CN105709761B - A kind of method for preparing hydrotreating catalyst - Google Patents
A kind of method for preparing hydrotreating catalyst Download PDFInfo
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- CN105709761B CN105709761B CN201410714720.4A CN201410714720A CN105709761B CN 105709761 B CN105709761 B CN 105709761B CN 201410714720 A CN201410714720 A CN 201410714720A CN 105709761 B CN105709761 B CN 105709761B
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Abstract
The invention discloses a kind of method for preparing hydrotreating catalyst.This method includes：Siliceous and the preparation of the alumina-based supports of boron and the load of hydrogenation active metals, the wherein siliceous and preparation process of the alumina-based supports of boron includes water-soluble silicon oil and soluble boron-containing compound sequentially or simultaneously introducing alumina-based supports, after Overheating Treatment, the siliceous and alumina-based supports of boron are made.This method can adjust the distribution of acid centre and hydrogenation sites, make its mutually coordinated effect, improve the combination property of hydrotreating catalyst.
Description
Technical field
It is particularly a kind of to be suitable at heavy distillate hydrogenation the present invention relates to a kind of preparation method of hydrotreating catalyst
Manage the preparation method of catalyst.
Background technology
Loaded catalyst is most to be prepared using infusion process, such as various hydrogenation catalysts.Aluminum oxide is urged frequently as such
The carrier material of agent.But pure Al2O3The interaction force of active metal and carrier on surface is larger, is easily formed inactive
Species（Such as form nickel aluminate）, it is not easy complete cure and forms the II type activity phase with high hydrogenation activity.Meanwhile catalyst
The activity of surface acidity confrontation hydrogenation catalyst has considerable influence, removes the hetero atom in raw material, it is necessary to which catalyst has hydrogenolysis
Activity, this is occurred on the acid centre of catalyst, therefore, how to be weakened the strong interaction of metal and carrier, how to be made
Catalyst has suitable acidity, turns into the key of high-activity hydrogenation catalyst preparation.A lot of properties of catalyst are by carrier
Determine, thus it is one of key factor for developing catalyst to develop suitable carrier.
At present, the method being modified to alumina support is a lot, wherein introduce auxiliary agent such as silicon, phosphorus, fluorine, boron, zirconium,
Titanium, magnesium, gallium, vanadium, manganese, copper, zinc etc., it can be used for improving the property of alumina support, but due to introducing dosage, the species of auxiliary agent
It is different with mode, the property of alumina support can be made different, or even difference is very big.
CN00110018.1 discloses a kind of hydrogenation catalyst and preparation method thereof, and the catalyst is with group VIB and VIII race
Metal is hydrogenation active component, and auxiliary agent is fluorine, while supports one kind in boron, silicon, phosphorus, magnesium, titanium, zirconium, gallium or it is mixed into and helped
Agent, its key problem in technology are prepared using coprecipitation.
CN200910236166.2 discloses a kind of preparation method of catalyst for hydrorefining pertroleum wax.This method includes：
Boehmite is weighed, adds 6%~17% silicon-containing compound and 2%~20% organic phosphorus compound solution, is being squeezed
Extruded moulding on bar machine, through drying and being calcined, the siliceous and γ-Al of phosphorus are made2O3Carrier；Silicon-containing compound is SiO2Weight is dense
The Ludox or nano silicon of degree 30%.
Above-mentioned prior art adds auxiliary agent with coprecipitation or in shaping, and the former can cause the auxiliary agents such as active metal and Si
Enter body phase in coprecipitation process, and many kinds of substance precipitates simultaneously, and identical deposition condition can not possibly be a variety of things simultaneously
The optimal deposition condition of matter, and the acid adjustment effect of formation and catalyst of the auxiliary agent to active metal activity phase does not have
Selectivity, so as to influence the combination property of final catalyst；And the latter adds the auxiliary agents such as Si in kneading and compacting, it is unfavorable for auxiliary agent
Dispersed, not only the utilization rate of auxiliary agent reduces, and the acid and active equal comprehensive adjustment effect to catalyst compared with
It is weak, it is unfavorable for the raising of catalyst combination property.
The content of the invention
For the deficiencies in the prior art, the present invention provides a kind of method for preparing hydrotreating catalyst.The party
The siliceous and alumina-based supports of boron modification that hydrotreating catalyst prepared by method uses, by the thing for improving catalyst carrier
Change property, be allowed to be more beneficial for the carrier as hydrogenation catalyst, there is higher add with the hydrotreating catalyst of its preparation
Hydrogen denitrification activity, especially suitable for catalyst for hydro-processing heavy distillate.
The preparation method of hydrotreating catalyst provided by the invention, including the siliceous and alumina-based supports of boron systems
It is standby, using infusion process load hydrogenation active metal component, through dry and roasting, obtain hydrotreating catalyst, wherein it is siliceous and
The preparation method of the alumina-based supports of boron, including：Water-soluble silicon oil and soluble boron-containing compound are sequentially or simultaneously introduced
Alumina-based supports, after Overheating Treatment, the siliceous and alumina-based supports of boron are made.
In the inventive method, the silicone content being introduced into by water-soluble silicon oil in carrier accounts for modified oxidized aluminium base in terms of silica
The 0.1%~5.0% of vehicle weight, preferably 0.2%~2.0%, more preferably 0.2% ~ 0.9%.
In the inventive method, the Boron contents being introduced into by soluble boron-containing compound in carrier account for modification in terms of diboron trioxide
The 0.1%~10.0% of alumina-based supports weight, preferably 0.3%~6.0%, more preferably 0.5% ~ 3.0%.
In the inventive method, the dosage of water-soluble silicon oil and soluble boron-containing compound is introduced respectively with silica and oxidation
The mol ratio of boron meter is 0.02 ~ 40.0, preferably 0.04 ~ 10.0, more preferably 0.1 ~ 2.0.
Water-soluble silicon oil described in the inventive method, refers to the silicone oil that can be dissolved in water, and preferred property is as follows：It is viscous at 25 DEG C
It is 30 ~ 100 DEG C, preferably 40 ~ 65 DEG C to spend for 200 ~ 7000mPa.s, preferably 500 ~ 5000mPa.s, cloud point.Described is water-soluble
Property silicone oil be usually to be obtained using the method for group modified silicone oil, such as polyether modified silicon oil.
Alumina-based supports of the present invention refer to using aluminum oxide as key component, can be free of adjuvant component, also may be used
So that containing adjuvant component, wherein adjuvant component can be the one or more in fluorine, silicon, phosphorus, titanium, zirconium, boron etc., and adjuvant component is in oxygen
Change the content in alumina-based support in below 30wt%, preferably below 20wt%, more preferably below 15wt%.Institute in the present invention
Alumina-based supports are aluminium hydroxide（Such as boehmite）Obtained after high-temperature roasting, the condition of high-temperature roasting
It is as follows：1.0h~20.0h, the h of preferably 3.0 h ~ 8.0 are calcined at 450 DEG C~1000 DEG C.Described alumina-based supports can be with
Prepared using conventional method, according to the needs of practical application, shaping carrier can be made, i.e., again through height after aluminium hydroxide is molded
Temperature roasting obtains alumina-based supports.Spherical, bar shaped can be made as needed for the shape of carrier（Such as clover, bunge bedstraw herb
Or cylindrical bars）Etc. suitable shape, conventional shaping assistant, such as extrusion aid, peptization acid, adhesive can be added in forming process
Deng.The property of the alumina-based supports is as follows：Specific surface area is 120 ~ 420m2/ g, preferably 220 ~ 320m2/g；Pore volume is
0.4 ~ 1.3mL/g, preferably 0.6 ~ 1.0mL/g；Pore volume shared by hole of the bore dia less than 4nm accounts for less than the 20% of total pore volume, excellent
Choosing accounts for less than 10%, more preferably less than 5%.
In the inventive method, soluble boron-containing compound refers to one kind or several in boric acid, ammonium pentaborate, tetraboric acid ammonium etc.
The combination of kind.
In the inventive method, water-soluble silicon oil and soluble boron-containing compound are simultaneously or successively incorporated on carrier, you can
First water-soluble silicon oil is incorporated on carrier, then soluble boron-containing compound is incorporated on carrier again；Or by water solubility
Silicone oil and soluble boron-containing compound are incorporated on carrier simultaneously, and its incorporation way uses infusion process, and infusion process can wait body
Product dipping or excessive dipping；Can be multiple dipping or single-steeping.To improve efficiency, preferably use
Once isometric co-impregnation.
In the inventive method, using two sections of heat treatments, first paragraph is 60 DEG C~150 DEG C in temperature, excellent for described heat treatment
Elect 90 DEG C~120 DEG C as, processing time is 0.5h~20.0h, preferably 1.0h~6.0h, second segment temperature be 180 DEG C~
400 DEG C, preferably 200 DEG C~350 DEG C, processing time is 0.5h~20.0h, preferably 1.0h~6.0h.Heat treatment can be
Carried out in oxygen-containing atmosphere, oxygen concentration is not particularly limited, such as air atmosphere, can also carried out in an inert atmosphere, than
Such as nitrogen atmosphere.
Hydrogenation active metal component described in the inventive method is the active metal component that hydrotreating catalyst is commonly used,
One or more generally in vib metals and group VIII metal, wherein vib metals are preferably W and/or Mo,
Group VIII metal is preferably Co and/or Ni.
Hydrotreating catalyst prepared by the inventive method, on the basis of the weight of catalyst, modified oxidized alumina-based support
Content be 55.0wt% ~ 94.5wt%, preferably 58.0wt% ~ 90.0wt%, vib metals oxide content is
5.0wt% ~ 30.0wt%, preferably 8.0wt% ~ 30.0wt%, group VIII metal oxide content are 0.5wt% ~ 15.0
The wt% of wt%, preferably 2.0 wt% ~ 12.0.
In hydrotreating catalyst preparation method of the present invention, hydrogenation active metal component is to support carrier by infusion process
On, it can be incipient impregnation or excessive dipping, can be step impregnation or co-impregnation, be preferably isometric
Co-impregnation.Dipping method is well-known to those skilled in the art.After hydrogenation active metal component solution impregnating carrier, through dry
Final catalyst is made in dry and roasting.Method for preparing catalyst is known to technical staff.Dipping solution is by using containing the VIth B
Prepared by the compound of race or group VIII metal, its solution concentration can be adjusted by the dosage of each compound, refer to so as to prepare
Determine the catalyst of active component content, the compound method of solution is known to those skilled in the art.With containing active metal component
Aqueous solution dipping said catalyst carrier, by drying and calcination stepses after dipping.The condition of the drying and roasting is
Conventional, for example, drying temperature is 60 DEG C~200 DEG C, preferably 90 DEG C~160 DEG C, drying time is 0.5h~20h, preferably
For 1h~6h；Sintering temperature is 300 DEG C~700 DEG C, and preferably 300 DEG C~500 DEG C, roasting time is 0.5h~20h, is preferably
1h~6h.
The siliceous and alumina-based supports of boron used by the inventive method, with a small amount of specific water-soluble silicon oil-impregnated
Alumina-based supports, the effect using the hydrophilic and hydrophobic grouping of water-soluble silicon oil make it load to alumina-based supports surface
On ad-hoc location, and make while or the boron-containing compound that impregnates afterwards evenly spread to around silica group, pass through suitable heat
Processing, the more preferable coordinative role of Si, B energy loaded, forms the silicon hydroxyl being more evenly distributed in carrier surface ad-hoc location
Base is engaged with boron, carrier surface is formed more acid suitable acid centres, and with the ortho acid of carrier surface
Property position be engaged, make the acidity of carrier and acid distribution more reasonable, on the other hand, be advantageous to adjust the activity gold subsequently loaded
Belong to the distribution of the hydrogenation sites formed, and the cooperation of the acid centre of hydrogenation sites and carrier surface, from
And improve the performance of catalyst.
The hydrogenation removing impurities matter of hydrotreating catalyst prepared by the inventive method especially suitable for heavy distillate（As sulphur,
Nitrogen etc.）Catalyst, especially hydrodenitrogenationactivity activity increase rate are larger.
Embodiment
In the present invention, cloud point refers to stop after the water-soluble silicon oil solution that mass concentration is 1% is heated into muddiness
Heating, stir temperature when the lower observation aqueous solution becomes limpid by muddiness.
According to the preparation method of modified oxidized alumina-based support provided by the invention, it can specifically use following steps：
1st, soluble boron-containing compound is configured to solution A, wherein boron-containing compound concentration is calculated as 0.1g/ with boron oxide
100mL~20g/100mL；
2nd, water-soluble silicon oil is configured to solution B, wherein water-soluble silicon oil concentration with silica be calculated as 0.1g/100mL ~
20g/100mL；
3rd, soluble boron-containing compound and water-soluble silicon oil are hybridly prepared into solution C, wherein boron-containing compound concentration with
Boron oxide is calculated as 0.1g/100mL ~ 10g/100mL, and water-soluble silicon oil concentration is calculated as 0.1g/100mL ~ 10g/ with silica
100mL；
4th, water-soluble silicon oil and boron-containing compound are guided in alumina-based supports using a kind of at least following mode：
I, with solution C oxide impregnation alumina-based support, after health, by two sections of heat treatments, modified aluminas base load is obtained
Body；In wherein two sections heat treatments, first paragraph is 60 DEG C~150 DEG C in temperature, and preferably 90 DEG C~120 DEG C, processing time is
0.5h~20.0h, preferably 1.0h~6.0h, second segment are 180 DEG C~400 DEG C in temperature, preferably 200 DEG C~350 DEG C, are located
The reason time is 0.5h~20.0h, preferably 1.0h~6.0h；
II, with solution B oxide impregnation alumina-based support, after health, pass through Low Temperature Heat Treatment, then dipping solution A, health
Afterwards, by two sections of heat treatments, modified oxidized alumina-based support is obtained；Wherein Low Temperature Heat Treatment be 60 DEG C~150 DEG C, preferably 90
DEG C~120 DEG C, processing time is 0.5h~20.0h, preferably 1.0h~6.0h；In two sections of heat treatments, first paragraph is in temperature
60 DEG C~150 DEG C, preferably 90 DEG C~120 DEG C, processing time is 0.5h~20.0h, preferably 1.0h~6.0h, and second segment exists
Temperature is 180 DEG C~400 DEG C, and preferably 200 DEG C~350 DEG C, processing time is 0.5h~20.0h, preferably 1.0h~6.0h.
In the inventive method, heat treatment can be carried out in oxygen-containing atmosphere, oxygen concentration is not particularly limited, such as air
Atmosphere etc., it can also carry out in an inert atmosphere, such as nitrogen atmosphere etc..
The inventive method is not specifically limited to the conditioned time after dipping solution, and conditioned time is to can guarantee that water-soluble silicon
Oil and the uniform adsorption of boron-containing compound component are defined, and those skilled in the art can be according to the viscosity situation of solution and the suction of solution
Attached situation is judged, to determine conditioned time.
The technical scheme that the invention is further illustrated by the following examples, but invention should not be deemed limited to this reality
Apply in example.In the present invention, wt% is mass fraction, no specified otherwise, is air atmosphere.
In the present invention, the sulfur content S in feedstock oil and hydrotreatment products（wt%）Using ultraviolet fluorescence method（SH/T
0689-2000）Measure, nitrogen content N（µg/g）Using boat sample introduction chemoluminescence method（SH/T 0704-2001）Measure.
In the embodiment of the present invention and comparative example, the hydrodesulfurization activity of catalyst is pressed by 1.7 grades of calculating, hydrodenitrogenationactivity activity
1 grade of calculating, sulfur content unit when hydrodesulfurization activity calculates are μ g/g, and nitrogen content unit when hydrodenitrogenationactivity activity calculates is
μ g/g, circular are as follows：
Hydrodesulfurization activity=1/ (sulfur content in product)0.7- 1/ (sulfur content in raw material)0.7
Hydrodenitrogenationactivity activity=ln [nitrogen content in nitrogen content/product in feedstock oil]
The relative hydrodesulfurization activity of the catalyst of embodiment and comparative example and relative hydrodenitrogenationactivity activity in the present invention,
It is that reference, catalyst DCAT6 relative hydrodesulfurization are used as using catalyst DCAT6 hydrodesulfurization activity and hydrodenitrogenationactivity activity
Activity is designated as 100%, and catalyst DCAT6 relative hydrodenitrogenationactivity activity is designated as 100%；
The relative hydrodesulfurization activity of other catalyst is：
（The hydrodesulfurization activity ÷ catalyst DCAT6 of catalyst hydrodesulfurization activity）×100%；
The relative denitrification activity of other catalyst is：
（The hydrodenitrogenationactivity activity ÷ catalyst DCAT6 of catalyst hydrodenitrogenationactivity activity）×100%.
In embodiment, water-soluble silicon oil A used is produced by the industrial organosilicon new material company in Qingdao, SiO2Content is
15wt%, viscosity（25℃）1500 ~ 5000 mPa.s, cloud point are 47 DEG C；Water-soluble silicon oil B is by Laiyang Shunming Chemical Co., Ltd
Production, SiO2Content is 9wt%, viscosity（25℃）For 500~1500mPa.s, cloud point is 45~55 DEG C；Water-soluble silicon oil C is by Lay
Yang Shengbang organosilicons Science and Technology Ltd. produces, SiO2Content is 30wt%, viscosity（25℃）For 600~5000mPa.s, cloud point
For 42~46 DEG C.
The pore structure of aluminum hydroxide solid elastomer powder used is as shown in table 1 in embodiment and comparative example：
The pore structure of aluminum hydroxide solid elastomer powder used in the embodiment of table 1 and comparative example
| Project | SB powder | Macropore aluminum hydroxide solid elastomer powder |
| Specific surface area, m2/g | 239 | 316 |
| Pore volume, mL/g | 0.53 | 1.18 |
| Pore size distribution, % | ||
| ＜ 4nm | 4.4 | 1.0 |
| 4~8nm | 78.5 | 14.6 |
| 8~15nm | 15.3 | 34.1 |
| ＞ 15nm | 1.8 | 50.3 |
Embodiment 1
Macropore aluminum hydroxide solid elastomer powder 3800g, SB powder 200g is taken, adds citric acid and each 160g of sesbania powder, is well mixed.
Then diluted nitric acid aqueous solution 2900g is uniformly added into, wherein concentration of nitric acid is 2.9wt%.By material kneading 15min, then roll
20min, with diameter 1.7mm clover orifice plate extrusion.500 DEG C of roasting 4h after 120 DEG C of dry 4h.Carrier after roasting is designated as
Z。
Alumina support Z physico-chemical property is as shown in table 2：
The alumina support Z of table 2 physico-chemical property
| Project | Alumina support Z |
| Specific surface area, m2/g | 293 |
| Pore volume, mL/g | 0.66 |
| Pore size distribution, % | |
| ＜ 4nm | 3.1 |
| 4~8nm | 60.9 |
| 8~15nm | 31.7 |
| ＞ 15nm | 4.3 |
| Infrared total acid, mmol/g | 0.409 |
| Bulk density, g/100mL | 62 |
| Saturation liquid absorption, mL/100g | 78 |
Embodiment 2
Tetraboric acid ammonium 7.5g is weighed, adds appropriate amount of deionized water dissolving, it is 105mL, obtained solution A1 to make volume.Weigh water
Dissolubility silicone oil A 16.5g, appropriate amount of deionized water dissolving is added, it is 105mL, obtained solution B1 to make volume., will under stirring
35mL B1 solution is poured slowly into 35mL A1 solution, and adds appropriate amount of deionized water, and it is 78mL to make final volume, is configured to C1
Solution.
Take 100g alumina support Z, by solution C 1 uniformly sprinkling on the alumina support, after health 10 hours, through 105 DEG C
3h is heat-treated, 230 DEG C of heat treatment 2h, obtains modified carrier S 1.
35mL solution Bs 1 are diluted to 78mL with deionized water, are uniformly sprayed on alumina support Z, health 10 hours,
76mL is diluted to deionized water after 100 DEG C are heat-treated 2h, then by 35mL A1 solution, is uniformly sprayed on this carrier, health
After 3 hours, through 105 DEG C of heat treatment 3h, 230 DEG C of heat treatment 2h, modified carrier S 2 is obtained.
Distinguish incipient impregnation S1, S2 with the maceration extract containing Mo, Ni, P, through 120 DEG C of dry 3h, after 450 DEG C are calcined 2h, obtain
The catalyst obtained is designated as CAT1 and CAT2 respectively.
Embodiment 3
Boric acid 1.8g, water-soluble silicon oil B 16.0g are weighed, adds appropriate amount of deionized water dissolving, it is 78mL to make volume, is made
Solution C 2.
Take 100g alumina support Z, by solution C 2 uniformly sprinkling on the alumina support, after health 10 hours, through 100 DEG C
2h is heat-treated, 220 DEG C of heat treatment 2h, obtains modified carrier S 3.
Tetraboric acid ammonium 1.7g, boric acid 1.8g, water-soluble silicon oil B 16.0g are weighed, appropriate amount of deionized water dissolving is added, makes body
Product is 78mL, obtained solution C3.
Take 100g alumina support Z, by solution C 3 uniformly sprinkling on the alumina support, after health 10 hours, in nitrogen
Under atmosphere, through 100 DEG C of heat treatment 2h, 350 DEG C of heat treatment 2h, modified carrier S 4 is obtained.
Distinguish incipient impregnation S3 and S4 with the maceration extract containing Mo, Ni, P, through 120 DEG C of drys 3h, after 450 DEG C are calcined 2h,
The catalyst of acquisition is designated as CAT3 and CAT4 respectively.
Embodiment 4
Boric acid 1.8g, water-soluble silicon oil C 1.7g are weighed, adds appropriate amount of deionized water dissolving, it is 78mL to make volume, is made
Solution C 3.
Take 100g alumina support Z, by solution C 3 uniformly sprinkling on the alumina support, after health 10 hours, through 110 DEG C
2h is heat-treated, 260 DEG C of heat treatment 3h, obtains modified carrier S 5.
With the maceration extract incipient impregnation S5 containing Mo, Ni, P, through 120 DEG C of dry 3h, after 450 DEG C are calcined 2h, acquisition is urged
Agent is designated as CAT5 respectively.
Embodiment 5
Ammonium pentaborate 6.8g, the g of water-soluble silicon oil C 9.0 are weighed, adds appropriate amount of deionized water dissolving, it is 78mL to make volume,
Obtained solution C4.
Take 100g alumina support Z, by solution C 4 uniformly sprinkling on the alumina support, after health 10 hours, through 110 DEG C
2h is heat-treated, 260 DEG C of heat treatment 3h, obtains modified carrier S 6.
With the maceration extract incipient impregnation S6 containing Mo, Ni, P, through 120 DEG C of dry 3h, after 450 DEG C are calcined 2h, acquisition is urged
Agent is designated as CAT6 respectively.
Comparative example 1
Macropore aluminum hydroxide solid elastomer powder 190g, SB powder 10g is taken, adds citric acid and each 8g of sesbania powder, is well mixed.Weigh
Water-soluble silicon oil B 24.0g, tetraboric acid ammonium 2.6g, boric acid 2.7g, then add in aqueous solution of nitric acid, after stirring, obtain
155g acid solutions, wherein concentration of nitric acid are 2.7wt%.By material kneading 15min, 20min is then rolled, with the three of diameter 1.7mm
Leaf grass orifice plate extrusion.500 DEG C of roasting 4h after 120 DEG C of dry 4h.Carrier after roasting is designated as DS1.
By the carrier S 4 in embodiment 3 change carrier DS1 into made of catalyst be designated as DCAT1.
Comparative example 2
Water-soluble silicon oil A 5.5g are weighed, add appropriate amount of deionized water dissolving, it is 78mL, obtained solution B2 to make volume.Take
100g alumina support Z, by solution B 2 uniformly sprinkling on the alumina support, after health 10 hours, through 105 DEG C of heat treatment 3h,
230 DEG C of heat treatment 2h, obtain modified carrier DS2.
By the carrier S 2 in embodiment 2 change carrier DS2 into made of catalyst be designated as DCAT2.
Comparative example 3
Tetraboric acid ammonium 7.5g is weighed, adds appropriate amount of deionized water dissolving, it is 78mL to make volume, is configured to A2 solution.Take
100g alumina support Z, by solution A 2 uniformly sprinkling on the alumina support, after health 10 hours, through 105 DEG C of heat treatment 3h,
230 DEG C of heat treatment 2h, obtain modified carrier DS3.
By the carrier S 2 in embodiment 2 change carrier DS3 into made of catalyst be designated as DCAT3.
Comparative example 4
Compared with the preparation method of carrier S 2 in embodiment 2, this comparative example is first to introduce aluminium salt, introduces water-soluble silicon afterwards
Oil, detailed process are as follows：
100g alumina support Z are taken, 35mL A1 solution is diluted to 78mL with deionized water, is uniformly sprayed at the carrier
On, after health 3 hours, 76mL is diluted to deionized water through 100 DEG C of heat treatment 2h, then by 35mL solution Bs 1, is uniformly sprayed at
On carrier Z, health 10 hours, through 105 DEG C of heat treatment 3h, 230 DEG C of heat treatment 2h, modified carrier DS4 is obtained.
By the carrier S 2 in embodiment 2 change carrier DS4 into made of catalyst be designated as DCAT4.
Comparative example 5
Boric acid 2.0g, water-soluble silicon oil C 45.5g are weighed, adds appropriate amount of deionized water dissolving, it is 78mL to make volume, is made
Solution C 5.
Take 100g alumina support Z, by solution C 5 uniformly sprinkling on the alumina support, after health 10 hours, through 110 DEG C
2h is heat-treated, 260 DEG C of heat treatment 3h, obtains modified carrier DS5.
By the carrier S 5 in embodiment 4 change carrier DS5 into made of catalyst be designated as DCAT5.
Comparative example 6
With the maceration extract incipient impregnation carrier Z containing Mo, Ni, P, through 120 DEG C of dry 3h, after 450 DEG C of roasting 2h, acquisition
Catalyst is designated as DCAT6.
The embodiment of table 3 and comparative example carrying alumina volume property
| Aluminum oxide is numbered | Z | S1 | S2 | S3 | S4 | S5 | S6 |
| Introduce B2O3, % | - | 1.5 | 1.5 | 1.0 | 2.0 | 1.0 | 5.5 |
| Introduce SiO2, % | - | 0.8 | 0.8 | 1.4 | 1.4 | 0.5 | 2.5 |
| Specific surface area, m2/g | 293 | 289 | 287 | 283 | 280 | 290 | 277 |
| Pore volume, mL/g | 0.66 | 0.65 | 0.64 | 0.63 | 0.63 | 0.65 | 0.61 |
| Infrared total acid, mmol/g | 0.409 | 0.515 | 0.499 | 0.512 | 0.532 | 0.506 | 0.500 |
Continued 3
| Aluminum oxide is numbered | DS1 | DS2 | DS3 | DS4 | DS5 |
| Introduce B2O3Amount, wt% | 2.0 | - | 1.5 | 1.5 | 1.0 |
| Introduce SiO2Amount, wt% | 1.4 | 0.8 | - | 0.8 | 12.0 |
| Specific surface area, m2/g | 302 | 295 | 292 | 290 | 242 |
| Pore volume, mL/g | 0.65 | 0.66 | 0.66 | 0.64 | 0.53 |
| Infrared total acid, mmol/g | 0.461 | 0.439 | 0.430 | 0.459 | 0.405 |
The composition and property of the catalyst of table 4
| Catalyst forms | CAT1 | CAT2 | CAT3 | CAT4 | CAT5 | CAT6 |
| MoO3, wt% | 20.22 | 20.19 | 20.39 | 20.31 | 20.29 | 20.35 |
| NiO, wt% | 3.95 | 4.05 | 4.01 | 4.10 | 4.12 | 4.03 |
| P, wt% | 1.35 | 1.36 | 1.33 | 1.34 | 1.31 | 1.33 |
| Catalyst property | ||||||
| Infrared total acid, mmol/g | 0.394 | 0.382 | 0.391 | 0.399 | 0.388 | 0.383 |
Continued 4
| Catalyst forms | DCAT1 | DCAT2 | DCAT3 | DCAT4 | DCAT5 | DCAT6 |
| MoO3, wt% | 20.31 | 20.16 | 20.33 | 20.28 | 20.25 | 20.25 |
| NiO, wt% | 4.08 | 4.16 | 4.09 | 4.10 | 4.03 | 4.09 |
| P, wt% | 1.33 | 1.35 | 1.36 | 1.32 | 1.37 | 1.33 |
| Catalyst property | ||||||
| Infrared total acid, mmol/g | 0.336 | 0.325 | 0.318 | 0.337 | 0.293 | 0.309 |
Embodiment 6
The present embodiment is catalyst CAT1 ~ CAT6 and comparative catalyst DCAT1 ~ DCAT6 active appraisal experiment.
Catalyst activity evaluation experimental is carried out on 100mL small hydrogenation devices, catalyst is carried out before activity rating pre-
Vulcanization.Evaluating catalyst condition is the h of volume space velocity 1.0 in reaction stagnation pressure 9.0MPa, liquid-1, hydrogen to oil volume ratio 800：1, reaction
Temperature is 380 DEG C.Active appraisal experiment is shown in Table 5 with raw material oil nature, and Activity evaluation is shown in Table 6.
The raw material oil nature of table 5
| Feedstock oil | |
| Density (20 DEG C), g/cm3 | 0.9086 |
| Sulfur content, wt% | 2.26 |
| Nitrogen content, μ g/g | 1437 |
| Boiling range, DEG C | |
| IBP/ EBP | 301/535 |
The catalyst activity evaluation result of table 6
| Catalyst | CAT1 | CAT2 | CAT3 | CAT4 | CAT5 | CAT6 |
| With respect to denitrification activity, % | 139 | 138 | 133 | 134 | 139 | 126 |
| It is relatively desulphurizing activated, % | 126 | 126 | 124 | 124 | 126 | 120 |
Continued 6
| Catalyst | DCAT1 | DCAT2 | DCAT3 | DCAT4 | DCAT5 | DCAT6 |
| With respect to denitrification activity, % | 105 | 107 | 103 | 108 | 102 | 100 |
| It is relatively desulphurizing activated, % | 103 | 105 | 101 | 106 | 101 | 100 |
From table 6, compared with comparative example catalyst, with hydrotreating catalyst of the present invention, hydrodesulfurization and denitrogenation are lived
Property improves a lot, especially the activity of hydrodenitrogeneration.
Claims (26)
1. a kind of preparation method of hydrotreating catalyst, including the siliceous and alumina-based supports of boron preparations, using dipping
Method loads hydrogenation active metal component, through drying and being calcined, hydrotreating catalyst is obtained, wherein siliceous and boron alumina base
The preparation method of carrier includes：Water-soluble silicon oil and soluble boron-containing compound are sequentially or simultaneously introduced into alumina-based supports,
After Overheating Treatment, the alumina-based supports of silicon and boron are made；
Wherein, water-soluble silicon oil and soluble boron-containing compound sequentially or simultaneously introduce the incorporation way use of alumina-based supports
Infusion process；The silicone content being introduced into by water-soluble silicon oil in carrier accounts for modified oxidized alumina-based support weight in terms of silica
0.1%~5.0%, the Boron contents being introduced into by soluble boron-containing compound in carrier account for modified oxidized alumina-based support in terms of boron oxide
The 0.1%~10.0% of weight.
2. in accordance with the method for claim 1, it is characterised in that：The silicone content being introduced into by water-soluble silicon oil in carrier is with dioxy
SiClx meter accounts for the 0.2%~3.0% of modified oxidized alumina-based support weight, and the boron being introduced into by soluble boron-containing compound in carrier contains
Amount accounts for the 0.3%~6.0% of modified oxidized alumina-based support weight in terms of boron oxide.
3. in accordance with the method for claim 2, it is characterised in that：The silicone content being introduced into by water-soluble silicon oil in carrier is with dioxy
SiClx meter accounts for the 0.2% ~ 0.9% of modified oxidized alumina-based support weight, the Boron contents being introduced into by soluble boron-containing compound in carrier
The 0.5%~3.0% of modified oxidized alumina-based support weight is accounted in terms of boron oxide.
4. in accordance with the method for claim 1, it is characterised in that：Introduce the use of water-soluble silicon oil and soluble boron-containing compound
Amount is respectively using the mol ratio that silica and boron oxide are counted as 0.02 ~ 40.0.
5. in accordance with the method for claim 4, it is characterised in that：Introduce the use of water-soluble silicon oil and soluble boron-containing compound
Amount is respectively using the mol ratio that silica and boron oxide are counted as 0.04 ~ 10.0.
6. in accordance with the method for claim 5, it is characterised in that：Introduce the use of water-soluble silicon oil and soluble boron-containing compound
Amount is respectively using the mol ratio that silica and boron oxide are counted as 0.1 ~ 2.0.
7. in accordance with the method for claim 1, it is characterised in that：The property of described water-soluble silicon oil is as follows：At 25 DEG C
Viscosity is 200 ~ 7000mPa.s, and cloud point is 30 ~ 100 DEG C.
8. in accordance with the method for claim 7, it is characterised in that：The property of described water-soluble silicon oil is as follows：At 25 DEG C
Viscosity is 500 ~ 5000mPa.s, and cloud point is 40 ~ 65 DEG C.
9. in accordance with the method for claim 1, it is characterised in that：Described water-soluble silicon oil is polyether modified silicon oil.
10. in accordance with the method for claim 7, it is characterised in that：Described water-soluble silicon oil is polyether modified silicon oil.
11. in accordance with the method for claim 1, it is characterised in that：It using aluminum oxide is main that described alumina-based supports, which are,
Component, contains or not contain adjuvant component, and wherein adjuvant component is the one or more in fluorine, silicon, phosphorus, titanium, zirconium, boron, auxiliary agent
Content of the component in alumina-based supports is in below 30wt%.
12. in accordance with the method for claim 1, it is characterised in that：Alumina-based supports used are aluminium hydroxide through too high
Obtained after temperature roasting, the condition of high-temperature roasting is as follows：1.0h~20.0h is calcined at 450 DEG C~1000 DEG C.
13. in accordance with the method for claim 12, it is characterised in that：Alumina-based supports used are aluminium hydroxide through too high
Obtained after temperature roasting, the condition of high-temperature roasting is as follows：3.0h ~ 8.0h is calcined at 450 DEG C~1000 DEG C.
14. according to any described method of claim 1 ~ 13, it is characterised in that：The property of the alumina-based supports is as follows：
Specific surface area is 120 ~ 420m2/ g, pore volume are 0.4 ~ 1.3mL/g, and the pore volume shared by hole of the bore dia less than 4nm accounts for total pore volume
Less than 20%.
15. in accordance with the method for claim 1, it is characterised in that：Described soluble boron-containing compound is boric acid, five boric acid
One or more in ammonium, tetraboric acid ammonium.
16. in accordance with the method for claim 1, it is characterised in that：The heat treatment is using two sections of heat treatments, and first paragraph is in temperature
Spend for 60 DEG C~150 DEG C, processing time is 0.5h~20.0h, and second segment is 180 DEG C~400 DEG C in temperature, and processing time is
0.5h~20.0h.
17. in accordance with the method for claim 1, it is characterised in that：The heat treatment is using two sections of heat treatments, and first paragraph is in temperature
Spend for 90 DEG C~120 DEG C, processing time is 1.0h~6.0h, and second segment is 200 DEG C~350 DEG C in temperature, and processing time is
1.0h~6.0h.
18. in accordance with the method for claim 1, it is characterised in that：Water-soluble silicon oil and soluble boron-containing compound draw successively
Enter onto carrier, its incorporation way uses infusion process, i.e., first water-soluble silicon oil is impregnated on carrier, after health, by low
Soluble boron-containing compound, is then impregnated on carrier by warm processing again, by two sections of heat treatments, obtains modified oxidized aluminium base
Carrier；Wherein Low Temperature Heat Treatment is that processing time is 0.5h~20.0h at 60 DEG C~150 DEG C；In two sections of heat treatment, the
One section is 60 DEG C~150 DEG C in temperature, and processing time is 0.5h~20.0h, and second segment is 180 DEG C~400 DEG C in temperature, processing
Time is 0.5h~20.0h.
19. in accordance with the method for claim 18, it is characterised in that：The dipping solution that soluble boron-containing compound is made into
In, boron-containing compound concentration is calculated as 0.1g/100mL ~ 20g/100mL with boron oxide；The dipping solution that water-soluble silicon oil is made into
In, water-soluble silicon oil concentration is calculated as 0.1g/100mL ~ 20g/100mL with silica.
20. in accordance with the method for claim 1, it is characterised in that：Water-soluble silicon oil and soluble boron-containing compound draw simultaneously
Enter onto carrier, its incorporation way uses infusion process, i.e., water-soluble silicon oil and soluble boron-containing compound is impregnated into load simultaneously
On body, after health, by two sections of heat treatments, modified oxidized alumina-based support is obtained.
21. in accordance with the method for claim 20, it is characterised in that：Soluble boron-containing compound and water-soluble silicon oil are mixed
In the dipping solution of preparation, boron-containing compound concentration is calculated as 0.1g/100mL ~ 10g/100mL with boron oxide, and water-soluble silicon oil is dense
Degree is calculated as 0.1g/100mL ~ 10g/100mL with silica.
22. according to any described method of claim 18 ~ 21, it is characterised in that：Two sections of described heat treatments, first paragraph is in temperature
Spend for 90 DEG C~120 DEG C, processing time is 1.0h~6.0h, and second segment is 200 DEG C~350 DEG C in temperature, and processing time is
1.0h~6.0h.
23. according to any described method of claim 18 ~ 21, it is characterised in that：Infusion process uses an incipient impregnation.
24. in accordance with the method for claim 1, it is characterised in that：Described hydrogenation active metal component is vib metals
With the one or more in group VIII metal, wherein vib metals are W and/or Mo, group VIII metal be Co and/or
Ni。
25. in accordance with the method for claim 24, it is characterised in that：On the basis of the weight of catalyst, modified oxidized aluminium base
The content of carrier is 55.0wt% ~ 94.5wt%, and vib metals oxide content is 5.0wt% ~ 30.0wt%, VIII
Family metal oxide content is the wt% of 0.5wt% ~ 15.0.
26. in accordance with the method for claim 25, it is characterised in that：On the basis of the weight of catalyst, modified oxidized aluminium base
The content of carrier is 58.0wt% ~ 90.0wt%, and vib metals oxide content is 8.0wt% ~ 30.0wt%, VIII
Family metal oxide content is the wt % of 2.0 wt % ~ 12.0.
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| CN1274000A (en) * | 1999-05-18 | 2000-11-22 | 中国石油化工集团公司 | Hydrorefining catalyst for fraction oil and its preparing process |
| CN1444506A (en) * | 2000-07-28 | 2003-09-24 | 日本凯金株式会社 | Hydroprocessing catalyst for heavy oils and its use |
| JP2008081324A (en) * | 2006-09-25 | 2008-04-10 | Sumitomo Chemical Co Ltd | METHOD FOR PRODUCING alpha-ALUMINA MOLDING |
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|---|---|---|---|---|
| CN1274000A (en) * | 1999-05-18 | 2000-11-22 | 中国石油化工集团公司 | Hydrorefining catalyst for fraction oil and its preparing process |
| CN1444506A (en) * | 2000-07-28 | 2003-09-24 | 日本凯金株式会社 | Hydroprocessing catalyst for heavy oils and its use |
| JP2008081324A (en) * | 2006-09-25 | 2008-04-10 | Sumitomo Chemical Co Ltd | METHOD FOR PRODUCING alpha-ALUMINA MOLDING |
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