CN104368352B - A kind of hydrogenation activity guard catalyst and preparation and application thereof - Google Patents
A kind of hydrogenation activity guard catalyst and preparation and application thereof Download PDFInfo
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Abstract
A kind of hydrogenation activity guard catalyst and preparation and application thereof; described catalyst contain have structure of double peak holes containing at least one selected from boron, silicon and the alumina support of fluorine auxiliary agent; characterizing with mercury injection method, the pore volume of described carrier is 0.3 0.8 mls/g, and specific surface area is 70 220 meters2/ gram, wherein, the pore volume in a diameter of 6 10nm holes accounts for the 8 25% of total pore volume, and the pore volume in a diameter of 85 160nm holes accounts for the 40 75% of total pore volume.Compared with prior art, the hydrogenation activity guard catalyst that the present invention provides has and preferably holds metallicity.
Description
Technical field
The present invention relates to a kind of hydrogenation activity guard catalyst and preparation and application thereof.
Background technology
Along with crude quality is deteriorated, in crude oil, the impurity content such as colloid, asphalitine and organo-metallic compound increases
Height, the existence of these impurity easily causes the rapid decrease of catalyst activity so that inactivating.Solve this to ask
The effective ways of topic are the protective agents in the filling of hydrogenation catalyst bed top with hydrogenation activity.Have bigger
The hydrogenation protecting catalyst of pore volume and bore dia holds metal and appearance charcoal ability is strong, it is possible to play protection downstream hydrogenation
The effect of host, extends the service life of host.
In prior art about hydrogenation protecting catalyst and preparation thereof example such as:
CN200610113493.5 discloses a kind of hydrogenation protecting agent and preparation thereof, this protective agent contain one or
The heat-resistant inorganic oxide of several porous, it is characterised in that the total pore volume of described protective agent is 0.3-1.5
Millimeter/gram, wherein containing grade macropore, grade macropore bore dia is 0.1～1.5 micron, grade
Macropore pore volume is 0.05～0.7 ml/g.The preparation method of described hydrogenation protecting agent, including by one or
The heat-resistant inorganic oxide of several porous and/or the precursor of the heat-resistant inorganic oxide of porous and at least one
Organic substance mixing, molding, dry and roasting, wherein, described organic compound is that fusing point is between 30～200
DEG C, particle diameter 0.3～2.5 millimeters and water-fast solid particle.
CN201010220850.4 discloses a kind of protectant preparation method of hydrotreating.The method aoxidizes
Alumina supporter is to use two kinds of different boehmite dry glue powder kneading methods to prepare, then supported active gold
Belong to；Wherein the first crystallization degree of pseudo-boehmite is relatively small, and pore volume is big, it is possible to provide bore dia 30nm～
The hole of 100nm, the second crystallization degree of pseudo-boehmite is of a relatively high, it is possible to provide micron-sized hole, again because of it
Acidity indexes is high, presents extremely hard bulk after drying, and after being pulverized, 100% passes through 50 mesh, not only can
Increase the quantity of micrometer grade hole, also can improve the intensity of catalyst carrier.By adjusting mixing between the two
Ratio, can make the hydrotreating protective agent that intensity is high, bulk density is big, pore volume is big and wear rate is low.
CN98111379.6 discloses hydrogenation protecting catalyst and preparation method thereof, and this catalyst carrier is ultra-large aperture,
Aperture is the bimodal hole of 0.1-30 μm, and catalyst pore volume is 0.1-0.8ml/g, specific surface 0.1-
20m2/ g, containing group vib metallic element 6.65m%-20.0m and/or VIII race's metallic element 8.71% ,-
26.13m%.Preparation method is to use the granule method of piling up to prepare alumina support, then uses containing molybdenum solution and contains
Nickel solution equivalent impregnation, the catalyst after dipping is at 100-120 DEG C of dry 2-5h, 500-550 DEG C of roasting
2-5h.
CN00110019.X discloses a kind of Hydrogenation active protective agent and preparation method thereof, protective agent used carrier
Middle contain γ mono-aluminium oxide and δ-aluminium oxide simultaneously;In protective agent containing group vib metal-oxide 3-22m% and
VIII family metal oxide 0.5-5m%, containing IA family metal oxide 0-2m%, phosphorous 0-3m%, specific surface 100-
250m2/g.Pore volume 0.4-0.8ml/g.
CN200910206230.2 discloses a kind of hydrotreating guard catalyst for residual oil and application thereof.This catalyst pores
Rong great, aperture is big, and porosity is high, reasonable pore distribution, and outer surface orifice is relatively big, and duct penetrability is good,
More than 1000nm contains more than 36% in duct.In particular in residue fixed-bed hydrogenation method, can make
The metal of abjection homogeneously precipitates in whole beds, impurity vanadium and calcium and can be deposited in inside duct, carries
The high utilization rate of hole, keeps long-term operation.
CN1765509A discloses a kind of macropore alumina supporter, with aluminium oxide as main component, containing oxidation
Boron, it is characterised in that boron oxide weight content in the carrier is 1.0%～15.0%, average pore size 10～
20nm, carrier >=350 DEG C of meleic acids are 0.05～0.3mmol/g, the pore volume of carrier be 0.5～
1.0cm3/ g, specific surface area is 150～270m2/g.This patent controls to introduce boron in aluminium oxide precursor
Temperature, claims to adopt in this way while obtaining macropore alumina supporter, and the acid amount in carrier increases.
Above-mentioned prior art, for the problem in hydrogenation protecting catalyst use, gives various different solution
Scheme.But, when this kind of catalyst is used for processing of heavy oil, its performance still suffers from the sky of significant improvement
Between.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of hydrogenation protecting new, that hold metal ability higher and urges
Agent and its preparation method and application.
Usually, prepare hydrogenation protecting catalyst carrier and there is bimodal porous.The present inventor sends out
Existing, the feature that the aluminium oxide article shaped with bimodal porous of prior art offer is universal is, in bimodal hole
The aperture of macroperforation or (such as, more than 1000nm disclosed in CN200910206230.2) bigger than normal.
When being used for preparing hydrogenation protecting catalyst by this kind of carrier, it holds metallicity and still suffers from the biggest improvement
Space.
The content that the present invention relates to includes:
1, a kind of hydrogenation protecting catalyst, containing have structure of double peak holes containing at least one selected from boron, silicon
With the alumina support of fluorine auxiliary agent, with mercury injection method characterize, the pore volume of described carrier be 0.3-0.8 milliliter/
Gram, specific surface area is 70-220 rice2/ gram, wherein, the pore volume in a diameter of 6-10nm hole accounts for total pore volume
8-25%, the pore volume in a diameter of 85-160nm hole accounts for the 40-75% of total pore volume.
2, according to the hydrogenation protecting catalyst described in 1, it is characterised in that the pore volume of described carrier is 0.4-
0.7 ml/g, specific surface area is 80-210 rice2/ gram, wherein, the pore volume in a diameter of 6-10nm hole accounts for
The 10-20% of total pore volume, the pore volume in a diameter of 85-160nm hole accounts for the 45-70% of total pore volume.
3. according to the catalyst described in 1, it is characterised in that described auxiliary agent boron in terms of oxide, the containing of silicon
Amount is for 0.1-8 weight %, and the Oil repellent counted with element is for 0.1-8 weight %.
4. according to the catalyst described in 3, it is characterised in that described auxiliary agent boron in terms of oxide, the containing of silicon
Amount is for 1-6 weight %, and the Oil repellent counted with element is for 1-6 weight %.
5. according to the catalyst described in 4, it is characterised in that described auxiliary agent boron in terms of oxide, the containing of silicon
Amount is for 1-4 weight %, and the Oil repellent counted with element is for 1-4 weight %.
6. according to the catalyst described in 1, it is characterised in that the hydrogenation active metals component in described catalyst
Selected from least one metal component of group VIII and at least one metal component of group VIB, in terms of oxide and with
On the basis of catalyst, the content of described VIII race's metal component is more than 0 to less than or equal to 4 weight %, the VIth B
The content of race's metal component is more than 0 to less than or equal to 10 weight %.
7. according to the catalyst described in 6, it is characterised in that described metal component of group VIII selected from cobalt and/
Or nickel, metal component of group VIB is selected from molybdenum and/or tungsten, counts and on the basis of catalyst by oxide, described
The content of VIII race's metal component is 1-3 weight %, and the content of metal component of group VIB is 3-6 weight %.
8., according to the preparation method of the hydrogenation activity guard catalyst described in 1, including preparation, there is bimodal hole
Structure containing at least one selected from boron, silicon and the alumina support of fluorine auxiliary agent, the preparation method bag of described carrier
Include one hydrated alumina is mixed with a kind of Alpha-alumina and introduced in the mixture and select containing at least one
From boron, silicon and the compound of fluorine auxiliary agent, molding, being dried and roasting, sintering temperature is 750-1000 DEG C, roasting
The burning time is 1-10 hour, and wherein, the hydrated alumina in terms of butt with the mixing ratio of Alpha-alumina is
15-70:30-85, the pore volume of described hydrated alumina is 0.3-1.1 ml/g, and specific surface is 150-350
Rice2/ gram, most probable bore dia 5-20nm.
9, according to the method described in 8, it is characterised in that described sintering temperature is 800-950 DEG C, during roasting
Between be 2-8 hour, wherein, the mixing ratio of the hydrated alumina counted with butt and Alpha-alumina is as 30-
70:30-70, the pore volume of described hydrated alumina is 0.35-1.0 ml/g, and specific surface is 150-300 rice2/ gram, most probable bore dia 6-15nm.
10, according to the method described in 8 or 9, it is characterised in that described hydrated alumina is selected from intending thin water aluminum
Stone.
11. according to the method described in 8, it is characterised in that on the basis of described carrier, in terms of oxide
Described auxiliary agent boron, the introduction volume of silicon make boron in final carrier, the content of silicon is 0.1-8 weight %, with element
The introduction volume of the fluorine of meter makes the content of fluorine in final carrier be 0.1-8 weight %.
12. according to the method described in 11, it is characterised in that described auxiliary agent boron in terms of oxide, the drawing of silicon
Entering that amount makes boron in final carrier, the content of silicon is 1-6 weight %, the introduction volume of the fluorine in terms of element makes finally
In carrier, the content of fluorine is 1-6 weight %.
13. according to the method described in 12, it is characterised in that described auxiliary agent boron in terms of oxide, the drawing of silicon
Entering that amount makes boron in final carrier, the content of silicon is 1-4 weight %, the introduction volume of the fluorine in terms of element makes finally
In carrier, the content of fluorine is 1-4 weight %.
14. according to the method described in 8, it is characterised in that described method is included in supported on carriers hydrogenation and lives
Property metal component, the described method in supported on carriers hydrogenation active metals component is infusion process, including preparation
The solution of the compound containing hydrogenation active metals also uses this solution impregnating carrier, be dried afterwards, roasting or
Not roasting, described hydrogenation active metals component selected from the metal component of at least one group VIB and at least one
The metal component of the VIIIth race, counts and on the basis of catalyst by oxide, the described change containing hydrogenation active metals
The consumption of compound concentration in described solution and described solution makes the metal of the group VIB in final catalyst
The content of component is more than 0 to less than or equal to 10 weight %, and the content of the metal component of described VIIIth race is more than 0
To less than or equal to 4 weight %；Described drying condition includes: temperature is 100-250 DEG C, and the time is that 1-10 is little
Time；Described roasting condition includes: temperature is 360-500 DEG C, and the time is 1-10 hour.
15. according to the method described in 14, it is characterised in that the metal component of described group VIB selected from molybdenum and/
Or tungsten, the metal component of the VIIIth race is selected from cobalt and/or nickel, counts and on the basis of catalyst by oxide, institute
State the compound containing hydrogenation active metals and make final catalyst in the concentration of described solution and the consumption of described solution
In the content of metal component of vib be 3-6 weight %, the content of the metal component of the VIIIth race is 1-3
Weight %；Described drying condition includes: temperature is 100-140 DEG C, and the time is 1-6 hour；Described roasting bar
Part includes: temperature is 360-450 DEG C, and the time is 2-6 hour.
In 16. claim 1-7, the hydrogenation activity guard catalyst described in any one processes at hydrocarbon oil hydrogenation
In application.
The catalyst provided according to the present invention, wherein, characterizes with mercury injection method, and the pore volume of described shaping carrier is
0.3-0.8 ml/g, specific surface area is 70-220 rice2/ gram, wherein, the hole body in a diameter of 6-10nm hole
The long-pending 8-25% accounting for total pore volume, the pore volume in a diameter of 85-160nm hole accounts for the 40-75% of total pore volume；Preferably
The pore volume of described shaping carrier is 0.4-0.7 ml/g, and specific surface area is 80-210 rice2/ gram, wherein,
The pore volume in a diameter of 6-10nm hole accounts for the 10-20% of total pore volume, and the pore volume in a diameter of 85-160nm hole accounts for
The 45-70% of total pore volume.
On the basis of carrier, in described carrier, the content of auxiliary agent is 0.1-8 weight %, preferably 1-6 weight
%, more preferably 1-4 weight %.Wherein, boron and silicon are in terms of oxide, and fluorine is in terms of element.
In the present invention, hydrogenation active metals component and content thereof in described catalyst are usually urged for hydrogenation protecting
Hydrogenation active metals component that agent is conventional and content, such as, selected from least one the VIIIth race's base metal group
Divide and at least one vib metals component.The metal component of preferred VIIIth race is nickel and/or cobalt, excellent
The metal component of the vib of choosing is molybdenum and/or tungsten, counts and on the basis of described catalyst by oxide,
The content of described group VIII metal is to less than or equal to 4 weight % more than 0, preferably 1～3 weight %, institute
State the content of vib metals component for more than 0 to less than or equal to 10 weight %, preferably 3～6 weight
%。
The catalyst provided according to the present invention, it is also possible to provide the property of catalyst containing any present invention that do not affects
Maybe can improve the adjuvant component of the catalyst performance that the present invention provides.As the components such as phosphorus can be contained, with unit
Element is counted and on the basis of catalyst, and the content of described auxiliary agent is less than 10 weight %, preferably 0.5-5 weight
Amount %.
According to the preparation method of the hydrogenation protecting catalyst that the present invention provides, the preparation side of wherein said carrier
Method, including being mixed with a kind of Alpha-alumina by one hydrated alumina and introducing in the mixture containing at least
A kind of selected from boron, silicon and the compound of fluorine auxiliary agent, molding, dry and roasting, sintering temperature is 750-1000
DEG C, preferably 800-950 DEG C, roasting time is 1-10 hour, preferably 2-8 hour, wherein, with dry
The hydrated alumina of base meter and the mixing ratio of Alpha-alumina be 15-70:30-85(wherein, 15-70 refers to often
In the hydrated alumina (in terms of butt) of hundred parts and the mixture of Alpha-alumina, hydrated alumina number
Value changes between 15-70, and 30-85 refers to hydrated alumina (in terms of butt) parts per hundred parts and α-oxygen
Changing in the mixture of aluminum, the value of Alpha-alumina number changes between 30-85), preferably 30-
70:30-70.The pore volume of described hydrated alumina is 0.3-1.1 ml/g, preferably 0.35-1 milliliter/
Gram, specific surface is 150-350 rice2/ gram be preferably 150-300 rice2/ gram, most probable bore dia is 5-
20nm, preferably 6-15nm.It is preferably the hydrated alumina containing boehmite.Here, described hydration
The pore volume of aluminium oxide, specific surface area and can and aperture, be in 600 DEG C of roastings 4 by described hydrated alumina
After hour, BET nitrogen absorption under low temperature characterize and obtain.
Introduce containing at least one selected from boron, silicon and fluorine in described hydrated alumina with Alpha-alumina mixture
The method of auxiliary compound is conventional method, for example, it may be directly by the desired amount of containing described adjuvant component
Compound be mixed in Alpha-alumina mixed process at aforesaid hydrated alumina.
In a concrete embodiment preparing carrier, mix with Alpha-alumina to described hydrated alumina
Introducing in compound containing at least one method being selected from boron, silicon and fluorine auxiliary compound is will to be selected from containing at least one
Boron, silicon and fluorine auxiliary compound are configured to aqueous solution, by this aqueous solution at described hydrated alumina and α-oxygen
It is mixed into or again that this is water-soluble after described hydrated alumina mixes with Alpha-alumina while changing aluminum mixing
Liquid is mixed into, aftershaping, be dried and roasting.Compound containing described auxiliary agent is in they water soluble compounds
One or more.Such as, one or more in the water-soluble inorganic salt containing described auxiliary agent.
Wherein, described Alpha-alumina can be commercially available commodity (commodity alpha-alumina), it is also possible to is
Hydrated alumina (alumina hydrate powder) is obtained through high-temperature roasting.Be enough to hydrated alumina roasting phase
Becoming under conditions of being converted into Alpha-alumina, this process can use arbitrary existing method to realize, to this
The present invention does not limit.
Depending on different, aluminium oxide shaping carrier in the present invention, requires that can be made into various easily operated molding carries
Body, the most spherical, cellular, nest like, tablet or bar shaped (Herba Trifolii Pratentis, butterfly, cylinder etc.).
Molding can be carried out according to a conventional method.When molding, such as extruded moulding, for ensureing that described molding is entered smoothly
OK, water, extrusion aid and/or adhesive can be added in described mixture, with or without expanding agent,
Then extrusion molding, is dried and roasting afterwards.Described extrusion aid, the kind of peptizer and consumption are
Known to one of skill in the art, the most common extrusion aid can be selected from sesbania powder, methylcellulose,
One or more in starch, polyvinyl alcohol, PVOH, described peptizer can be mineral acid and/or have
Machine acid, described expanding agent can be the one in starch, synthetic cellulose, polymeric alcohol and surfactant
Or it is several.Synthetic cellulose therein be preferably hydroxymethyl cellulose, methylcellulose, ethyl cellulose,
One or more in hydroxyl fiber fat alcohol polyethylene ether, polymeric alcohol be preferably Polyethylene Glycol, poly-propanol,
One or more in polyvinyl alcohol, surfactant be preferably fat alcohol polyethylene ether, fatty alkanol amide and
Its derivant, molecular weight be the one in the propenyl copolymer of 200-10000 and maleic acid copolymer or
Several.
In the present invention, described molding, dry and roasting method are conventional method.Wherein, the condition of roasting
Preferably including sintering temperature and be 750-1000 DEG C, roasting time is 1-10 hour, further preferred roasting
Condition includes that sintering temperature is 800-950 DEG C, and roasting time is 2-8 hour.
According to the preparation method of the hydrogenation protecting catalyst that the present invention provides, add including introducing on described carrier
The step of hydrogen activity metal component, hydrogenation active metals component therein is selected from least one the VIIIth race's non-noble gold
Belong to and the combination selected from least one vib metals.Preferably the metal component of vib be molybdenum and/
Or tungsten, to count and on the basis of described catalyst by oxide, the introduction volume of described vib metals component makes
In final catalyst, the content of group vib metal component is to less than or equal to 10 weight % more than 0, is preferably
3～6 weight %, the introduction volume of described metal component of group VIII makes metal component of group VIII in final catalyst
Content is to less than or equal to 4 weight % more than 0, preferably 1～3 weight %.
On described carrier introduce hydrogenation active metals component can be those skilled in the art inform any
Method, for example, it is possible to by with described in the solution impregnation of the compound containing described hydrogenation active metals component
Carrier, is dried, roasting or the step of not roasting afterwards.
In the present invention, the described compound containing vib metals selected from they soluble compound in
One or more.Such as, the one during the compound containing molybdenum can be molybdenum oxide, molybdate, paramolybdate
Or several, molybdenum oxide preferably wherein, ammonium molybdate, ammonium paramolybdate；Tungstenic compound is selected from tungstates, partially
One or more in tungstates, ethyl metatungstate, ammonium metatungstate preferably wherein, ethyl metatungstic acid
Ammonium.
The described compound containing group VIII metal selected from they soluble compound in one or more.
Such as, one during the compound containing cobalt can be cobalt nitrate, cobaltous acetate, basic cobaltous carbonate, cobaltous chloride or
Several, preferably cobalt nitrate, basic cobaltous carbonate；Nickel compound containing can be nickel nitrate, nickel acetate, alkali formula
One or more in nickelous carbonate, Nickel dichloride., preferably nickel nitrate, basic nickel carbonate.
According to the present invention, various solvents commonly used in the art can be used to prepare containing described active component
The solution of compound, as long as described compound can be dissolved in described solvent, forms the solution of stable homogeneous
?.Such as: described solvent can be water or alcohol (such as: ethanol) that carbon number is 1～5, is preferably
Water and/or ethanol, more preferably water.
The method of described dipping can be various dipping methods commonly used in the art, such as, can be the saturated leaching in hole
Stain method.The present invention was not particularly limited for the time of described dipping and the number of times of dipping, as long as being able to ensure that
The amount of the active component with catalytic action on the catalyst finally given meets concrete use and requires i.e.
Can.Usually, the time of described dipping can be 0.5～12 hour.
According to the present invention, the carrier for the compound by being loaded with described hydrogenation active metals component is done
Dry method and condition are not particularly limited.Usually, described dry temperature can be 80～350 DEG C,
It is preferably 100～300 DEG C；The described dry time can be 0.5～24 hour, and preferably 1～12 is little
Time.
When catalyst after drying needs to carry out roasting, described method of roasting and condition are not had by the present invention
It is particularly limited to, can be conventional method and the condition of this area.Usually, the temperature of described roasting is permissible
It is 350～650 DEG C, preferably 400～500 DEG C；The time of described roasting can be 0.2～12 hour,
It is preferably 1～10 hour.Described roasting can be carried out in oxygen-containing atmosphere, it is also possible to enters in an inert atmosphere
OK.
The preparation method provided according to the present invention, when in described catalyst possibly together with during selected from components such as phosphorus, also
Including introducing the step of the components such as phosphorus, the introducing method of the component such as described phosphorus can pass through number of ways, example
As, can be that direct for the compound containing the described auxiliary agent mixture with hydrated alumina with Alpha-alumina is mixed
Conjunction, molding roasting；Can be by the compound containing described auxiliary agent and containing hydrogenation active metals component
Compound contacts with described carrier after being configured to mixed solution；Can also is that independent for the compound containing auxiliary agent
Contact and roasting with described carrier after preparation solution.When auxiliary agent and hydrogenation active metals introduce described carrier respectively
Time, first contact and roasting with described carrier with containing auxiliary compound solution, add with containing the most again
The solution contact of the compound of hydrogen activity metal component, such as, by the method for dipping, described sintering temperature is
250-600 DEG C, preferably 350-500 DEG C, roasting time is 2-8 hour, preferably 3-6 hour.
The protective agent that the present invention provides is applicable to the protective agent when heavier hydrocarbon feeds is processed, the suitableeest
Also include the protective agent of decompression residuum for making the heavy raw oil of high-sulfur height nitrogen height tenor inferior, adding
This protective agent is loaded on hydrogen catalyst top, can effectively solve industry hydrogenation plant bed fouling, blocking, pressure drop
Excessive and be forced stop work problem, extend downstream hydrogenation catalyst service life.
Detailed description of the invention
The present invention is described further for example below.
Agents useful for same in example, except as expressly described, is chemically pure reagent.
Pressure hydrargyrum method (RIPP149-90) measures the specific surface area of aluminium oxide shaping carrier, pore volume and hole and divides
(Yang Cui is fixed, Petrochemical Engineering Analysis method, publishing house of academy of science, 1990,421-423 for cloth etc.
Page).
BET nitrogen absorption under low temperature method (RIPP151-90) measure the specific surface area of hydrated alumina, pore volume with
And pore size distribution etc. (Yang Cui is fixed, Petrochemical Engineering Analysis method, publishing house of academy of science, 1990,424-
Page 426).
Butt assay method is for taking appropriate amount of sample, in 600 DEG C of roasting temperature 3h, afterwards, after calculating roasting
Before sample and roasting, the mass percent of sample, is the butt of this sample.
XRF method (RIPP132-90) is used to measure auxiliary agent and the content (poplar of active metal component in catalyst
Kingfisher is fixed, Petrochemical Engineering Analysis method, publishing house of academy of science, and 1990, the 371-375 page).
Embodiment 1
(being available commercially from Yantai Heng Hui Chemical Co., Ltd., butt is 72 weight % to weigh 200g hydrated alumina.
Pore volume is 0.50 ml/g, and specific surface area is 290 meters2/ gram, most probable bore dia is 7nm), 70 grams
Alpha-alumina (by the present embodiment use hydrated alumina at 1400 DEG C roasting 6 hours and
Become), after 9 grams of sesbania powder mixing and 15 grams of Borax mix homogeneously, by this mixture with concentration be at room temperature
The ammonia spirit of 4% 220 milliliters mixing, after mix homogeneously, kneading use φ in double screw banded extruder
The cylindrical orifice plate extrusion of 2.0mm, afterwards, wet bar is little in 850 DEG C of roastings 2 after 120 DEG C are dried 4 hours
Time, obtain carrier T-1 of the present invention.Measure the specific surface of carrier T-1, can several apertures, pore volume, hole divide
Cloth, the results are shown in Table 1.
Embodiment 2
(being available commercially from Zibo neat cyclopentadienyl catalyst factory, butt is 68 weight % to weigh 180g dry glue powder.Pore volume is
0.55 ml/g, specific surface area is 278 meters2/ gram, most probable bore dia is 8nm), 120 grams of α-oxygen
Change aluminium powder (being available commercially from Beijing Shun Chuan Environmental Protection Technology Co., Ltd), 9 grams of sesbania powder mixing and 8 grams of boron oxides
Mix homogeneously, adds the aqueous solution 205 milliliters containing 10 grams of sodium borate, afterwards at double spiral shells after mix homogeneously
Kneading extruding with the cylindrical orifice plate of φ 2.0mm in bar banded extruder, afterwards, wet bar is dried 4 through 120 DEG C
In 850 DEG C of roastings 2 hours after hour, obtain carrier T-2 of the present invention.Measure carrier T-2 specific surface,
Can several apertures, pore volume, pore size distribution, the results are shown in Table 1.
Embodiment 3
(being available commercially from Yantai Heng Hui Chemical Co., Ltd., butt is 72 weight % to weigh 150g dry glue powder.Pore volume
Being 0.50 ml/g, specific surface area is 255 meters2/ gram, most probable bore dia is 9nm), 150 grams of α-
Alumina powder (with embodiment 2), 9 grams of sesbania powder, 9 grams of methylcellulose and 20 grams of Borax mixing are all
Even, add the aqueous solution 205 milliliters mixing containing 35 grams of ammonium hydrogen carbonate afterwards, according to rolling after mix homogeneously
Ball forming method molding, obtaining particle diameter is 5.5-6.5mm spheroidal particle.Wet bar is dried 4 hours through 120 DEG C
After in 800 DEG C of roastings 2 hours, obtain carrier T-3 of the present invention.Measure carrier T-3 specific surface, can be several
Aperture, pore volume, pore size distribution, the results are shown in Table 1.
Embodiment 4
Weigh 260g dry glue powder (with embodiment 1), 140 grams of alpha-aluminas (with embodiment 1), 9
Gram sesbania powder, 9 grams of methylcellulose and 10 grams of "Antifungin". mix homogeneously, add afterwards containing 10 grams of boric acid
5% ammonia spirit 206 milliliters mixing, after mix homogeneously in double screw banded extruder kneading use φ
The cylindrical orifice plate extrusion of 2.0mm, wet bar in 800 DEG C of roastings 2 hours, obtains after 120 DEG C are dried 4 hours
To carrier T-4 of the present invention.Measure carrier T-4 specific surface, can several apertures, pore volume, the results are shown in Table 1.
Embodiment 5
Weigh 260g dry glue powder (with embodiment 2), 140 grams of alpha-aluminas (with embodiment 1), 9
Gram sesbania powder, 9 grams of methylcellulose mixing, add containing 7.5 grams of nitric acid afterwards, ammonium fluosilicate (is analyzed
Pure, Shanghai reagent three factory) aqueous solution 230 milliliters of 6 grams, extruded moulding after mix homogeneously, wet bar warp
120 DEG C are dried after 4 hours in 800 DEG C of roastings 2 hours, obtain carrier T-4 of the present invention.Measure carrier T-4
Specific surface, can several apertures, pore volume, the results are shown in Table 1.
Comparative example 1
Weigh 300 grams of dry glue powders (with embodiment 3), 9 grams of sesbania powder, add containing nitric acid after mix homogeneously
200 milliliters of mixed-formings of the solution of 12 grams, wet bar is dried after 4 hours in 850 DEG C of roastings 2 through 120 DEG C
Hour, obtain carrier D-1.Measure carrier D-1 specific surface, can several apertures, pore volume, the results are shown in Table
1。
Comparative example 2
(being available commercially from Chang Ling oil refining catalyst factory, butt is 65 weight % to weigh 300 grams of dry glue powders.Pore volume is
0.8 ml/g, specific surface area is 320 meters2/ gram, most probable bore dia is 9nm), 9 grams of sesbania powder,
Adding the 200 milliliters of mixed-formings of solution containing 12 grams of nitric acid after mix homogeneously, it is little that wet bar is dried 4 through 120 DEG C
In in 850 DEG C of roastings 2 hours time after, obtain carrier D-2.Measure carrier D-2 specific surface, can several holes
Footpath, pore volume, the results are shown in Table 1.
Comparative example 3
((being available commercially from Chang Ling oil refining catalyst factory, butt is 65 weight % to weigh dry glue powder.Pore volume is 0.8
Ml/g, specific surface area is 290 meters2/ gram, most probable bore dia is 10nm)) 300 grams, add carbon
24 grams of black powder, the mixing of 12 grams of sesbania powder, add afterwards containing the phosphoric acid 2.4 grams that concentration is 85 weight %
Aqueous solution 260 milliliters, kneading 15 minutes, double screw banded extruder is extruded into the butterfly bar of Φ 1.5mm,
Wet bar in 950 DEG C of roastings 2 hours, obtains carrier D-3 after 120 DEG C are dried 4 hours.Measure carrier D-3
Specific surface, can several apertures, pore volume, the results are shown in Table 1.
Comparative example 4
(being available commercially from Chang Ling oil refining catalyst factory, butt is 65 weight % to weigh 300 grams of dry glue powders.Pore volume
Being 0.65 ml/g, specific surface area is 288 meters2/ gram, most probable bore dia is 9nm), 9 grams of sesbanias
Powder and 20 grams of Borax mix homogeneously, add the aqueous solution 360 milliliters mixing containing 35 grams of ammonium hydrogen carbonate afterwards
Molding, wet bar in 950 DEG C of roastings 2 hours, obtains carrier D-4 after 120 DEG C are dried 4 hours.Measure
The specific surface of carrier D-4, can several apertures, pore volume, the results are shown in Table 1.
Table 1
The result that table 1 is given shows, the alumina support that the present invention provides is except having bigger most probable hole
Footpath, and pore size distribution to be concentrated mainly on bore dia be 6-10nm and 85-160nm, be i.e. 6-10nm at bore dia
It is obvious bimodal distribution with 85-160nm scope.
Embodiment 6
Take drying and roasting after 100 grams of T1 dippings of carrier, (contain with saturated leaching mode molybdenum oxide containing 1.2g
MoO399.9%) and the solution 82 milliliters dipping of 0.7g nickel nitrate (containing NiO25%), 120 after dipping
DEG C be dried 4 hours, 420 DEG C of roastings 3 hours guard catalyst TC-1 of the present invention.Wherein, hydrogenation is lived
The content of property metal component is listed in table 2.
Embodiment 7
Take 100 grams of T2 of carrier, in saturated leaching mode with the ammonium molybdate containing 6.42g (containing MoO382%) and 4.35g
The solution of nickel nitrate (containing NiO51%) 80 milliliters dipping, is dried 4 hours at 120 DEG C after dipping,
420 DEG C of roastings obtain guard catalyst TC-2 of the present invention in 3 hours.Wherein, the content of hydrogenation active metals component
It is listed in table 2.
Embodiment 8
Take 20 grams of T3 of carrier, in saturated leaching mode with the ammonium molybdate containing 1.2g (containing MoO382%) and 2.0g nitre
The solution 15 milliliters dipping of acid nickel (containing NiO25%), is dried 4 hours at 120 DEG C after dipping, at 420 DEG C
Roasting obtains guard catalyst TC-3 of the present invention in 3 hours.Wherein, the content of hydrogenation active metals component is listed in table
2。
Embodiment 9
Take 20 grams of T4 of carrier, in saturated leaching mode with the ammonium molybdate containing 0.86g (containing MoO382%) and 1.25g
The solution of nickel nitrate (containing NiO25%) 16 milliliters dipping, is dried 4 hours at 120 DEG C after dipping, 420
DEG C roasting 3 hours guard catalyst TC-4 of the present invention.Wherein, the content of hydrogenation active metals component is listed in
Table 2.
Embodiment 10
Take 20 grams of T5 of carrier, in saturated leaching mode with the ammonium molybdate containing 1.45g (containing MoO382%) and 1.30g
The solution of nickel nitrate (containing NiO25%) 13 milliliters dipping, is dried 4 hours at 120 DEG C after dipping, 420
DEG C roasting 3 hours guard catalyst TC-5 of the present invention.Wherein, the content of hydrogenation active metals component is listed in
Table 2.
Comparative example 5
Take 20 grams of D4 of carrier, in saturated leaching mode with the ammonium molybdate containing 1.2g (containing MoO382%) and 2.0g nitre
The solution 12 milliliters dipping of acid nickel (containing NiO25%), is dried 4 hours at 120 DEG C after dipping, at 420 DEG C
Roasting obtains guard catalyst DC-1 of the present invention in 3 hours.Wherein, the content of hydrogenation active metals component is listed in table
2。
Comparative example 6
Take 20 grams of D1 of carrier, in saturated leaching mode with the ammonium molybdate containing 0.86g (containing MoO382%) and 1.25g
The solution of nickel nitrate (containing NiO25%) 11 milliliters dipping, is dried 4 hours at 120 DEG C after dipping, 420
DEG C roasting 3 hours guard catalyst DC-2 of the present invention.Wherein, the content of hydrogenation active metals component is listed in
Table 2.
Table 2
The embodiment 11-12 explanation present invention provides hydrogenation protecting agent performance prepared by carrier.
Embodiment 11
Evaluating protective agent TC-1 on the medium-sized evaluating apparatus of 200ml, raw materials used oil is for mixing slag poor quality wax
Oil.Appreciation condition is reaction temperature 360 DEG C, hydrogen dividing potential drop 8.0MPa, volume space velocity 0.8h-1, hydrogen oil volume
Compare 700:1.Evaluate after 2000h Fe deposition and coke content in sample analysis protective agent.Result is listed in table
3。
XRF method (XRF semi-quantitative analysis (B-U)) is used to measure element of Fe content in solid sample.
(Yang Cui is fixed, stone to use infrared absorption method (RIPP106-90) to measure carbon deposit content in protective agent
Oiling work point analysis method, publishing house of academy of science, page 1990,302).
Embodiment 12
According to condition evaluating protective agent TC-2 identical with example 11, evaluate sample analysis after 2000h
Fe deposition and coke content in protective agent.Result is listed in table 3.
Comparative example 7
According to the condition evaluating DC-1 identical with example 11.Fe in sample analysis protective agent after evaluation 2000h
Deposition and coke content.Result is listed in table 3.
Comparative example 8
According to the condition evaluating DC-2 identical with example 11.Fe in sample analysis protective agent after evaluation 2000h
Deposition and coke content.Result is listed in table 3.
Table 3
| Example number | Catalyst is numbered | Fe deposits total amount, w% | Carbon content, w% |
| Embodiment 11 | TC-1 | 1.85 | 11.0 |
| Embodiment 12 | TC-2 | 1.98 | 10.3 |
| Comparative example 7 | DC-1 | 0.37 | 17.87 |
| Comparative example 8 | DC-2 | 0.2 | 18.8 |
Above evaluation result shows, compared with the hydrogenation protecting agent that prior art provides, the present invention provides
The protective agent prepared by carrier hold metal ability and anti-carbon deposition ability and significantly improve.
Claims (15)
1. a hydrogenation protecting catalyst, containing have structure of double peak holes containing at least one selected from boron,
Silicon and the alumina support of fluorine auxiliary agent, characterize with mercury injection method, and the pore volume of described carrier is 0.3-0.8 milli
Rise/gram, specific surface area is 70-220 rice2/ gram, wherein, the pore volume in a diameter of 6-10nm hole accounts for always
The 8-25% of pore volume, the pore volume in a diameter of 85-160nm hole accounts for the 40-75% of total pore volume；Described urge
Hydrogenation active metals component in agent is selected from least one metal component of group VIII and at least one the VIth B
Race's metal component, counts and on the basis of catalyst by oxide, and the content of described VIII race's metal component is big
In 0 to less than or equal to 4 weight %, the content of metal component of group VIB is more than 0 to less than or equal to 10
Weight %.
Hydrogenation protecting catalyst the most according to claim 1, it is characterised in that described carrier
Pore volume is 0.4-0.7 ml/g, and specific surface area is 80-210 rice2/ gram, wherein, a diameter of 6-
The pore volume in 10nm hole accounts for the 10-20% of total pore volume, and the pore volume in a diameter of 85-160nm hole accounts for total hole
The 45-70% held.
Hydrogenation protecting catalyst the most according to claim 1, it is characterised in that in terms of oxide
Described auxiliary agent boron, the content of silicon be 0.1-8 weight %, the Oil repellent counted with element is for 0.1-8 weight
Amount %.
Hydrogenation protecting catalyst the most according to claim 3, it is characterised in that in terms of oxide
Described auxiliary agent boron, the content of silicon be 1-6 weight %, the Oil repellent counted with element is for 1-6 weight %.
Hydrogenation protecting catalyst the most according to claim 4, it is characterised in that in terms of oxide
Described auxiliary agent boron, the content of silicon be 1-4 weight %, the Oil repellent counted with element is for 1-4 weight %.
Hydrogenation protecting catalyst the most according to claim 1, it is characterised in that described VIIIth race
Metal component is selected from cobalt and/or nickel, and metal component of group VIB is selected from molybdenum and/or tungsten, in terms of oxide also
On the basis of catalyst, the content of described VIII race's metal component is 1-3 weight %, group VIB metal group
The content divided is 3-6 weight %.
The preparation method of hydrogenation protecting catalyst the most according to claim 1, has including preparation
Structure of double peak holes containing at least one selected from boron, silicon and the alumina support of fluorine auxiliary agent, described carrier
Preparation method includes one hydrated alumina is mixed with a kind of Alpha-alumina and introduced in the mixture
Containing at least one selected from boron, silicon and the compound of fluorine auxiliary agent, molding, it is dried and roasting, sintering temperature
For 750-1000 DEG C, roasting time is 1-10 hour, wherein, and the hydrated alumina in terms of butt and α
The mixing ratio of-aluminium oxide is 15-70:30-85, the pore volume of described hydrated alumina be 0.3-1.1 milliliter/
Gram, specific surface area is 150-350 rice2/ gram, most probable bore dia 5-20nm.
Preparation method the most according to claim 7, it is characterised in that described sintering temperature is
800-950 DEG C, roasting time is 2-8 hour, wherein, and the hydrated alumina in terms of butt and α-oxygen
Change aluminum mixing ratio be 30-70:30-70, the pore volume of described hydrated alumina be 0.35-1.0 milliliter/
Gram, specific surface area is 150-300 rice2/ gram, most probable bore dia 6-15nm.
9. according to the preparation method described in claim 7 or 8, it is characterised in that described aqua oxidation
Aluminum is selected from boehmite.
Preparation method the most according to claim 7, it is characterised in that with described carrier as base
Standard, the described auxiliary agent boron in terms of oxide, the introduction volume of silicon make boron in final carrier, the content of silicon is
0.1-8 weight %, the introduction volume of the fluorine counted with element makes in final carrier the content of fluorine for 0.1-8 weight
Amount %.
11. preparation methoies according to claim 10, it is characterised in that the institute in terms of oxide
State auxiliary agent boron, the introduction volume of silicon makes boron in final carrier, the content of silicon is 1-6 weight %, in terms of element
The introduction volume of fluorine make the content of fluorine in final carrier be 1-6 weight %.
12. preparation method according to claim 11, it is characterised in that the institute in terms of oxide
State auxiliary agent boron, the introduction volume of silicon makes boron in final carrier, the content of silicon is 1-4 weight %, in terms of element
The introduction volume of fluorine make the content of fluorine in final carrier be 1-4 weight %.
13. preparation methoies according to claim 7, it is characterised in that described method is included in load
Hydrogenation active metals component, the described method in supported on carriers hydrogenation active metals component is loaded on body
For infusion process, including the solution of the preparation compound containing hydrogenation active metals and carry by this solution impregnation
Body, is dried, roasting or not roasting afterwards, and described hydrogenation active metals component is selected from least one
The metal component of group VIB and the metal component of at least one the VIIIth race, in terms of oxide and with catalyst
On the basis of, the described compound containing hydrogenation active metals concentration in described solution and described solution
Consumption makes the content of the metal component of the group VIB in final catalyst more than 0 to less than or equal to 10 weights
Amount %, the content of the metal component of described VIIIth race is more than 0 to less than or equal to 4 weight %；Described dry
Condition includes: temperature is 100-250 DEG C, and the time is 1-10 hour；Described roasting condition includes: temperature
Degree is for 360-500 DEG C, and the time is 1-10 hour.
14. preparation methoies according to claim 13, it is characterised in that the gold of described group VIB
Belonging to component and be selected from molybdenum and/or tungsten, the metal component of the VIIIth race is selected from cobalt and/or nickel, in terms of oxide also
On the basis of catalyst, the described compound containing hydrogenation active metals is in the concentration of described solution and described
The consumption of solution makes the content of the metal component of the vib in final catalyst be 3-6 weight %, the
The content of the metal component of VIII race is 1-3 weight %；Described drying condition includes: temperature is 100-
140 DEG C, the time is 1-6 hour；Described roasting condition includes: temperature is 360-450 DEG C, and the time is
2-6 hour.
In 15. claim 1-6, the hydrogenation protecting catalyst described in any one is in hydrocarbon oil hydrogenation processes
Application.
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| CN1188216C (en) * | 2002-10-10 | 2005-02-09 | 中国石油化工股份有限公司 | Method for preparing alumina supporter |
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