CN106268969A - A kind of catalyst carrier and preparation method thereof and Hydrodemetalation catalyst - Google Patents
A kind of catalyst carrier and preparation method thereof and Hydrodemetalation catalyst Download PDFInfo
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Abstract
The present invention relates to catalyst field, disclose a kind of catalyst carrier and preparation method thereof and the Hydrodemetalation catalyst comprising this catalyst carrier.Described catalyst carrier is stacked by the aluminium oxide monomer of multiple nano bar-shapes and forms, and described catalyst carrier has the duct of opening, a length of 100-500nm of the aluminium oxide monomer of each nano bar-shape, a diameter of 10-50nm.The catalyst carrier of the present invention has bigger pore volume aperture, and has preferable hole character, permeability and appearance amount of metal concurrently；The preparation method of the catalyst carrier of the present invention is simple, it is not necessary to adding the multiple additives such as pore creating material, plasticizer, cost is relatively low；Further, the appearance amount of metal of the Hydrodemetalation catalyst of the present invention is high, activity and good stability.
Description
Technical field
The present invention relates to catalyst field, in particular it relates to a kind of catalyst carrier, this catalyst carrier
Preparation method, the method the catalyst carrier prepared, and comprise this catalyst carrier hydrogenation take off
Metallic catalyst.
Background technology
Recently as the sharp increase of private motor vehicles quantity, cause being doubled and redoubled of vehicle fuel aggregate demand.
The scarcity of resources caused due to the exhaustive exploitation of crude oil makes the heaviness of raw oil, in poor quality the tightest
Weight, brings severe challenge to the refinement treatment process of oil product.The oil caused due to crude oil heaviness in poor quality
Product density rises viscosity and increases, and impurity content is particularly containing the increase of metal based compound, except may be right
Environment and motor vehicle components cause outside bigger impact, also can to oil refining the course of processing, product quality and
Light oil yield produces serious influence, and becomes the key factor that restriction Business Economic Benefit improves.
In petroleum distillate containing metal ingredient owing to influencing whether the processes such as the hydrodesulfurization in downstream, denitrogenation,
Cause catalyst poisoning, inefficacy, therefore HDM has particularly significant for whole unifining process
Meaning.HDM technology it is critical only that Hydrodemetalation catalyst.For many years, the de-gold of hydrogenation
Metal catalyst carrier commonly used Ni (Co)-Mo (W) is as active component, and carries out catalyst carrier
Improvement can significantly improve catalyst performance.Therefore, research has focused largely on novel carriers and novel preparation
In the exploitation of method.
Hydrodemetalation catalyst carrier typically use boehmite to prepare aluminium oxide, from recent years
Research from the point of view of, catalyst carrier is mostly extruded spherical or amorphous carrier, and these carriers are opened
Begin gradually to bigger aperture and pore volume, bigger specific surface area and the dispersion of higher metal active constituent
The direction of property is developed.This is because the catalyst carrier containing certain proportion macroporous structure more conforms to heavy oil
The mechanism of HDM reaction, has the stronger ability accommodating metal, can effectively reduce heavy oil and exist
Reaction resistance in course of reaction, improves the diffusion coefficient of heavy oil, is suitable for the residual oil higher to tenor
It is processed.
CN103657667A discloses a kind of new macroporous structure catalyst for heavy oil hydrogenation demetal carrier.
Its preparation process is 1) by industry boehmite powder and extrusion aid (sesbania powder) and peptizer (nitre
Acid or acetic acid) it is mixed with and obtains Alumina gel；2) using asphaltic residue powder as pore creating material and Alumina gel
It is mixed with the catalyst carrier with macroporous structure.The method utilize asphaltic residue as pore creating material,
Introduce and remain the original micropore of boehmite and mesopore while macropore, and specific surface area, intensity and
Pore volume is all not less than traditional catalyst carrier, can effectively reduce the resistance to mass tranfer of HDM reaction,
Improve the appearance metal ability of catalyst；But, owing to its building-up process taking supercritical fluid extraction
Drying mode, appointed condition costly and complicated, and the method use extrusion aid, peptizer and
The multiple additives such as pore creating material, make complex process, cost increase.
CN103657739A discloses the preparation method of a kind of mesopore-macropore composite construction alumina support,
The method comprises the following steps: 1) prepare macropore PS template, obtains macropore PS after crushing, sieving
Template particles；2) boehmite is mixed with water, obtain, with nitric acid regulation, the aluminium oxide that pH is 3-4
The hydrosol；3) under vacuum condition, prepared alumina hydrosol is filled to macropore PS template, repeatedly
Macroporous aluminium oxide-PS the granule that filling obtains after drying；4) by step 3) macroporous aluminium oxide-PS that obtains
Granule and two kinds of different boehmite dry powder blend, through peptization, kneading, molding, drying
And roasting, obtain mesopore-macropore composite alumina support.This carrier make the pore volume of catalyst be 0.8～
1.1mL/g, specific surface area is 120～160m2/g.The advantage of the method is to be drawn by more macropore
Enter catalyst carrier, keep the other kinds of pore structure parameter of catalyst not change simultaneously.But the party
Method manufacturing cycle is long, technique very complicated.
CN102441437A discloses a kind of alumina support making Hydrodemetalation catalyst and system thereof
Preparation Method.The preparation method of this catalyst carrier is that boehmite dry glue powder is carried out pressurized thermal water process
Rear kneading becomes plastic, and adds expanding agent；Be dried after plastic molding, roasting i.e. can get macropore oxygen
Change alumina supporter.Hydrodemetalation catalyst prepared by the method has bigger pore volume aperture, the hole of concentration
Distribution, moderate mechanical strength, and there is higher activity and stability；But the method needs kneading
Becoming plastic and carry out plastic molding, technique is the most succinct, and the method needs to add expanding agent,
Increase cost to a certain extent.
TW201336585A in JIUYUE, 2013 is up-to-date to be disclosed a kind of spherical Hydrodemetalation catalyst and carries
Body.This catalyst is with the sphere material of a kind of a diameter of 2.0mm as carrier.The preparation of this ball type carrier
Method use aluminum sulfate and titanium sulfate as aluminum source and titanium source, pH be 7.2～9.0 and temperature 50～
Separate out titania alumina when 80 DEG C, be then passed through washing and add peptizer after drying, form slurry
Rear entrance in drippage tower forms spherical particle, 980 DEG C～1060 DEG C of roastings 1～obtains dioxy after 3 hours
Change titanium aluminum oxide carrier.The catalyst that this carrier prepares has higher stability, but the nickel when 395 DEG C
Removal efficiency be only 52.4%, conversion ratio is relatively low.
Summary of the invention
The hole character that it is an object of the invention to overcome existing catalyst carrier is the best, permeability and/
Or hold the shortcoming that amount of metal is not high enough, and overcome the complicated process of preparation of existing catalyst carrier, make
Problem with more additive, it is provided that a kind of catalyst carrier and preparation method thereof, and comprise this and urge
The Hydrodemetalation catalyst of agent carrier.The catalyst carrier of the present invention have concurrently preferable hole character,
Permeability and appearance amount of metal；The preparation method of the catalyst carrier of the present invention is simple, it is not necessary to interpolation pore creating material,
The multiple additives such as plasticizer, cost is relatively low；Further, the appearance gold of the Hydrodemetalation catalyst of the present invention
Genus amount is high, activity and good stability.
First aspect present invention provides a kind of catalyst carrier, and this catalyst carrier is by multiple nano bar-shapes
Aluminium oxide monomer stacking form, described catalyst carrier have opening duct, each nano bar-shape
The a length of 80-500nm, a diameter of 10-50nm of aluminium oxide monomer.
Second aspect present invention provides a kind of method of catalyst carrier preparing the present invention, the method bag
Include following steps:
(1) in a solvent by alkali and aluminium salt hybrid reaction, the colloidal liquid that pH value is 4-6 is obtained；
(2) described colloidal liquid is carried out hydrothermal treatment consists, and the mixture obtained is carried out solid-liquid separation,
Being dried and roasting by gained solid, after then being mixed with peptizer by roasting gained solid, extrusion becomes
Type.
Third aspect present invention provides the catalyst carrier that the method according to the invention prepares.
Fourth aspect present invention provides a kind of Hydrodemetalation catalyst, and this Hydrodemetalation catalyst contains
Having carrier and active metal component, described carrier is the catalyst carrier of the present invention.
It was found by the inventors of the present invention that the catalyst carrier of prior art is in order to obtain larger aperture, generally
Needing to add pore creating material, on the one hand this add cost, the duct on the other hand obtained by this method
The most open inadequate, it is easy to blocking, thus severely impacted the permeability of catalyst and held amount of metal.
Therefore, the present inventor is through substantial amounts of thinking and research, and creatively expecting can be with abandoning tradition
The idea of " pore-creating ", but obtain duct by the monomer of catalyst carrier being carried out stacking.This
Creative preparation thinking can bring a lot of benefit: one, the duct obtained by this method has
Extraordinary opening, so that catalyst has the permeability of excellence and holds amount of metal；Its two, this
Preparation thinking determines preparation method without using the multiple additives such as pore creating material, plasticizer, preparation method
Simple and cost is lower；Its three, under conditions of not adding plasticizer, still can use relatively low roasting
Burn temperature (sintering temperature is relatively low typically requires the substantial amounts of plasticizer of addition to prior art in order to make)；Its four,
The open duct that the catalyst of the present invention has due to it, not easy in inactivation and blocking, have higher
Activity and stability.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with
Detailed description below is used for explaining the present invention together, but is not intended that limitation of the present invention.?
In accompanying drawing:
Fig. 1 is the SEM figure of catalyst carrier I1 prepared by embodiment 1.
Fig. 2 is the XRD figure of catalyst carrier I1 prepared by embodiment 1.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
First aspect present invention provides a kind of catalyst carrier, and this catalyst carrier is by multiple nano bar-shapes
Aluminium oxide monomer stacking form, described catalyst carrier have opening duct, each nano bar-shape
The a length of 80-500nm, a diameter of 10-50nm of aluminium oxide monomer.
The length of the aluminium oxide monomer of described nano bar-shape and the uniformity coefficient of diameter are not had by the present invention
Particularly limit, length can 80-500nm in a big way in fluctuation, preferably at 80-250nm
In a big way in fluctuation, diameter can 10-50nm in a big way in fluctuation, preferably exist
The interior in a big way fluctuation of 15-30nm.
In the present invention, there is good opening in described catalyst carrier duct, so even at pore volume and
In the case of aperture is close with prior art, the catalyst carrier of the present invention still has more preferable permeability
With appearance amount of metal and other performances.Usually, the specific surface area of described catalyst carrier is 80-200
m2/ g, pore volume is 0.3-0.8cm3/ g, aperture is 10-35nm；Preferably, described catalyst carrier
Specific surface area is 100-160m2/ g, pore volume is 0.5-0.8cm3/ g, aperture is 15-35nm.
In the present invention, described aluminium oxide is preferably γ-Al2O3。
Second aspect present invention provides a kind of method of catalyst carrier preparing the present invention, the method bag
Include following steps:
(1) in a solvent by alkali and aluminium salt hybrid reaction, the colloidal liquid that pH value is 4-6 is obtained；
(2) described colloidal liquid is carried out hydrothermal treatment consists, and the mixture obtained is carried out solid-liquid separation,
Being dried and roasting by gained solid, after then being mixed with peptizer by roasting gained solid, extrusion becomes
Type.
It was found by the inventors of the present invention that prior art generally uses boehmite as raw material, cause institute
The structure of the catalyst carrier prepared is restricted by structure of similar to thin diaspore, it is difficult to prepare at morphosis
On there is the product of breakthrough innovation.Therefore, the present inventor has abandoned the direct use thin water aluminum of plan
Masonry is the traditional method of raw material, but prepares the presoma of boehmite by aluminium salt oneself, and in situ
Carry out hydrothermal treatment consists, thus the catalyst obtaining having on morphosis the present invention of breakthrough innovation carries
Body.
In the present invention, by the mode of alkali Yu aluminium salt hybrid reaction, there is no particular limitation in a solvent,
In a kind of preferred embodiment, it is respectively configured aluminum salt solution and alkali liquor with described solvent, in stirring
Under conditions of alkali liquor is slowly added in aluminum salt solution, until the pH value of milky colloidal liquid of gained
For 4-6, preferably 4-5；It is highly preferred that wherein, in described aluminum salt solution, the concentration of aluminium salt is 0.5-3M,
Being preferably 1-2M, in described alkali liquor, the concentration of alkali is 0.5-3M, preferably 0.5-1.5M.Described slowly
There is no particular limitation for the speed added, preferably 5-40mL/min.The speed of described stirring does not has yet
Particularly limit, preferably 300-1000r/min, more preferably 300-700r/min.
In the present invention, all there is no particular limitation for the kind of described solvent, aluminium salt and alkali, uses ability
The conventional use of kind in territory.Such as, described solvent can be deionized water, ethanol or both is mixed
Close liquid；Described aluminium salt can be one or more in aluminum nitrate, aluminum sulfate, aluminum chloride and aluminum isopropylate.,
It is preferably one therein, more preferably aluminum chloride；Described alkali selects the material with alkalescence, example
As being one or more in sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonia and sodium metaaluminate.
In the present invention, the condition of described hydrothermal treatment consists can be that this area is prepared during catalyst carrier conventional
The condition of the hydrothermal treatment consists used, such as, wherein, the condition of described hydrothermal treatment consists may include that temperature
For 100-220 DEG C, the time is 6-48h；Preferably, the condition of described hydrothermal treatment consists includes: temperature is
160-200 DEG C, the time is 14-24h.Described hydrothermal treatment consists is preferably carried out in closed environment, such as, exist
Water heating kettle commonly used in the art is carried out.
In the present invention, there is no particular limitation for the mode of described solid-liquid separation, and this area can be used normal
The mode of the solid-liquid separation of rule, such as, can be filtration, sucking filtration or centrifugal, it is preferred to use centrifugal mode
Carry out solid-liquid separation.After solid-liquid separation, it is preferable that gained solid is washed with deionized 2-5
Secondary.
In the present invention, there is no particular limitation for described dry condition, such as, may include that temperature is
60-120 DEG C, the time is 6-24 hour；Preferably, temperature is 100-120 DEG C, and the time is 6-12 hour.
In the present invention, the condition of described roasting may include that temperature is 400-750 DEG C, and the time is 2-6h；
Preferably, the condition of described roasting includes: temperature is 500-650 DEG C, and the time is 3-5h.The present invention is not
Need to add plasticizer, temperature be 500-650 DEG C, the time be 3-5h roasting condition under i.e. can be real
The bigger pore volume aperture of the catalyst carrier of the existing present invention, and if prior art is without plasticizer
Words, then need to use the sintering temperature of up to 800 DEG C can reach the catalyst carrier phase with the present invention
Near pore volume aperture.
After the method preparing described catalyst carrier of the present invention is additionally included in hydrothermal treatment consists, solid-liquid separation
Before, hydrothermal treatment consists gained mixture is cooled to room temperature.Room temperature of the present invention refers to not to temperature
Particularly test and control, the most close with ambient temperature, generally 10-40 DEG C.
In the preferred case, the method preparing described catalyst carrier of the present invention be additionally included in carry out described
Auxiliary agent is added, to improve the performance of catalyst carrier further before hydrothermal treatment consists.The addition of described auxiliary agent
Time, there is no particular limitation, can before alkali and aluminium salt are carried out hybrid reaction or during add,
Can also add after obtaining colloidal liquid.There is no particular limitation for the kind of described auxiliary agent, it is preferable that
One or more in sodium chloride, carbamide, citric acid, ammonium chloride, Alumen and starch of described auxiliary agent.
In the present invention, after described roasting, just obtain nano bar-shape aluminium oxide monomer of the present invention,
These monomers are stacked and have just obtained the catalyst carrier of the present invention.In order to make the catalyst of the present invention
Carrier has fixing shape, can be mixed with described nano bar-shape aluminium oxide monomer by appropriate peptizer,
Then extruded moulding becomes the shape needed.There is no particular limitation for the kind of described peptizer, uses routine
Peptizer, can be such as nitric acid and/or acetic acid.Consumption and the concentration of described peptizer do not have spy
Other restriction, such as, relative to the described nano bar-shape aluminium oxide monomer of 100 weight portions, described peptization
The consumption of agent is 1-4 weight portion, and concentration is 10%-20%.
Third aspect present invention provides the catalyst carrier that the method according to the invention prepares, and this is urged
Agent carrier is stacked by the aluminium oxide monomer of multiple nano bar-shapes and forms, and has the duct of opening, thus
There are more preferable hole character, permeability and appearance amount of metal.
Fourth aspect present invention provides a kind of Hydrodemetalation catalyst, and this Hydrodemetalation catalyst contains
Having carrier and active metal component, described carrier is the catalyst carrier of the present invention.Work in this catalyst
Property metal component there is no particular limitation, can be the conventional active metal component in this area, for example,
One or more in Ni, Co, Mo and W.The content of described active metal component the most particularly limits
Fixed, such as, on the basis of the gross weight of catalyst, the content of described active metal component can be 4-15
Weight %, preferably 6-10 weight %.
In the present invention, there is no particular limitation for the preparation method of described Hydrodemetalation catalyst, uses
The preparation method that this area is conventional.According to one detailed description of the invention of the present invention, the de-gold of described hydrogenation
The preparation method of metal catalyst may comprise steps of: nickel source and molybdenum source are dissolved in deionized water by (1)
In obtain nickel molybdenum mixed solution, the content of the nickel counted with NiO in this nickel molybdenum mixed solution for 2-4 weight %,
With MoO3The content of the molybdenum of meter is 5-7 weight %；(2) at room temperature, by described nickel molybdenum mixed solution
Impregnate the catalyst carrier of the present invention with equi-volume impregnating and keep 8-16 hour obtaining predecessor；(3)
Step (2) gained predecessor is dried 8-16 hour in the baking oven of 70-90 DEG C, then at 400-600 DEG C
Lower roasting 3-6h.Wherein, described nickel source can be various to prepare conventional use of nickel source, example during catalyst
As one or more in nickel nitrate, nickel sulfate, Nickel dichloride. and nickel acetate, preferably nitric acid can be selected from
Nickel；Described molybdenum source can be various to prepare conventional use of molybdenum source during catalyst, such as, can be selected from two molybdenums
One or more in acid ammonium, ammonium tetramolybdate, ammonium heptamolybdate and ammonium octamolybdate, preferably ammonium heptamolybdate.
The Hydrodemetalation catalyst of the present invention can first vulcanize before the use, and the process of sulfuration can
Think the sulfidation that this area is conventional, such as, may include that the Hydrodemetalation catalyst of the present invention
It is placed on the quartz ampoule of fixed bed high pressure microreactor, first uses N2Purge is also warming up to
350-450 DEG C, then use H2S and H2Gaseous mixture purge and keep 2.5-4h.Wherein, institute
State N2Flow be 50-70mL/min, described H2S and H2The flow of gaseous mixture be 50-70mL/min；
Wherein, described H2S and H2Gaseous mixture in H2The content of S is 12-18 volume %.This preparation method
Also include finally gained catalyst being cooled to room temperature.
Hereinafter will be described the present invention by embodiment.
Embodiment 1-8 and comparative example 1 are for catalyst carrier that the present invention is described and preparation method thereof.Its
In, the form of gained catalyst carrier, length and the diameter Flied emission scanning electricity by Li Ao company of Germany
Sub-microscope LEO-1530 (SEM) is observed, and the specific surface area of catalyst carrier, pore volume and aperture are divided
Cloth test completes on Micromeritics Tristar 3000 type Full-automatic physical chemical adsorption instrument.Compare table
Areal calculation uses multilamellar physical adsorption process (i.e. BET equation), and pore volume and pore-size distribution are adopted
Coagulate method (BJH) with capillary tube to calculate.
Embodiment 1
Compound concentration is the aluminum chloride aqueous solution of 2M and concentration is the ammonia spirit of 1M, by ammonia spirit
Being added dropwise in aluminum chloride aqueous solution, the pH value making gained milky colloidal liquid is 4.5.Gained is gluey
Liquid is transferred in water heating kettle, naturally cools to after being heated to 160 DEG C of insulations 24 hours in being placed in baking oven
Room temperature.Reacted product is performing centrifugal separation on, and is placed in baking oven 120 DEG C with deionized water cyclic washing
Being dried, drying time is 12 hours, obtains boehmite presoma.Gained presoma air will be added
Heat is incubated 2 hours to 550 DEG C, then by gained solid and peptizer (concentration is the nitric acid of 15%) with
Extruded moulding after the weight ratio mixing of 100:2, obtains catalyst carrier I1, and character is as shown in table 1.
I1 is carried out SEM detection, acquired results as shown in Figure 1, as can be seen from Figure 1: this catalysis
Agent carrier regular shape, smooth surface, be about 20nm, a length of 100-200nm by a series of diameters
Nanometer rods stacking form, duct is opening, and permeability is preferable.I1 is carried out X-ray diffraction (XRD)
Detection, result as shown in Figure 2, as can be seen from Figure 2 I1 sample 2 θ be 19.4 °, 37.6 °,
There is stronger diffraction maximum at 39.5 °, 45.8 °, 66.7 ° and 85.0 °, belong to γ-Al2O3Diffraction
Peak, therefore may certify that its aluminium oxide is γ-Al2O3。
Embodiment 2
Compound concentration is the aluminum chloride aqueous solution of 2M and concentration is the aqueous sodium carbonate of 1M, by carbonic acid
Sodium water solution is added dropwise in aluminum chloride aqueous solution, and the pH value making gained milky colloidal liquid is 4.9.Will
Gained colloidal liquid is transferred in water heating kettle, be heated in being placed in baking oven 200 DEG C insulation 24 hours after from
So it is cooled to room temperature.Reacted product is performing centrifugal separation on, and is placed on baking with deionized water cyclic washing
In case, 120 DEG C are dried, and drying time is 8 hours, obtains boehmite presoma.By gained presoma
Being heated to 550 DEG C in air and be incubated 4 hours, then by gained solid, (concentration is 15% with peptizer
Acetic acid) with extruded moulding after the weight ratio mixing of 100:2, obtain catalyst carrier I2, character such as table
Shown in 1.
Embodiment 3
Compound concentration is the aluminum sulfate aqueous solution of 2M and concentration is the aqueous sodium carbonate of 1M, by carbonic acid
Sodium water solution is added dropwise in aluminum nitrate aqueous solution, and the pH value making gained milky colloidal liquid is 4.7.Will
Gained colloidal liquid is transferred in water heating kettle, be heated in being placed in baking oven 180 DEG C insulation 24 hours after from
So it is cooled to room temperature.Reacted product is performing centrifugal separation on, and is placed on baking with deionized water cyclic washing
In case, 110 DEG C are dried, and drying time is 12 hours, obtains boehmite presoma.By gained forerunner
Being heated to 600 DEG C in body air and be incubated 3 hours, then by gained solid, (concentration is 15% with peptizer
Nitric acid) mix with the weight ratio of 100:2 after extruded moulding, obtain catalyst carrier I3, character is such as
Shown in table 1.
Embodiment 4
Compound concentration is the aluminum chloride aqueous solution of 1M and concentration is the sodium hydrate aqueous solution of 1M, by hydrogen
Aqueous solution of sodium oxide is added dropwise in aluminum chloride aqueous solution, and the pH value making gained milky colloidal liquid is
4.2.Gained colloidal liquid is transferred in water heating kettle, is heated to 200 DEG C of insulations 24 in being placed in baking oven little
Room temperature is naturally cooled to time after.Reacted product is performing centrifugal separation on, and with after deionized water cyclic washing
Being placed in baking oven 100 DEG C to be dried, drying time is 12 hours, obtains boehmite presoma.By institute
Obtain and presoma air is heated to 450 DEG C of insulations 4 hours, then by gained solid and peptizer (concentration
It is the acetic acid of 15%) with extruded moulding after the weight ratio mixing of 100:2, obtain catalyst carrier I4,
Character is as shown in table 1.
Embodiment 5
Compound concentration is the aluminum nitrate aqueous solution of 2M and concentration is the ammonia spirit of 2M, by ammonia spirit
Being added dropwise in aluminum nitrate aqueous solution, the pH value making gained milky colloidal liquid is 4.5.Gained is gluey
Liquid is transferred in water heating kettle, naturally cools to after being heated to 200 DEG C of insulations 24 hours in being placed in baking oven
Room temperature.Reacted product is performing centrifugal separation on, and is placed in baking oven 110 DEG C with deionized water cyclic washing
Being dried, drying time is 12 hours, obtains boehmite presoma.Gained presoma air will be added
Heat is incubated 4 hours to 500 DEG C, then by gained solid and peptizer (concentration is the nitric acid of 10%) with
Extruded moulding after the weight ratio mixing of 100:4, obtains catalyst carrier I5, and character is as shown in table 1.
Embodiment 6
Compound concentration is the aluminum chloride ethanol solution of 2M and sodium hydroxide ethanol solution that concentration is 1M,
Sodium hydroxide ethanol solution is added dropwise in aluminum chloride ethanol solution, makes gained milky colloidal liquid
PH value is 4.7.Gained colloidal liquid is transferred in water heating kettle, in being placed in baking oven, is heated to 200 DEG C of guarantors
Temperature naturally cooled to room temperature after 24 hours.Reacted product is performing centrifugal separation on, and anti-with deionized water
After backwashing is washed and is placed in baking oven 110 DEG C and is dried, and drying time is 6 hours, obtains boehmite presoma.
It is incubated 4 hours by gained presoma air is heated to 550 DEG C, then that gained solid is (dense with peptizer
Degree is the acetic acid of 20%) with extruded moulding after the weight ratio mixing of 100:1, obtain catalyst carrier I6,
Character is as shown in table 1.
Embodiment 7
Compound concentration is the aluminum chloride aqueous solution of 1M and concentration is the ammonia spirit of 0.5M, and ammonia is molten
Drop adds in aluminum chloride aqueous solution, and the pH value making gained milky colloidal liquid is 4.9.At gained glue
Shape liquid adds 5.8g sodium chloride stir and be transferred in water heating kettle, be heated in being placed in baking oven
200 DEG C insulation 24 hours after naturally cool to room temperature.Reacted product is performing centrifugal separation on, and spends
Ionized water cyclic washing is placed in baking oven 110 DEG C and is dried, and drying time is 6 hours, must intend thin water aluminum
Stone presoma.It is incubated 4 hours, then by gained solid by gained presoma air is heated to 550 DEG C
Extruded moulding after mixing with the weight ratio of 100:2 with peptizer (concentration is the nitric acid of 15%), obtains
Catalyst carrier I7, character is as shown in table 1.
Embodiment 8
Carry out according to the method for embodiment 1, except that, colloidal liquid is being transferred in water heating kettle
Before, in colloidal liquid, auxiliary agent carbamide, final prepared catalyst carrier I8, character such as table 1 are first added
Shown in.
Embodiment 9
Changing the ammonia in embodiment 1 into sodium metaaluminate, remaining is with embodiment 1, prepares catalyst carrier
I9, character is as shown in table 1.
Comparative example 1
Catalyst carrier D1 is prepared according to method disclosed in the embodiment 1 of patent CN1206037A,
Record its character as shown in table 1.
Table 1
Embodiment 10-13 and comparative example 2 are for illustrating the Hydrodemetalation catalyst of the present invention.
Embodiment 10-13 and comparative example 2 respectively will above gained catalyst carrier I1, I5, I6, I8 and
D1 prepares Hydrodemetalation catalyst respectively, and sulfuration obtains the de-gold of hydrogenation of sulphided state further
Metal catalyst I10-13 (the most corresponding I1, I5, I6, I8) and D2 (corresponding D1), concrete grammar is such as
Under:
Nickel nitrate and ammonium heptamolybdate being dissolved in deionized water and obtain nickel molybdenum mixed solution, this nickel molybdenum mixes
In solution, the content of nickel in terms of NiO is 2.5 weight %, with MoO3The content of the molybdenum of meter is 7 weight %；
The most at room temperature, described nickel molybdenum mixed solution is impregnated embodiment 1,5,6,8 with equi-volume impregnating
With catalyst carrier I1 of comparative example 1, I5, I6, I8 and D1, and keep 12 hours, obtain forerunner
Thing；Gained predecessor is dried 12 hours in the baking oven of 80 DEG C, then roasting 4h at 500 DEG C,
Obtain a series of Hydrodemetalation catalyst；
Above-mentioned a series of Hydrodemetalation catalysts are loaded in fixed bed high-pressure hydrogenation reactor respectively,
Handled residual oil raw material is identical with test condition, continuously runs 2000h, and de-contaminant characteristics is shown in Table 2.
Reacted catalyst icp ms (ICP-MS-4500v) directly measures appearance gold
Genus amount, the results are shown in Table shown in 3.Handled residual oil raw material character is as follows: sulfur content is 3.8 weight %,
Nitrogen content is 2410ug/g, and nickel content is 35.1ug/g, and content of vanadium is 94.2ug/g.Test condition is:
Reaction temperature 390 DEG C, hydrogen-oil ratio 1000, resid feed volume space velocity 1.2h-1, pressure 15MPa.
Table 2
From Table 2, it can be seen that compared with D2, the catalyst that the present invention provides has higher hydrogenation
Metal removal activity, and maintain preferable hydrodesulfurization activity and hydrodenitrogenationactivity activity.
Table 3
Even if in conjunction with table 1 and table 3 it can be seen that the pore volume of the catalyst carrier of the present invention is less than comparative example,
The catalyst that the present invention provides still has significantly higher appearance amount of metal.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
Claims (10)
1. a catalyst carrier, it is characterised in that this catalyst carrier is by the oxygen of multiple nano bar-shapes
Changing aluminum monomer stacking to form, described catalyst carrier has the duct of opening, the oxygen of each nano bar-shape
Change a length of 80-500nm, a diameter of 10-50nm of aluminum monomer.
Catalyst carrier the most according to claim 1, wherein, the specific surface of described catalyst carrier
Amass as 80-200m2/ g, pore volume is 0.3-0.8cm3/ g, aperture is 10-35nm.
3. the method preparing catalyst carrier described in claim 1 or 2, the method include with
Lower step:
(1) in a solvent by alkali and aluminium salt hybrid reaction, the colloidal liquid that pH value is 4-6 is obtained；
(2) described colloidal liquid is carried out hydrothermal treatment consists, and the mixture obtained is carried out solid-liquid separation,
Being dried and roasting by gained solid, after then being mixed with peptizer by roasting gained solid, extrusion becomes
Type.
Method the most according to claim 3, wherein, described mixes alkali with aluminium salt in a solvent
The mode of reaction includes: be respectively configured alkali liquor and aluminum salt solution with described solvent, then in the condition of stirring
Lower alkali liquor is slowly added in aluminum salt solution；
Preferably, described in the speed that is slowly added to be 5-40mL/min, the speed of described stirring is
300-1000r/min；
Preferably, in described alkali liquor, the concentration of alkali is 0.5-3M, and in described aluminum salt solution, the concentration of aluminium salt is
0.5-3M。
5. according to the method described in claim 3 or 4, wherein, described alkali is sodium hydroxide, carbonic acid
One or more in sodium, sodium bicarbonate, ammonia and sodium metaaluminate；
Preferably, the one or many during described aluminium salt is aluminum sulfate, aluminum nitrate, aluminum chloride and aluminum isopropylate.
Kind.
6. according to the method described in claim 3 or 4, wherein, the condition of described hydrothermal treatment consists includes:
Temperature is 100-220 DEG C, and the time is 6-48h；Preferably, temperature is 160-200 DEG C, and the time is 14-24h.
7. according to the method described in claim 3 or 4, wherein, the condition of described roasting includes: temperature
Degree is for 400-750 DEG C, and the time is 2-6h；Preferably, temperature is 500-650 DEG C, and the time is 3-5h.
8. according to the method described in claim 3 or 4, wherein, the method be additionally included in carry out described
Adding auxiliary agent before hydrothermal treatment consists, this auxiliary agent is selected from sodium chloride, carbamide, citric acid, ammonium chloride, Alumen
With one or more in starch.
9. the catalyst carrier prepared according to the method described in any one in claim 3-8.
10. a Hydrodemetalation catalyst, this Hydrodemetalation catalyst contains carrier and active metal
Component, it is characterised in that described carrier is the catalyst in claim 1-2 and 9 described in any one
Carrier.
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