CN104368350B - A kind of hydrogenation protecting catalyst and preparation method and application - Google Patents
A kind of hydrogenation protecting catalyst and preparation method and application Download PDFInfo
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Abstract
A kind of hydrogenation protecting catalyst and preparation method and application; this catalyst contains carrier and load hydrogenation active metals component on this carrier; described carrier is the aluminium oxide article shaped with structure of double peak holes; characterized with mercury injection method; the pore volume of described article shaped is 0.3 0.8 mls/g, and specific surface area is 70 220 meters2/ gram, the pore volume in a diameter of 6 10nm holes accounts for the 8 25% of total pore volume, the pore volume in a diameter of 85 160nm holes accounts for the 40 75% of total pore volume, described hydrogenation active metals group is selected from least one metal component of group VIII and at least one Group VB metal component, counted and on the basis of catalyst by oxide, the content of described metal component of group VIII is that the content of Group VB metal component is to less than or equal to 5 weight % more than 0 more than 0 to less than or equal to 0.8 weight %.Compared with prior art, the hydrogenation protecting catalyst that the present invention provides has more preferable appearance metallicity.
Description
Technical field
The present invention relates to a kind of hydrogenation protecting catalyst and preparation method and application.
Background technology
It is deteriorated with crude quality, in crude oil, the impurity content such as colloid, asphalitine and organo-metallic compound increases, these
The presence of impurity easily causes the rapid decrease of catalyst activity so that inactivating.The effective ways solving this problem are to add
The filling of hydrogen catalyst bed top has the protective agent of hydrogenation activity.There is the hydrogenation protecting catalyst of larger pore volume and bore dia
Hold metal and hold charcoal ability by force, the effect of protection downstream hydrogenation host can be played, extend the service life of host.
In prior art with regard to hydrogenation protecting catalyst and its preparation example such as：
CN200610113493.5 discloses a kind of hydrogenation protecting agent and its preparation, and it is many that this protective agent contains one or more
The heat-resistant inorganic oxide in hole it is characterised in that the total pore volume of described protective agent be 0.3-1.5 millimeter/gram, wherein contain in the least
Meter level macropore, grade macropore bore dia is 0.1～1.5 micron, and grade macropore pore volume is 0.05～0.7 ml/g.Described
The preparation method of hydrogenation protecting agent, including by the heat resistant inorganic of the heat-resistant inorganic oxide of one or more porous and/or porous
The precursor of oxide mix with least one Organic substance, molding, drying roasting, wherein, described organic compound is fusing point
Between 30～200 DEG C, 0.3～2.5 millimeter of particle diameter and water-fast solid particle.
CN201010220850.4 discloses a kind of protectant preparation method of hydrotreating.Alumina support in the method
It is the boehmite dry glue powder kneading method preparations different using two kinds, then supported active metals；Wherein the first plan is thin
Diaspore degree of crystallinity is relatively small, and pore volume is big, it is possible to provide the hole of bore dia 30nm～100nm, and second boehmite crystallizes
Degree is of a relatively high, it is possible to provide micron-sized hole, and because its acidity indexes is high, presents extremely hard bulk, pulverized after being dried
100% passes through 50 mesh afterwards, not only can increase the quantity of micrometer grade hole, also can improve the intensity of catalyst carrier.By adjusting two
Mixed proportion between person, 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 0.1-30 μm of bimodal hole, and catalyst pore volume is 0.1-0.8ml/g, specific surface 0.1-20m2/ g, containing group vib gold
Belong to element 6.65m%-20.0m and/or VIII race's metallic element 8.71%, -26.13m%.Preparation method is to pile up method using granule
Prepare alumina support, then adopt containing molybdenum solution and solution containing nickel equivalent impregnation, the catalyst after dipping is at 100-120 DEG C
2-5h is dried, in 500-550 DEG C of roasting 2-5h.
CN00110019.X discloses a kind of Hydrogenation active protective agent and preparation method thereof, in protective agent used carrier simultaneously
Containing γ mono- aluminium oxide and δ-aluminium oxide；The 3-22m% of metal-oxide containing group vib and VIII family metal oxide 0.5- in protective agent
5m%, the 0-2m% of family metal oxide containing IA, 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 its application.This catalyst pore volume is big,
Aperture is big, and porosity is high, reasonable pore distribution, and outer surface orifice is larger, and duct penetrability is good, and more than 1000nm contains 36% in duct
More than.In particular for the metal of abjection in residue fixed-bed hydrogenation method, can be made to homogeneously precipitate in whole beds,
Impurity vanadium and calcium can be deposited in inside duct, improve the utilization rate of hole, keep long-term operation.
Above-mentioned prior art is directed to the problem in hydrogenation protecting catalyst use, gives various different solutions.
It is not difficult to find out, carrier porous therein（Including pore volume, aperture, the property such as pore size distribution）Directly decide the property of such catalyst
Energy.
Content of the invention
The technical problem to be solved in the present invention be provide a kind of new aluminium oxide article shaped with bimodal pore distribution and its
Preparation method, and the hydrogenation protecting catalyst using the preparation of this carrier.
Content according to the present invention includes：
1st, a kind of hydrogenation protecting catalyst, containing carrier and load hydrogenation active metals component on this carrier, described
Carrier is the aluminium oxide article shaped with structure of double peak holes, is characterized with mercury injection method, described molding
The pore volume of thing is 0.3-0.8 ml/g, and specific surface area is 70-220 rice2/ gram, 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, described hydrogenation active metals
Group is selected from least one metal component of group VIII and at least one Group VB metal component, in terms of oxide and with catalyst is
Benchmark, the content of described metal component of group VIII is to less than or equal to 0.8 weight %, the content of Group VB metal component more than 0
It is to less than or equal to 5 weight % more than 0.
2nd, the catalyst according to 1, it is characterised in that the pore volume of described article shaped is 0.4-0.7 ml/g, compares table
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, a diameter of 85-160nm
The pore volume in hole accounts for the 45-70% of total pore volume；Described metal component of group VIII is selected from nickel and/or cobalt, and Group VB metal component selects
From vanadium and/or niobium, counted and on the basis of catalyst by oxide, the content of described metal component of group VIII is 0.1-0.7 weight
Amount %, the content of Group VB metal component is 1-4 weight %.
3rd, it is characterised in that being counted and on the basis of catalyst by oxide, described VIII race is golden for the catalyst according to 2
The content belonging to component is 0.1-0.6 weight %, and the content of the Vth B race metal component is 1.5-3.5 weight %.
4th, the catalyst according to 1 is it is characterised in that containing selected from one of IA and IIA in described article shaped
Or several adjuvant component, counted and on the basis of described article shaped total amount by oxide, the content of described adjuvant component is 10 weight %
Below.
5th, the catalyst according to 4 is it is characterised in that described IA is selected from one or more of lithium, sodium and potassium, described
IIA is selected from one or more of magnesium, calcium and barium, is counted and on the basis of described article shaped total amount by oxide, described auxiliary agent group
The content divided is 2.5-5.5 weight %.
6th, a kind of preparation method of hydrogenation protecting catalyst, comprises the steps：
（1）Prepare carrier, including a kind of hydrated alumina is mixed with a kind of Alpha-alumina, molding, drying roasting, roasting
Burn temperature and be 750-1000 DEG C, roasting time is 1-10 hour, wherein, hydrated alumina in terms of butt is mixed with Alpha-alumina
Composition and division in a proportion 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；
（2）In step（1）Hydrogenation active metals component is introduced on the carrier obtaining, described hydrogenation active metals group is selected from
At least one metal component of group VIII and at least one Group VB metal component, are counted and on the basis of catalyst by oxide, institute
Stating the introduction volume of metal component of group VIII, to make the content of the metal component of group VIII in final catalyst be to being less than or equal to more than 0
0.8 weight %, it is big that the introduction volume of described Group VB metal component makes the content of the Group VB metal component in final catalyst
In 0 to less than or equal to 5 weight %, it is dried afterwards and roasting, described drying condition includes：Temperature is 100-250 DEG C, and the time is
1-10 hour, roasting condition includes：Temperature is 360-500 DEG C, and the time is 1-10 hour.
7th, the method according to 6 is it is characterised in that described step（1）In sintering temperature be 800-950 DEG C, roasting
Time is 2-8 hour, and the hydrated alumina counted with butt and the mixing ratio of Alpha-alumina are as 30-70:30-70, described hydration oxygen
The pore volume changing aluminum is 0.35-1 ml/g, and specific surface is 150-300 rice2/ gram, most probable bore dia 6-15nm；Described VIIIth race
Metal component be selected from nickel and/or cobalt, the metal component of Group VB is selected from vanadium and/or niobium, in terms of oxide and with catalyst is
Benchmark, it is 0.1-0.7 that the introduction volume of described metal component of group VIII makes the content of the metal component of group VIII in final catalyst
Weight %, it is 1-4 weight that the introduction volume of described Group VB metal component makes the content of the Group VB metal component in final catalyst
Amount %, described step（2）Drying condition include：Temperature is 100-140 DEG C.
8th, the method according to 7 is it is characterised in that the introduction volume of described metal component of group VIII makes in final catalyst
The content of metal component of group VIII be 0.2-0.6 weight %, the introduction volume of described Group VB metal component makes final catalyst
In Group VB metal component content be 1.5-3.5 weight %.
9. the method according to 6,7 or 8 any one is it is characterised in that described introduce hydrogenation active metals on carrier
The method of component is infusion process.
10th, the method according to 6 or 8 is it is characterised in that described hydrated alumina is selected from boehmite.
11st, the method according to 6 is it is characterised in that in described step（1）By a kind of hydrated alumina and a kind of α-
In aluminium oxide mixing, including introducing the step being selected from one or more of IA and IIA adjuvant component, in terms of oxide and with institute
On the basis of stating article shaped total amount, the introduction volume of described adjuvant component is below 10 weight %.
12nd, the method according to 11 is it is characterised in that described IA is selected from one or more of lithium, sodium and potassium, described
IIA is selected from one or more of magnesium, calcium and barium, is counted and described adjuvant component on the basis of described article shaped total amount by oxide
Introduction volume be 2.5-5.5 weight %.
Hydrogenation activity guard catalyst described in any one answering in hydrocarbon oil hydrogenation process in 13. claim 1-5
With.
The article shaped providing according to the present invention, can be made into various easily operated article shaped depending on different requirements, for example spherical,
Cellular, nest like, tablet or bar shaped（Herba Trifolii Pratentis, butterfly, cylinder etc.）.Molding can be carried out according to a conventional method, for example, rolling
One of ball, tabletting and extruded moulding method or the combination of several method.In molding, such as extruded moulding, for ensureing institute
State molding to be smoothed out, water, extrusion aid and/or adhesive can be added in described material to be formed, with or without reaming
Agent, then extrusion molding, it is dried afterwards and roasting.Described extrusion aid, the species of peptizer and consumption are art technology
Well known to personnel, for example common extrusion aid can be in sesbania powder, methylcellulose, starch, polyvinyl alcohol, PVOH
One or more, described peptizer can be mineral acid and/or organic acid, and described expanding agent can be starch, synthetic fibers
One or more of element, polymeric alcohol and surfactant.Synthetic cellulose therein is preferably hydroxymethyl cellulose, methyl fibre
One or more of dimension element, ethyl cellulose, hydroxyl fiber fat alcohol polyethylene ether, polymeric alcohol is preferably Polyethylene Glycol, gathers
One or more of propanol, polyvinyl alcohol, surfactant is preferably fat alcohol polyethylene ether, fatty alkanol amide and its derives
Thing, molecular weight are one or more of propylene alcohol copolymer and maleic acid copolymer of 200-10000.
The preparation method of the aluminium oxide article shaped that the present invention provides includes hydrated alumina is mixed with Alpha-alumina, become
Type, drying roasting obtains.
Wherein, described Alpha-alumina can be commercially available commodity（Commodity alpha-alumina）Or by aqua oxidation
Aluminum（Alumina hydrate powder）Obtain through high-temperature roasting.In the condition enough to hydrated alumina roasting phase transformation to be converted into Alpha-alumina
Under, this process can be realized using arbitrary existing method, and this present invention is not limited.
Described hydrated alumina is selected from arbitrary pore volume and is 0.35-1.1 ml/g, preferably 0.35-1.0 ml/g,
Specific surface is 150-350 rice2/ gram, preferably 150-300 rice2/ gram, most probable bore dia is 5-20nm, preferably 6-15nm, enters
One step is preferably the hydrated alumina of 6-10nm；Described hydrated alumina is preferably the hydrated alumina containing boehmite.
Here, the pore volume of described hydrated alumina, specific surface area and can and aperture, be in 600 DEG C of roastings 4 by described hydrated alumina
After hour, characterized by BET nitrogen absorption under low temperature and obtain.
In the present invention, described hydrated alumina adopts conventional method with the mixing of Alpha-alumina, and meets in terms of butt
Hydrated alumina is 15-70 with the mixing ratio of Alpha-alumina:30-85（Wherein, 15-70 refers to hydrated alumina parts per hundred parts（With
Butt meter）In the mixture of Alpha-alumina, the value of hydrated alumina number changes between 15-70；30-85 refers to every hundred
The hydrated alumina of part（In terms of butt）In the mixture of Alpha-alumina, the value of Alpha-alumina number is in the anaplasia of 30-85
Change）, preferably 30-70:30-70.
In the present invention, the drying of described article shaped is conventional method and condition.The method of described roasting is conventional method,
The condition of described roasting preferably includes sintering temperature and is 600-1000 DEG C, and roasting time is 1-10 hour, further preferred roasting
Condition include sintering temperature be 700-950 DEG C, roasting time be 2-8 hour.
According in the aluminium oxide article shaped that the present invention provides, can also contain and help selected from one or more of IA and IIA
Agent component, on the basis of described article shaped total amount, the content of described adjuvant component is calculated as below 10 weight % with oxide, preferably
For 2.5 weight %-5.5 weight %.Wherein, described IA preferably is selected from one or more of lithium, sodium and potassium, further preferred sodium and/
Or potassium, described IIA preferably is selected from one or more of magnesium, calcium and barium, further preferred magnesium and/or calcium.
When also including adjuvant component in described article shaped, the preparation method of described article shaped includes introducing adjuvant component
Step, is counted and on the basis of described article shaped total amount by oxide, and the introduction volume of described adjuvant component is below 10 weight %, excellent
Elect 2.5-5.5 weight % as.
The introducing method of described adjuvant component is conventional method, for example, it may be directly by the desired amount of containing adjuvant component
Compound be mixed in aforesaid hydrated alumina with the mixed process of Alpha-alumina, or the compound containing adjuvant component is joined
Make aqueous solution, afterwards this aqueous solution is mixed in aforesaid hydrated alumina with the mixed process of Alpha-alumina.
In an embodiment specifically preparing carrier, in the mixture with Alpha-alumina for the described hydrated alumina
The method introducing the compound containing adjuvant component is that the compound containing adjuvant component is configured to aqueous solution, by this aqueous solution in institute
State be mixed into while hydrated alumina is mixed with Alpha-alumina or after described hydrated alumina is mixed with Alpha-alumina again
This aqueous solution is mixed into, aftershaping, drying roasting.The compound of described alkali metal containing can be arbitrary alkali-metal water
One or more of soluble compound.For example, in the water-soluble inorganic salt of alkali-metal water-soluble inorganic salt and alkaline-earth metal
One or more.
The micropore property of the aluminium oxide article shaped that the present invention provides is at a diameter of 5-12nm and a diameter of 80-200nm two
In obvious bimodal distribution.The aluminium oxide article shaped with attribute of the present invention, in addition to can using as common adsorbents, also may be used
Used using the filler being used for reaction unit as implant.When this article shaped is prepared hydrogenation class catalyst as carrier, special
It is not suitable as the carrier as catalyst such as Hydrogenation active protective agent to use.
The hydrogenation protecting catalyst providing according to the present invention, wherein, described hydrogenation active metals component the preferably the VIIIth race gold
Genus group is divided into cobalt and/or nickel, and the metal component of Group VB is vanadium and/or niobium, is counted and on the basis of catalyst by oxide, described
The content of metal component of group VIII is to less than or equal to 0.8 weight %, preferably 0.1-0.7 weight % more than 0, more preferably
0.2-0.6 weight %, the content of described Group VB metal component is to less than or equal to 4 weight %, preferably 1-4 weight % more than 0,
More preferably 1.5-3.5 weight %.
Enough to, on the premise of described hydrogenation active metals component is carried on described carrier, the present invention is to described negative
Support method is not particularly limited, and preferred method is infusion process, including the dipping solution of the compound prepared containing described metal, it
Afterwards with the carrier described in this solution impregnation, drying, roasting or roasting.Described dipping method is conventional method, for example, it may be
Excessive immersion stain, hole saturation infusion process.The described solubility being selected from containing the metal component compound selected from V B race in them
One or more of compound, for example, it is possible to selected from as many in vanadic anhydride, ammonium vanadate, ammonium metavanadate, Sulfovanadic acid, vanada
One or more of acid, ammonium metavanadate preferably wherein, ammonium vanadate.Described selects containing the compound selected from VIII race's metal component
One or more of soluble compound from them, such as cobalt nitrate, cobaltous acetate, basic cobaltous carbonate, cobaltous chloride and cobalt can
One or more of solubleness complex, preferably cobalt nitrate, basic cobaltous carbonate；Nickel nitrate, nickel acetate, basic nickel carbonate, chlorine
Change one or more of soluble complexes of nickel and nickel, preferably nickel nitrate, basic nickel carbonate.
In the present invention, the method and condition of described drying is not particularly limited.Usually, the temperature of described drying is permissible
For 80～350 DEG C, preferably 100～300 DEG C；The time of described drying can be 0.5～24 hour, preferably 1～12 hour.
When catalyst after drying needs to carry out roasting, the present invention is not special to described method of roasting and condition
Limit, can be conventional method and the condition of this area.Usually, the temperature of described roasting can be 350～650 DEG C, preferably
For 400～500 DEG C；The time of described roasting can be 0.2～12 hour, preferably 1～10 hour.Described roasting can contain
Carry out in oxygen atmosphere it is also possible to carry out in an inert atmosphere.
The catalyst providing according to the present invention, can also contain any present invention that do not affect provides performance or the energy of catalyst
The adjuvant component of the catalyst performance of present invention offer is provided.As the components such as phosphorus can be contained, in terms of element and with catalyst it is
Benchmark, the content of described auxiliary agent is less than 10 weight %, preferably 0.5-5 weight %.
Organize timesharing when also containing in described catalyst selected from phosphorus etc., also include the step introducing the components such as phosphorus, described phosphorus etc.
The introducing method of component can pass through number of ways, and preferred method is that the compound containing described auxiliary agent is lived with containing hydrogenation
The compound of property metal component is contacted with described carrier after being configured to mixed solution；Can also be the compound list containing auxiliary agent
Contact with described carrier and roasting after solely preparing solution.When auxiliary agent introduces described carrier respectively with hydrogenation active metals, preferably
First with contacting with described carrier and roasting containing auxiliary compound solution, afterwards again with the change containing hydrogenation active metals component
The solution contact of compound, the method for example passing through dipping, described sintering temperature is 250-600 DEG C, preferably 350-500 DEG C, roasting
The burning time is 2-8 hour, preferably 3-6 hour.
According to the conventional method in this area, described hydrotreating catalyst before the use, generally can exist in hydrogen
Under, with sulfur, hydrogen sulfide or carry out presulfurization containing sulfur feedstock at a temperature of 140-370 DEG C, this presulfurization can be carried out outside device
Also can be In-situ sulphiding in device, the active metal component that it is loaded is converted into metal sulfide component.
The present invention provide protective agent be applied to as heavier hydrocarbon feeds be processed when protective agent, be particularly suited for make
The heavy raw oil of the high nitrogen high metal content of high-sulfur inferior also includes the protective agent of decompression residuum, in the filling of hydrogenation catalyst top
This protective agent, can effectively solving industry hydrogenation plant bed fouling, blocking, pressure drop are excessive and the problem that is forced shut-down, under prolongation
The service life of trip hydrogenation catalyst.
Specific embodiment
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）Measure specific surface area, pore volume and pore size distribution of aluminium oxide shaping carrier etc.（Poplar
Emerald green fixed etc., Petrochemical Engineering Analysis method, publishing house of academy of science, 1990, the 421-423 page）.
BET nitrogen absorption under low temperature method（RIPP151-90）Measure specific surface area, pore volume and the pore size distribution of hydrated alumina
Deng（Yang Cui is fixed etc., Petrochemical Engineering Analysis method, publishing house of academy of science, and 1990, the 424-426 page）.
Butt assay method is to take appropriate amount of sample, in 600 DEG C of roasting temperature 3h, afterwards, calculates sample and roasting after roasting
The mass percent of sample before burning, is the butt of this sample.
Using XRF method（RIPP132-90）Measure the content of adjuvant component and hydrogenation active metals component in catalyst（Poplar
Emerald green fixed etc., Petrochemical Engineering Analysis method, publishing house of academy of science, 1990, the 371-375 page）.
Embodiment 1
Weigh 200g hydrated alumina（It is available commercially from Yantai Heng Hui Chemical Co., Ltd., butt is 72 weight %.Pore volume is
0.50 ml/g, specific surface area is 290 meters2/ gram, most probable bore dia is 7nm）, 70 grams of alpha-aluminas（By the present embodiment
Used in hydrated alumina roasting at 1400 DEG C form within 6 hours）, 9 grams of sesbania powder mixing, add 230 milliliters of water afterwards, mix
After closing uniformly, kneading the cylindrical orifice plate extrusion with φ 2.0mm in double screw banded extruder, afterwards, wet bar is through 120 DEG C of dryings
After 850 DEG C of roastings 2 hours, obtain carrier T-1 of the present invention within 4 hours.Measurement carrier T-1 specific surface, can several apertures, pore volume,
Pore size distribution, the results are shown in Table 1.
Embodiment 2
Weigh 180g dry glue powder（It is available commercially from Zibo neat cyclopentadienyl catalyst factory, butt is 68 weight %.Pore volume be 0.55 milliliter/
Gram, specific surface area is 278 meters2/ gram, most probable bore dia is 8nm）, 120 grams of alpha-aluminas（It is available commercially from Beijing Shun Chuan environmental protection
Science and Technology Ltd.）, the mixing of 9 grams of sesbania powders, add 205 milliliters of the aqueous solution containing 11.0 grams of potassium nitrate, mix homogeneously afterwards
Kneading the cylindrical orifice plate extrusion with φ 2.0mm in double screw banded extruder afterwards, afterwards, wet bar is after 120 DEG C of dryings 4 hours
In 850 DEG C of roastings 2 hours, obtain carrier T-2 of the present invention.Measurement carrier T-2 specific surface, can several apertures, pore volume, pore size distribution,
The results are shown in Table 1.
Embodiment 3
Weigh 150g dry glue powder（It is available commercially from Yantai Heng Hui Chemical Co., Ltd., butt is 72 weight %.Pore volume is 0.50 milli
Rise/gram, specific surface area is 255 meters2/ gram, most probable bore dia is 9nm）, 150 grams of alpha-aluminas（With embodiment 2）, 9 grams of fields
Cyanines powder, 9 grams of methylcellulose mixing and 7.0 grams of Calcium Carbonate（Chemical Reagent Co., Ltd., Sinopharm Group）Mixing, adds 200 afterwards
Milliliter water, according to roller forming method molding after mix homogeneously, obtaining particle diameter is 5.5-6.5mm spheroidal particle.Wet bar is through 120 DEG C
It is dried 4 hours after 800 DEG C of roastings 2 hours, obtain carrier T-3 of the present invention.Measurement carrier T-3 specific surface, can several apertures, hole
Appearance, 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 grams of sesbania powders, 9 grams of first
Base cellulose mixes, and adds 205 milliliters of the aqueous solution containing 16.5 grams of lithium nitrate afterwards, in double screw banded extruder after mix homogeneously
Simultaneously with the cylindrical orifice plate extrusion of φ 2.0mm, wet bar after 800 DEG C of roastings 2 hours, obtained middle kneading through 120 DEG C of dryings 4 hours
Carrier T-4 of the present invention.Measurement 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 grams of sesbania powders, 9 grams of first
Base cellulose and 9 grams of methylcellulose and 7.8 grams of magnesium hydroxide（Chemical Reagent Co., Ltd., Sinopharm Group）Mixing, adds afterwards
200 milliliters of aqueous solution, extruded moulding after mix homogeneously, wet bar, obtains after 800 DEG C of roastings 2 hours through 120 DEG C of dryings 4 hours
Carrier T-4 of the present invention.Measurement 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 powders, add the solution containing 12 grams of nitric acid after mix homogeneously
200 milliliters of mixed-formings, wet bar obtains carrier D-1 through 120 DEG C of dryings 4 hours after in 850 DEG C of roastings 2 hours.Measurement carrier
The specific surface of D-1, can several apertures, pore volume, the results are shown in Table 1.
Comparative example 2
Weigh 300 grams of dry glue powders（It is available commercially from Chang Ling oil refining catalyst factory, butt is 65 weight %.Pore volume be 0.8 milliliter/
Gram, specific surface area is 320 meters2/ gram, most probable bore dia is 9nm）, 9 grams of sesbania powders and magnesium nitrate（AlfaAesar (Tianjin) is changed
Learn company limited）6 grams, add the 220 milliliters of mixed-formings of solution containing 12 grams of nitric acid after mix homogeneously, wet bar is through 120 DEG C of dryings 4
Hour, after in 850 DEG C of roastings 2 hours, obtains carrier D-2.The specific surface of measurement carrier D-2, can several apertures, pore volume, result is shown in
Table 1.
Comparative example 3
Weigh dry glue powder（（It is available commercially from Chang Ling oil refining catalyst factory, butt is 65 weight %.Pore volume is 0.8 ml/g, than
Surface area is 290 meters2/ gram, most probable bore dia is 10nm））300 grams, add 24 grams of carbon black powder, 12 grams of mixing of sesbania powder, it
Add 260 milliliters of the aqueous solution of 2.4 grams of phosphoric acid being 85 weight % containing concentration afterwards, kneading 15 minutes, in double screw banded extruder
On be extruded into the butterfly bar of Φ 1.5mm, wet bar obtains carrier D-3 through 120 DEG C of dryings 4 hours after 950 DEG C of roastings 2 hours.Measurement
The specific surface of carrier D-3, can several apertures, pore volume, the results are shown in Table 1.
Comparative example 4
Weigh 300 grams of dry glue powders（It is available commercially from Chang Ling oil refining catalyst factory, butt is 65 weight %.Pore volume be 0.65 milliliter/
Gram, specific surface area is 288 meters2/ gram, most probable bore dia is 9nm）, 9 grams of sesbania powders, add after mix homogeneously and contain potassium nitrate 12
Gram 360 milliliters of mixed-formings of solution, wet bar obtains carrier D-4 through 120 DEG C of dryings 4 hours after in 950 DEG C of roastings 2 hours.
Measurement carrier D-4 specific surface, 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 removes has larger most probable pore size, and hole is divided
It is 6-10nm and 85-160nm that cloth is concentrated mainly on bore dia, is in significantly in bore dia for 6-10nm and 85-160nm scope
Bimodal distribution.
Embodiment 6
Take 100 grams of carrier T1, contain V with 110 milliliters2O528.6 g/l, NiO5 g/l of ammonium metavanadate and nickel nitrate mixing
Solution impregnation 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtains hydrogenation protecting catalyst TC1 of the present invention.Wherein,
The content of hydrogenation active metals component is listed in table 2.
Embodiment 7
Take 100 grams of carrier T2, contain V with 110 milliliters2O528.6 g/l, CoO5 g/l of ammonium metavanadate and cobalt nitrate mixing
Solution impregnation 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtains hydrogenation protecting catalyst TC2 of the present invention.Wherein,
The content of hydrogenation active metals component is listed in table 2.
Embodiment 8
Take 100 carrier T3, contain V with 110 milliliters2O525 g/l, NiO3 g/l of ammonium metavanadate and nickel nitrate mixed solution
Dipping 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtains hydrogenation protecting catalyst TC3 of the present invention.Wherein, it is hydrogenated with
The content of active metal component is listed in table 2.
Embodiment 9
Take 100 grams of carrier T4, contain V with 110 milliliters2O525 g/l, CoO3 g/l of ammonium metavanadate and cobalt nitrate mixing molten
Immersion stain 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtains hydrogenation protecting catalyst TC4 of the present invention.Wherein, plus
The content of hydrogen activity metal component is listed in table 2.
Embodiment 10
Take 100 grams of carrier T5, contain V with 110 milliliters2O519.0 g/l, NiO2 g/l of ammonium metavanadate and nickel nitrate mixing
Solution impregnation 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtains hydrogenation protecting catalyst TC5 of the present invention.Wherein,
The content of hydrogenation active metals component is listed in table 2.
Contrast row 5
Take 100 grams of carrier D1, contain V with 110 milliliters2O528.6 g/l, NiO5 g/l of ammonium metavanadate and nickel nitrate mixing
Solution impregnation 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtains hydrogenation protecting catalyst DC1.Wherein, hydrogenation is lived
The content of property metal component is listed in table 2.
Comparative example 6
Take 100 grams of carrier D4, contain V with 110 milliliters2O525 g/l, NiO3 g/l of ammonium metavanadate and nickel nitrate mixing molten
Immersion stain 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtains hydrogenation protecting catalyst DC2.Wherein, hydrogenation activity
The content of metal component is listed in table 2.
Table 2
Embodiment 11-12 illustrates that the present invention provides the hydrogenation protecting agent performance of carrier preparation.
Embodiment 11
Protective agent TC-1 is evaluated on the medium-sized evaluating apparatus of 200ml, raw materials used oil is for mixing slag faulty wax oil.Evaluate bar
Part is 360 DEG C of reaction temperature, hydrogen dividing potential drop 8.0MPa, volume space velocity 0.8h-1, hydrogen to oil volume ratio 700：1.Sample after evaluating 2000h
Fe deposition and coke content in analysis protectant.Result is listed in table 3.
Using XRF method（XRF semi-quantitative analyses（B-U））Measure element of Fe content in solid sample.
Using infrared absorption method（RIPP106-90）Measure carbon deposit content in protective agent（Yang Cui is fixed etc., Petrochemical Engineering 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, in sample analysis protective agent after evaluation 2000h
Fe deposition and coke content.Result is listed in table 3.
Comparative example 7
According to example 11 identical condition evaluating DC-1.Evaluate after 2000h in sample analysis protective agent Fe deposition and
Coke content.Result is listed in table 3.
Comparative example 8
According to example 11 identical condition evaluating DC-2.Evaluate after 2000h in sample analysis protective agent Fe 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 | 1.35 | 14.0 |
| Embodiment 12 | TC-2 | 1.58 | 12.8 |
| Comparative example 7 | DC-1 | 0.34 | 19.9 |
| Comparative example 8 | DC-2 | 0.2 | 20.08 |
Above evaluation result shows, compared with the hydrogenation protecting agent providing with prior art, the carrier institute that the present invention provides
The protective agent of preparation holds metal ability and anti-carbon deposition ability significantly improves.
Claims (13)
1. a kind of hydrogenation protecting catalyst, containing carrier and load hydrogenation active metals component on this carrier, described carrier
For having the aluminium oxide article shaped of structure of double peak holes, characterized with mercury injection method, the pore volume of described article shaped is 0.3-0.8 ml/g,
Specific surface area is 70-220 rice2/ gram, the pore volume in a diameter of 6-10nm hole accounts for the 8-25% of total pore volume, a diameter of 85-160nm
The pore volume in hole accounts for the 40-75% of total pore volume, described hydrogenation active metals group be selected from least one metal component of group VIII and
At least one Group VB metal component, is counted and on the basis of catalyst by oxide, and the content of described metal component of group VIII is
More than 0 to less than or equal to 0.8 weight %, the content of Group VB metal component is to less than or equal to 5 weight % more than 0.
2. catalyst according to claim 1 it is characterised in that described article shaped pore volume be 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, a diameter of 85-
The pore volume in 160nm hole accounts for the 45-70% of total pore volume；Described metal component of group VIII is selected from nickel and/or cobalt, Group VB metal group
It is selected from vanadium and/or niobium, is counted and on the basis of catalyst by oxide, the content of described metal component of group VIII is 0.1-0.7
Weight %, the content of Group VB metal component is 1-4 weight %.
3. catalyst according to claim 2 is it is characterised in that counted and on the basis of catalyst by oxide, and described VIII
The content of race's metal component is 0.1-0.6 weight %, and the content of the Vth B race metal component is 1.5-3.5 weight %.
4. catalyst according to claim 1 is it is characterised in that containing in IA and IIA in described article shaped
One or more adjuvant components, are counted and on the basis of described article shaped total amount by oxide, and the content of described adjuvant component is 10
Below weight %.
5. catalyst according to claim 4 is it is characterised in that described IA is selected from one or more of lithium, sodium and potassium,
Described IIA is selected from one or more of magnesium, calcium and barium, is counted and on the basis of described article shaped total amount by oxide, described helps
The content of agent component is 2.5-5.5 weight %.
6. a kind of preparation method of hydrogenation protecting catalyst, comprises the steps：
(1) prepare carrier, including a kind of hydrated alumina is mixed with a kind of Alpha-alumina, molding, drying roasting, roasting temperature
Spend for 750-1000 DEG C, roasting time is 1-10 hour, wherein, the mixing ratio of hydrated alumina in terms of butt and Alpha-alumina
For 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, may be used
A few bore dia 5-20nm；
(2) hydrogenation active metals component is introduced on the carrier that step (1) obtains, described hydrogenation active metals group is selected from least
A kind of metal component of group VIII and at least one Group VB metal component, are counted and on the basis of catalyst by oxide, and described the
It is to less than or equal to 0.8 more than 0 that the introduction volume of VIII race's metal component makes the content of the metal component of group VIII in final catalyst
Weight %, it is more than 0 that the introduction volume of described Group VB metal component makes the content of the Group VB metal component in final catalyst
To less than or equal to 5 weight %, it is dried afterwards and roasting, described drying condition includes：Temperature is 100-250 DEG C, and the time is 1-
10 hours, roasting condition included：Temperature is 360-500 DEG C, and the time is 1-10 hour.
7. method according to claim 6 is it is characterised in that sintering temperature in described step (1) is 800-950 DEG C,
Roasting time is 2-8 hour, and the hydrated alumina counted with butt and the mixing ratio of Alpha-alumina are as 30-70:30-70, described water
The pore volume closing aluminium oxide is 0.35-1 ml/g, and specific surface is 150-300 rice2/ gram, most probable bore dia 6-15nm；Described
The metal component of VIII race is selected from nickel and/or cobalt, and the metal component of Group VB is selected from vanadium and/or niobium, in terms of oxide and to be catalyzed
On the basis of agent, it is 0.1- that the introduction volume of described metal component of group VIII makes the content of the metal component of group VIII in final catalyst
0.7 weight %, it is 1-4 that the introduction volume of described Group VB metal component makes the content of the Group VB metal component in final catalyst
Weight %, the drying condition of described step (2) includes：Temperature is 100-140 DEG C.
8. method according to claim 7 is it is characterised in that the introduction volume of described metal component of group VIII makes finally to be catalyzed
The content of the metal component of group VIII in agent is 0.2-0.6 weight %, and the introduction volume of described Group VB metal component makes finally to urge
The content of the Group VB metal component in agent is 1.5-3.5 weight %.
9. the method according to any one of claim 6,7 or 8 is it is characterised in that described introduce hydrogenation activity on carrier
The method of metal component is infusion process.
10. the method according to claim 6 or 8 is it is characterised in that described hydrated alumina is selected from boehmite.
11. methods according to claim 6 are it is characterised in that in described step (1) by a kind of hydrated alumina and one
Plant in Alpha-alumina mixing, the step including introducing selected from one or more of IA and IIA adjuvant component, in terms of oxide simultaneously
On the basis of described article shaped total amount, the introduction volume of described adjuvant component is below 10 weight %.
12. methods according to claim 11 it is characterised in that described IA is selected from one or more of lithium, sodium and potassium,
Described IIA is selected from one or more of magnesium, calcium and barium, is counted and described auxiliary agent on the basis of described article shaped total amount by oxide
The introduction volume of component is 2.5-5.5 weight %.
Application in hydrocarbon oil hydrogenation process for the hydrogenation protecting catalyst described in any one in 13. claim 1-5.
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| CN1488441A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Method for preparing alumina supporter |
| CN102649067A (en) * | 2011-02-24 | 2012-08-29 | 中国石油化工股份有限公司 | Hydrogenation active protective agent with aluminum oxide as carrier and preparation as well as application thereof |
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| CN1488441A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Method for preparing alumina supporter |
| CN102649067A (en) * | 2011-02-24 | 2012-08-29 | 中国石油化工股份有限公司 | Hydrogenation active protective agent with aluminum oxide as carrier and preparation as well as application thereof |
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