is 2000-3000wppm, and more preferably described inferior feedstock oil is straight run
One or more in diesel oil, coker gasoline, coker gas oil and catalytic diesel oil.
Using the carrier of the present invention, even if only with Ni and W as metal active constituent element, can also obtain higher take off
Sulphur rate and denitrification percent, it can be seen that, not only activity is high to prepare catalyst using carrier of the invention, and low cost.
The present invention is described in detail below by embodiment, but the present invention is not limited to this.
The donut-like SBA-15 that following embodiments are used according to Sun Jinyu, Zhao Dongyuan, " bagel " shape high-sequential
The synthesis of big-pore mesoporous molecular sieve SBA-15, SCI, 2000,1 (21):21~23 preparation method system
It is standby.
SBA-15 samples 1：
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 that former powder is obtained after filtering, washing, drying
Material.Gained original powder mesoporous material is calcined 24 hours for 600 DEG C in Muffle furnace, template agent is removed, donut-like is obtained mesoporous
Material SBA-15 samples 1.
SBA-15 samples 2：
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 50 grams of distilled water and 30 grams of (4mol/L) hydrochloric acid, 20 grams of DMF is added at 30 DEG C.Stirring is adding 5.5 grams just after 1 hour
Silester (TEOS, Shenyang chemical reagent work), in 50 DEG C of stirring reactions 24 hours.The mesoporous material of former powder is obtained after filtering, washing, drying
Material.Gained original powder mesoporous material is calcined 24 hours for 400 DEG C in Muffle furnace, template agent is removed, the mesoporous material of donut-like is obtained
Material SBA-15 samples 2.
SBA-15 samples 3：
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 50 DEG C.Stirring is adding 4.5 grams just after 1 hour
Silester (TEOS, Shenyang chemical reagent work), in 60 DEG C of stirring reactions 24 hours.The mesoporous material of former powder is obtained after filtering, washing, drying
Material.Gained original powder mesoporous material is calcined 24 hours for 700 DEG C in Muffle furnace, template agent is removed, the mesoporous material of donut-like is obtained
Expect SBA-15 samples 3.
Table 1 is the pore structure parameter of the SBA-15 for preparing according to the method described above.
The parameters of donut-like SBA-15 in table 1, including internal diameter and external diameter ratio, average thickness, most probable hole
Footpath, pore volume, BET specific surface area and average particulate diameter are according to Sun Jinyu, Zhao Dongyuan, " bagel " shape high-sequential large aperture
The synthesis of mesoporous molecular sieve SBA-15, SCI, 2000,1 (21):Method of testing disclosed in 21~23 is surveyed
.
Prepare embodiment 1
Boehmite (alumina content is 80 weight %), SBA-15 samples 1 are contacted with acetic acid, wherein, contact
Condition includes：Acetic acid is 5 with the weight ratio of SBA-15 samples 1:100, boehmite in terms of aluminum oxide with SBA-15 samples 1
Weight ratio is 10:1, temperature is 60 DEG C, and the time is 3h, and the material after contact is heat-treated, and the temperature of heat treatment is 300
DEG C, the time is 4h, and the solid powder being thermally treated resulting in and aqueous solution of nitric acid (concentration is 45 weight %) then are carried out into kneading, institute
Plus nitric acid and the part by weight of solid powder are 1：1.6, extruded moulding, 120 DEG C of dryings 2 hours, 550 DEG C are calcined 4 hours, obtain
Carrier A.
Prepare embodiment 2
Boehmite (alumina content is 60 weight %), SBA-15 samples 2 are contacted with acetic acid, wherein, contact
Condition includes：Acetic acid is 10 with the weight ratio of SBA-15 samples 1:100, boehmite in terms of aluminum oxide with SBA-15 samples 1
Weight ratio be 6:1, temperature is 80 DEG C, and the time is 2h, and the material after contact is heat-treated, and the temperature of heat treatment is 400
DEG C, the time is 3h, and the solid powder that then will be thermally treated resulting in carries out kneading, institute with aqueous solution of nitric acid (concentration is 45 weight %)
Plus nitric acid and the part by weight of solid powder are 1：1.6, extruded moulding, 120 DEG C of dryings 2 hours, 550 DEG C are calcined 4 hours, obtain
Carrier B.
Prepare embodiment 3
Boehmite (alumina content is 70 weight %), SBA-15 samples 3 are contacted with acetic acid, wherein, contact
Condition includes：Acetic acid is 20 with the weight ratio of SBA-15 samples 1:100, boehmite in terms of aluminum oxide with SBA-15 samples 1
Weight ratio be 2:1, temperature is 100 DEG C, and the time is 1h, and the material after contact is heat-treated, and the temperature of heat treatment is 350
DEG C, the time is 3.5h, and the subsequently heat-treated solid powder for obtaining carries out kneading, institute with aqueous solution of nitric acid (concentration is 45 weight %)
Plus the part by weight of nitric acid and solid powder is 1：1.6, extruded moulding, 120 DEG C of dryings 2 hours, 550 DEG C are calcined 4 hours, obtain
Support C.
Prepare embodiment 4
According to the method for preparing embodiment 3, unlike, acetic acid is 50 with the weight ratio of SBA-15 samples 3:100, remaining
Condition all same, obtains carrier D.
Prepare embodiment 5
According to prepare embodiment 3 method, unlike, boehmite in terms of aluminum oxide with the weight of SBA-15 samples 3
Amount is than being 0.1:1, remaining condition all same obtains carrier E.
Prepare embodiment 6
Method according to embodiment 3 is prepared, unlike, by boehmite (alumina content be 70 weight %),
The temperature that SBA-15 samples 3 are contacted with acetic acid is 120 DEG C, and remaining condition all same obtains carrier F.
Prepare embodiment 7
Method according to embodiment 3 is prepared, unlike, the temperature of heat treatment is 480 DEG C, and remaining condition all same is obtained
To carrier G.
Prepare embodiment 8
Method according to embodiment 3 is prepared, unlike, after boehmite is mixed with SBA-15 samples 3, dry
To solid powder, kneading, shaping etc. then are carried out according to the method for preparing embodiment 3, obtain carrier H.
Prepare embodiment 9
After alumina powder (SB powder, German CONDEA companies production) is mixed with SBA-15 samples 3, according to preparation embodiment
3 method carries out kneading, shaping etc., obtains carrier I.
Prepare embodiment 10
Method according to embodiment 3 is prepared, unlike, boehmite is used into alumina powder (SB powder, Germany
CONDEA companies produce) replace, remaining condition all same obtains carrier J.
Embodiment 1-10
The maceration extract room temperature immersion 4 hours of carrier A-J tungstenics, nickel, 120 DEG C of dryings 6 hours, 450 DEG C are calcined 4 hours,
(wherein, NiO contents are 5 weight %, WO to obtain catalyst C1-C103Content is 30 weight %, and remaining is carrier).
Comparative example 1-2
Alumina powder and SBA-15 samples 3 are each obtained into shaped alumina according to the method kneading of preparation embodiment 3, shaping
Alumina supporter, is molded SBA-15 carriers；
Method according to embodiment 1-10 uses foregoing shaped alumina alumina supporter, and shaping SBA-15 carriers each prepare catalysis
(wherein, NiO contents are 5 weight %, WO to agent D1-D23Content is 30 weight %, and remaining is carrier).
Test case
Hydrogenation reaction performance of the catalyst for nitrogen inferior distillate oil high that this test case explanation present invention is provided.
(sulfur content is 2308.6wppm to the evaluation feedstock oil for using, and nitrogen content is 2739.3wppm, bromine index
It is 18200mgBr/100g) by the high-sulfur nitrogen inferior distillate oil miscella high of refinery of CNOOC offer.The feedstock oil belongs to high
The naphthene base crude oil of sulphur nitrogen high, is mixed by straight-run diesel oil, catalytic diesel oil, coker gasoline and coker gas oil.
Hydrogenation reaction performance is carried out to catalyst C1-C10 and D1-D2 using the fixed bed hydrogenation device of 200mL respectively
Evaluate.
Presulfiding of catalyst condition:Using containing 3wt%CS2Boat coal, with air speed 1.0h-1, hydrogen to oil volume ratio 500：1,
Under the operating pressure of 8.0MPa, presulfurization is carried out to catalyst.
Pre-vulcanization process is as follows：
Enter presulfurization oil at 120 DEG C, after oil-feed 2h, constant temperature vulcanization 2h；Start to warm up, 150 DEG C be warming up to 15 DEG C/h,
Constant temperature vulcanizes 4h；230 DEG C, constant temperature vulcanization 10h are warming up to 6 DEG C/h；290 DEG C, constant temperature vulcanization 6h are warming up to 6 DEG C/h；With 10
DEG C/h is warming up to 340 DEG C, constant temperature vulcanization 6h；200 DEG C are finally naturally cooling to, presulfurization terminates.
Hydrogenation reaction evaluation response condition is：Operating pressure 8.0MPa, 300 DEG C of reaction temperature, hydrogen to oil volume ratio 600：1,
Volume space velocity is 1.5h-1, evaluation result is shown in Table 2.
Table 2
| Catalyst source | Catalyst is numbered | Bearer number | Desulfurization degree, % | Denitrification percent, % |
| Embodiment 1 | C1 | A | 98.2 | 97.6 |
| Embodiment 2 | C2 | B | 97.5 | 97.5 |
| Embodiment 3 | C3 | C | 98.3 | 97.8 |
| Embodiment 4 | C4 | D | 95.7 | 95.8 |
| Embodiment 5 | C5 | E | 95.5 | 95.3 |
| Embodiment 6 | C6 | F | 94.8 | 95.0 |
| Embodiment 7 | C7 | G | 95.3 | 95.2 |
| Embodiment 8 | C8 | H | 94.2 | 94.8 |
| Embodiment 9 | C9 | I | 93.5 | 93.9 |
| Embodiment 10 | C10 | J | 92.8 | 92.7 |
| Comparative example 1 | D1 | Shaped alumina alumina supporter | 86.7 | 83.5 |
| Comparative example 2 | D2 | Shaping SBA-15 carriers | 52.6 | 53.9 |
Ni, W are used only as active metal component element using the carrier of the present invention it can be seen from the result of table 2,
Result in high desulfurization degree and denitrification percent.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in range of the technology design of the invention, various 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.
Additionally, can also be combined between a variety of implementation methods of the invention, 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 (12)
1. a kind of method of inferior feedstock oil hydrogenation desulfurization and denitrogenation, wherein, the method includes：Under the conditions of hydrogenation desulfurization and denitrogenation,
Inferior feedstock oil is contacted with hydrogen and catalyst, wherein, the catalyst includes：The hydrogenation of carrier and load on this carrier
Active component element, wherein, the carrier includes aluminum oxide and donut-like SBA-15, wherein, the carrier is as follows
Prepare：In the presence of acetic acid, boehmite is contacted with donut-like SBA-15, it is described by boehmite and donut-like
The condition of SBA-15 contacts includes：Acetic acid is 5-20 with donut-like SBA-15 consumption weight ratio:100, temperature is 50-100
DEG C, the time is 1-5h；Boehmite counts the weight ratio with donut-like SBA-15 as 0.1-100 with aluminum oxide:1.
2. according to the method described in claim 1, wherein, the internal diameter of the donut-like SBA-15 and the ratio of external diameter are 0.3-
0.9, average thickness is 0.1-2 μm of micron, and most probable pore size is 7-10nm, and pore volume is 0.5-3 mls/g, and specific surface area is
600-1000 meters squared per grams, average grain diameter is 3-20 μm.
3. method according to claim 1, wherein, the method for preparing the carrier also includes：By boehmite and face
Material after bag round SBA-15 contacts is heat-treated, by the solid powder after heat treatment and aqueous solution of nitric acid kneading, shaping
After be calcined, wherein, the condition of heat treatment includes：Temperature is 300-400 DEG C, and the time is 3-4h；The concentration of aqueous solution of nitric acid is 40-
The weight ratio of 50 weight %, nitric acid and solid powder is 1：1-2.
4. according to the method described in claim 1, wherein, weight of the boehmite in terms of aluminum oxide with donut-like SBA-15
Than for 1-50:1.
5. method according to claim 4, wherein, weight of the boehmite in terms of aluminum oxide with donut-like SBA-15
Than being 2-10:1.
6. method according to claim 1 and 2, wherein, the hydrogenation active component element is selected from group VIII metal
One or more in element and vib metals element.
7. method according to claim 6, wherein, on the basis of the gross weight of catalyst, in terms of oxide, hydrogenation activity group
The content divided is 10-50 weight %；The content of carrier is 50-90 weight %.
8. method according to claim 7, wherein, on the basis of the gross weight of catalyst, in terms of oxide, hydrogenation activity group
The content divided is 30-40 weight %；The content of carrier is 60-70 weight %.
9. method according to claim 1 and 2, wherein, the hydrogenation active component element is Ni and W, with catalyst
On the basis of gross weight, in terms of oxide, Ni content is that 2-10 weight %, W content are 25-35 weight %.
10. method according to claim 1 and 2, wherein, the hydrogenation desulfurization and denitrogenation condition includes：Pressure is 5-
15MPa, temperature is 300-450 DEG C, and volume space velocity is 0.5-3h during liquid-1, hydrogen to oil volume ratio is 500-1000.
11. method according to claim 1 or 2, wherein, nitrogen content is 2000-3000wppm in the inferior feedstock oil,
Sulfur content is 2000-3000wppm.
12. methods according to claim 11, wherein, the inferior feedstock oil is straight-run diesel oil, coker gasoline, coking bavin
One or more in oil and catalytic diesel oil.
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| CN101590424A (en) * | 2008-05-29 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | A kind of catalyst used for hydrogenation of distilled oil fraction and preparation method thereof |
| CN103055952A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Residual oil hydrotreating catalyst supporter and preparation method thereof |
| CN103285903A (en) * | 2012-02-29 | 2013-09-11 | 北京安耐吉能源工程技术有限公司 | Hydrogenation catalyst, and preparation method and application thereof |
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| CN101590424A (en) * | 2008-05-29 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | A kind of catalyst used for hydrogenation of distilled oil fraction and preparation method thereof |
| CN103055952A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Residual oil hydrotreating catalyst supporter and preparation method thereof |
| CN103285903A (en) * | 2012-02-29 | 2013-09-11 | 北京安耐吉能源工程技术有限公司 | Hydrogenation catalyst, and preparation method and application thereof |
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