CN104437579B - Distillate-oil hydrofining catalyst, and preparation and application thereof - Google Patents
Distillate-oil hydrofining catalyst, and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a distillate-oil hydrofining catalyst, and preparation and application thereof. The catalyst comprises a carrier, at least one non-noble metal composition selected from group VIII and supported on the carrier, at least one metal composition selected from group VI B, and phosphorus or a combined auxiliary agent composition of phosphorus and magnesium. Based on the catalyst in terms of oxides, the mass fraction of the group VIII metal composition is 0.1-6%, the mass fraction of the group VI B is 1-40 %, and the mass fraction of the auxiliary agent composition is 0.5-8%. The provided catalyst is especially suitable for hydrofining applied to light distillate oil and middle distillate oil and taking hydrodesulfurization and hydrodenitrogenation as purposes.
Description
Technical field
The present invention relates to a kind of catalyst for hydrorefining distillate oil and preparation thereof and application, more specifically to
A kind of distillate particularly light ends oil and the hydrodesulfurization of intermediate oil, hydrodenitrogenation catalyst and
Preparation and application.
Background technology
Hydrofinishing is the method that petroleum refining industry is conventional, and its main purpose is to remove in petroleum hydrocarbon
Sulfur, nitrogen, oxygen compound or metal etc..Such as oil raw materials used to reformer, typically entering reforming reaction system
Must carry out pre-hydrogenation before system, gasoline is sent out by the effect of hydrogenation catalyst under certain reaction condition with hydrogen
Raw following reaction: the hydrogenation such as sulfur, nitrogen, oxygen and chloride decomposes, and generates H2S, H2O, HCL etc. respectively；
Olefins hydrogenation；Metallorganic hydrogenation decomposes and deposits on a catalyst.For kerosene, diesel oil etc. its
His fraction, for ensureing product quality, the most also needs to carry out wanting hydrofinishing removing sulfur therein, nitrogen and aromatic hydrocarbons
Deng, to improve smoke point and diesel index etc..As a example by reformed pre-hydrogenated catalyst, represent external advanced at present
The reformed pre-hydrogenated catalyst of level has S-120, Creterion of the HR-306 of Inst Francais Du Petrole, Uop Inc.
The DN-200 catalyst of company, the domestic RS catalyst series mainly having Research Institute of Petro-Chemical Engineering, comfort
Also develop the reformed pre-hydrogenated catalyst of FH-40 series along Petroleum Chemical Engineering Institute, they are respectively provided with preferably
Desulphurizing activated and a small amount of denitrification activity, refining secondary is mixed for processing and generates the bigger raw material of gasoline proportionality,
Product is difficult to meet catalytic reforming feedstock requirement.
CN200510089847 and 200510089848 discloses a kind of method producing catalytic reforming raw material,
Secondary processing of gasoline raw material is cut into petroleum benzin fraction, middle matter gasoline fraction and heavy gasoline fractions, appoints
The straight-run naphtha of choosing contacts with the first Hydrobon catalyst together with hydrogen, carries out olefin saturation,
Reaction effluent directly contacts with the second Hydrobon catalyst without isolation, carries out hydrodesulfurization and hydrogenation is de-
Nitrogen reacts, and the reaction effluent of generation carries out cooling down, separating, and isolated hydrogen-rich gas recycles, point
The liquid separated out enters distillation dehydration tower and obtains Petroleum after imurity-removal.The method can be at lower pressure
The secondary processing of gasoline that the lower high sulfur-bearing of process is nitrogenous and olefin(e) centent is high, provides sulfur, nitrogen to contain for catalytic reforming
The amount acceptable material less than 0.5 μ g/g.
The CN1319644 of Compagnie Francise des Petroles's application discloses a kind of gasoline desulfating method, and the method is first
Full distillation gasoline (preferred catalytic cracking gasoline) is carried out removing alkadiene by selective hydrogenation, then this gasoline is divided
Evaporating is 4 fractions, wherein will second and the mixing of the 4th fraction after carry out selective hydrodesulfurization, and the 3rd
Individual fraction then carries out catalytic reforming after hydrofinishing.Its citing in mention by boiling range scope 95-150 DEG C it
Between the fraction full distillation gasoline after de-diene extract out, in reaction temperature 300 DEG C, hydrogen dividing potential drop
3.5MPa, hydrogen to oil volume ratio 150Nm3/m3And under conditions of volume space velocity 3h-1, use procatalyse
HR306 (the CoMo/Al of company2O3) catalyst carries out hydrofinishing to this fraction, in product, sulfur content is less than 1
μ g/g, olefin(e) centent is 0.9 volume %, and nitrogen content does not provide data, and this product can be as CONTINUOUS REFORMER
Charging.
CN1237919 discloses a kind of phosphorus-containing catalyst and uses this catalyst to carry out the side of oil hydrotreating
Method, this catalyst contains the MoO of the weight of the CoO, 10%-30% of 2%-10% weight3P with 4%-10% weight2O5,
The BET surface area of this catalyst is 100-300m2/ g, ESH crush values is more than 1.4MPa, average pore diameter
For 8-11nm, the pore volume in the diameter hole more than 14nm is less than the hole of 8nm less than 0.08ml/g, diameter
Pore volume is at most equal to 0.05ml/g, and the pore volume in the hole of a diameter of 8-14nm is 0.20-0.8ml/g, should
Embodiment of the method is mainly used in the hydrodesulfurization of straight-run naphtha.
The CN01106041 catalyst for hydrorefining distillate oil of Fushun Petrochemical Research Institute's application and preparation thereof
Method discloses a kind of catalyst for hydrorefining distillate oil and preparation method thereof, with containing silicon dioxide 5～15w%
Alumina globule be carrier, containing MoO321～28w%, NiO2～8w%, CoO0.03～2.0w%, adopt
Spray with two sections.This invention catalyst has higher hydrodesulfurization and hydrodenitrogenationactivity activity simultaneously, it is adaptable to
The inferior distillate oil hydrofinishing that sulfur-bearing nitrogen is more simultaneously.
CN00122922 catalyst for hydrodesulfurizationfraction fraction oil and preparation method thereof discloses a kind of distillate
Hydrobon catalyst and preparation method, catalyst is with aluminium oxide or silicon-containing alumina as carrier, with Mo-Ni
For active component, add phosphate builder.By using the Mo-Ni-P co-impregnated solution segmentation total immersion carrier of alkalescence, make
Obtain the Metal Distribution on catalyst more uniform, the activity of catalyst, particularly fraction oil hydrodesulfurizing activity
Significantly improved.
Changchun Huigong Purifying Industry Co., Ltd. CN100998952 discloses a kind of coking gasoline hydrogenation refining
Catalyst and preparation method thereof, product can meet the requirement of catalytic reforming feedstock, and this catalyst can be used for coking vapour
Hydrodesulfurization, denitrogenation and the alkene of oil are saturated.The feature of this method for preparing catalyst is first to prepare to urge
The co-impregnated solution of agent carrier and different atomic ratios more than one, secondly with one of which co-impregnated solution impregnated catalyst
Remove unnecessary residual liquid after carrier, and dry, roasting, then with being different from dipping co-impregnated solution atomic ratio for the first time
Co-impregnated solution again impregnate post-drying, roasting prepares Hydrobon catalyst.But from this catalyst
From the point of view of evaluation result, the desulfurization removing nitric activity of this catalyst is suitable with industry reference agent, is only merely alkene and satisfies
With the rising that rate has certain amplitude.
CN1169337 discloses the preparation method of a kind of catalyst for hydrorefining distillate oil, this catalyst be by
Gama-alumina load Ni, W, Co active component, it is also possible to add appointing in Mg, Zn, Fe, Ca
One element is as co-catalyst component, and this catalyst can be used for reformer feed, gasoline fraction and intermediate oil
Hydrotreating, has high hydrodesulfurization and hydrodenitrogenationactivity activity.
For the hydrofinishing of high nitrogen Petroleum, disclosed patent CN1289828 is authorized to disclose in China
A kind of preparation method of catalyst for hydrorefining distillate oil, catalyst with aluminium oxide or gama-alumina as carrier,
With W, Mo, Ni as active component, add phosphate builder, by the catalysis using segmentation total immersion technology to prepare
Agent, the activity of this catalyst particularly hydrodenitrogenationactivity activity is greatly improved.
Summary of the invention
The technical problem to be solved in the present invention be to provide a kind of new, there is high hydrodesulfurization, hydrogenation simultaneously
Denitrogenation and the catalyst for hydrorefining distillate oil of alkene saturated activity and methods for making and using same thereof.
The content that the present invention relates to includes:
1. a catalyst for hydrorefining distillate oil, containing carrier, load on this carrier at least one
Selected from the VIIIth race non-noble metal components, at least one selected from vib metal component and
Phosphorus or phosphorus and the composite assistants component of magnesium, count and on the basis of catalyst by oxide, and described the
The mass fraction of VIII race's metal component is 0.1-6%, and the mass fraction of vib metals component is
1-40 weight %, the mass fraction of adjuvant component is 0.5-8%.
2. according to the catalyst described in 1, it is characterised in that count and on the basis of catalyst by oxide,
The mass fraction of described metal component of group VIII is 1-6%, and the quality of vib metals component is divided
Number is 5-30%, and the mass fraction of adjuvant component is 1-6%.
3. according to the catalyst described in 2, it is characterised in that count and on the basis of catalyst by oxide,
The mass fraction of described metal component of group VIII is 1.5-5%, the quality of vib metals component
Mark is 10-20%, and the mass fraction of adjuvant component is 1-5%.
4. according to the catalyst described in 1,2 or 3 any one, it is characterised in that the non-noble of described VIIIth race
Metal component is nickel and cobalt, and the metal component of described group vib is molybdenum, and described adjuvant component is phosphorus
And magnesium.
5. according to the catalyst described in 4, it is characterised in that described nickel is 10-45 with the atomic ratio of cobalt, with
The phosphorus of oxide meter and the mol ratio of magnesium are 0.5-3.
6. according to the catalyst described in 5, it is characterised in that described nickel is 13-40 with the atomic ratio of cobalt, with
The phosphorus of oxide meter and the mol ratio of magnesium are 1-2.
7. according to the catalyst described in 1, it is characterised in that described carrier is a kind of bimodal porous aluminum oxide,
Characterizing with mercury injection method, the pore volume of described carrier is 0.9-1.2 ml/g, and specific surface area is 50-
300 meters2/ gram, the pore volume in a diameter of 10-30nm hole accounts for the 55-80% of total pore volume, a diameter of
The pore volume in 300-500nm hole accounts for the 10-35% of total pore volume.
8. according to the catalyst described in 7, it is characterised in that the pore volume of described carrier is 0.95-1.15 milli
Rise/gram, specific surface area is 80-200 rice2/ gram, the pore volume in a diameter of 10-30nm hole accounts for always
The 60-75% of pore volume, the pore volume in a diameter of 300-500nm hole accounts for the 15-30% of total pore volume.
9. a preparation method for catalyst for hydrorefining distillate oil, is included on carrier and introduces at least one
Selected from VIII race non-noble metal components, at least one selected from metal component of group vib and phosphorus or
Phosphorus and the composite assistants component of magnesium, be dried afterwards, count with oxide and with described catalyst as base
Standard, the consumption of each component makes the mass fraction of metal component of group VIII in described catalyst be 0.1-6
Weight %, the mass fraction of vib metals component is 1-40 weight %, the quality of adjuvant component
Mark is 0.5-8%.
10. according to the method described in 9, it is characterised in that count and on the basis of catalyst by oxide, respectively
The consumption of component makes the mass fraction of metal component of group VIII in described catalyst be 1-6%, the
The mass fraction of group vib metal component is 5-30%, and the mass fraction of adjuvant component is 1-6%.
11. according to the method described in 10, it is characterised in that count and on the basis of catalyst by oxide,
The consumption of each component makes the mass fraction of metal component of group VIII in described catalyst be 1.5-5%,
The mass fraction of vib metals component is 10-20%, and the mass fraction of adjuvant component is 1-
5%。
12. according to the method described in 9,10 or 11 any one, it is characterised in that described VIIIth race non-
Noble metal component is nickel and cobalt, and the metal component of described group vib is molybdenum, and described adjuvant component is
Phosphorus and magnesium.
13. according to the method described in 12, it is characterised in that described nickel is 10-45 with the atomic ratio of cobalt, with
The phosphorus of oxide meter and the mol ratio of magnesium are 0.5-3.
14. according to the method described in 13, it is characterised in that described nickel is 13-40 with the atomic ratio of cobalt, with
The phosphorus of oxide meter and the mol ratio of magnesium are 1-2.
15. according to the method described in 9, it is characterised in that described drying condition includes: temperature is 100-
210 DEG C, the time is 1-15 hour.
16. according to the method described in 15, it is characterised in that described drying condition includes: temperature 120-
190 DEG C, drying time is 2-4 hour.
17. according to the method described in 9, it is characterised in that the preparation method of described carrier includes containing intending
Hydrated alumina P1 and P1 of boehmite modifier P2 mixing, aftershaping, be dried also
Roasting, the Mixing ratio by weight of described P1 and P2 be the κ value of 20-95:5-80, P2 be 0 to
Less than or equal to 0.9, described κ=DI2/DI1, DI1For the hydrated alumina containing boehmite
The sour peptization index of P1, DI2Modifier P2 for the hydrated alumina P1 containing boehmite
Sour peptization index, described drying condition includes: temperature is 40-350 DEG C, and the time is that 1-24 is little
Time, roasting condition includes: temperature is that the time is 1-8 to less than or equal to 1200 DEG C more than 500
Hour.
18. according to the method described in 17, it is characterised in that the Mixing ratio by weight of described P1 and P2 is 70-
95:5-30, the k value of described P2 is 0 to less than or equal to 0.6；Described drying condition bag
Including: temperature is 100-200 DEG C, the time is 2-12 hour, and roasting condition includes: temperature is big
In 800 to less than or equal to 1000 DEG C, roasting time is 2-6 hour.
19. according to the method described in 17 or 18, it is characterised in that the pore volume of described P1 is 0.9-1.4 milli
Rise/gram, specific surface is 100-350 rice2/ gram, can and bore dia 8-30nm；Described P2 is
The particulate matter of 80-300 mesh.
20. according to the method described in 19, it is characterised in that the pore volume of described P1 be 0.95-1.3 milliliter/
Gram, specific surface is 120-300 rice2/ gram, can and bore dia 10-25nm；Described P2 is
The particulate matter of 100-200 mesh.
21. according to the method described in 17 or 18, it is characterised in that by one of P1 method being modified as P2
It is by described hydrated alumina P1 molding containing boehmite, is dried, afterwards that it is whole
Or part is ground, sieves, obtaining powder body thing is P2, and described dry condition includes: temperature
Degree is for 40-350 DEG C, and the time is 1-24 hour；The two of method are article shaped method one obtained
Roasting, sintering temperature is that roasting time is that 1-8 is little more than 350 to less than or equal to 1400 DEG C
Time, afterwards it is completely or partially ground, sieves, obtaining powder body thing is P2；Method it
Three is to dodge dry by the hydrated alumina P1 containing boehmite, dodge dry temperature be more than 150 to
Less than or equal to 1400 DEG C, flash-off time is 0.05-1 hour, and obtaining powder body thing is P2；Method
Four be by the one in one of method, the two of method and the modifier that obtains with the three of method or
Several it is mixed to get.
22. according to the method described in 21, it is characterised in that the condition bag being dried in described method one
Including: temperature is 100-200 DEG C, the time is 2-12 hour；Sintering temperature in the two of method is
500-1200 DEG C, roasting time is 0.1-6 hour；It is 200-that temperature is done in sudden strain of a muscle in the three of method
1000 DEG C, flash-off time is 0.1-0.5 hour.
23. according to the method described in 17 or 18 any one, it is characterised in that described P2 is 80-300 mesh
Particulate matter.
24. according to the method described in 23, it is characterised in that described P2 is the particulate matter of 100-200 mesh.
25. 1 kinds of distillate hydrogenation processing methods, including at hydrotreating reaction conditions, by raw oil with
Catalyst haptoreaction, it is characterised in that described catalyst is claim 1-8 any one
Described catalyst.
The catalyst provided according to the present invention, is combined as adjuvant component, described hydrogenation with phosphorus or phosphorus and magnesium
Active metal component at least one selected from the VIIIth race non-noble metal components, at least one is selected from vib
Metal component, counts and on the basis of catalyst by oxide, and the mass fraction of described metal component of group VIII is
0.1-6%, preferably 1-6%, more preferably 12.5-5%, the mass fraction of vib metals component
For 1-40 weight %, preferably 5-30%, more preferably 10-20%, the mass fraction of adjuvant component is
0.5-8%, preferably 1-6%, more preferably 1-5%.
In one preferred embodiment, the non-noble metal components of described VIIIth race is nickel and cobalt, described
The metal component of group vib is molybdenum, and described adjuvant component is phosphorus and magnesium.Further, described nickel therein with
The atomic ratio of cobalt is 10-45, preferably 13-40, the phosphorus counted with oxide and the mol ratio of magnesium as 0.5-3,
It is preferably 1-2.
The catalyst provided according to the present invention, wherein said carrier can be arbitrarily to urge frequently as preparing this type of
The carrier of agent, a kind of one preferred embodiment in, described carrier is a kind of bimodal porous aluminum oxide,
Characterizing with mercury injection method, the pore volume of described carrier is 0.9-1.2 ml/g, preferably 0.95-1.15 milliliter/
Gram, specific surface area is 50-300 rice2/ gram, preferably 80-200 rice2/ gram, a diameter of 10-30nm hole
Pore volume accounts for the 55-80% of total pore volume, preferably 60-75%, and the pore volume in a diameter of 300-500nm hole accounts for
The 10-35%, preferably 15-30% of total pore volume.
Depending on different requirements, the carrier in catalyst of the present invention can be made into various easily operated article shaped,
Such as, spherical, cellular, nest like, tablet or bar shaped (Herba Trifolii Pratentis, butterfly, cylinder etc.).Its
In, by the method that the modifier P2 of described hydrated alumina P1 and P1 containing boehmite mixes it is
Conventional method, such as, puts into P1 and P2 of powder body in stirring-type batch mixer according to ingredient proportion and mixes.
Described molding is carried out according to a conventional method, such as, a kind of method in spin, tabletting and extruded moulding or
The combination of several method.When molding, as a example by extruded moulding, for ensureing that described molding is smoothed out,
Water, extrusion aid and/or adhesive can be added, with or without expanding agent, then in described mixture
Extrusion molding, is dried and roasting afterwards.Described extrusion aid, the kind of peptizer and consumption are ability
Well known to field technique personnel.Wherein, the example of described extrusion aid such as sesbania powder, methylcellulose, shallow lake
One or more in powder, polyvinyl alcohol, described peptizer can be mineral acid and/or organic acid, described
Expanding agent can be one or more in starch, synthetic cellulose, polymeric alcohol and surfactant.Its
In synthetic cellulose be preferably hydroxymethyl cellulose, methylcellulose, ethyl cellulose, hydroxyl ferry grease
One or more in fat alcohol polyvinylether, polymeric alcohol is preferably in Polyethylene Glycol, poly-propanol, polyvinyl alcohol
One or more, surfactant be preferably fat alcohol polyethylene ether, fatty alkanol amide and derivant thereof,
Molecular weight is one or more in the propenyl copolymer of 200-10000 and maleic acid copolymer.
In the present invention, sour peptization index D I in the preparation of described carrier refers to the hydration containing boehmite
After aluminium oxide (including its modifier) adds nitric acid by certain acid aluminum ratio, by glue within certain response time
The molten hydrated alumina containing boehmite is with Al2O3The percent of meter, DI=(1-W2/W1)×
100%, W1And W2Before respectively intending thin water aluminum and acid reaction and with acid reaction after with Al2O3The weight of meter.
The mensuration of DI includes: (1) measure the calcination base content (calcination of the hydrated alumina containing boehmite
Base content (also referred to as butt) refers to quantitative boehmite in 600 DEG C of roastings 4 hours, after it burns
Weight weight ratio front with burning), it is calculated as a；(2) weigh the hydration oxygen containing boehmite with analytical balance
Change aluminum W0Gram, W0Amount meet with Al2O3The W of meter1It is 6 grams of (W1/a=W0), weigh deionized water W
Gram, W=40.0-W0, under stirring, the hydrated alumina containing boehmite weighed and deionized water are added
Beaker mixes；With 20mL pipet pipette 20mL, concentration is the dilute nitric acid solution of 0.74N, should
Acid solution joins in the beaker of step (2), the lower reaction of stirring 8 minutes；(4) after step (3) being reacted
Serosity be centrifuged in centrifuge separate, precipitate is inserted in the crucible weighed, afterwards, by it
Being dried 4 hours in 125 DEG C, in Muffle furnace, 850 DEG C of roastings 3 hours, weigh and obtain calcination sample size W2
Gram；(5) according to formula DI=(1-W2/W1) × 100% is calculated.
On the premise of being enough to make final carrier meet application claims, the present invention to described containing intend thin water aluminum
The hydrated alumina P1 of stone does not specially require, and can be the boehmite prepared of any prior art,
Can also be boehmite and the mixture of other hydrated alumina, other hydrated alumina choosing described
One or more in a water aluminium oxide, gibbsite and amorphous hydrated aluminium oxide.Such as, pore volume
For 0.9-1.4 ml/g, specific surface is 100-350 rice2/ gram, can and bore dia 8-30nm；Preferably
Pore volume is 0.95-1.3 ml/g, and specific surface is 120-300 rice2/ gram, can and bore dia 10-25nm
The hydrated alumina containing boehmite be just particularly suitable for the present invention.In the present invention, thin containing intending
The pore volume of the hydrated alumina of diaspore, specific surface area and can and aperture, be containing intending thin water aluminum by described
The hydrated alumina of stone, after 600 DEG C of roastings 4 hours, is characterized by BET N2 adsorption and obtains.
In further preferred embodiment, characterize with X diffraction, the described hydration containing boehmite
In aluminium oxide, boehmite content is not less than 50%, more preferably not less than 60%.
Inventors of the present invention have surprisingly found that, the hydrated alumina P1 containing boehmite is carried out heat
Processing modified, the peptization index of its modifier changes, by this modifier with the most thermally treated
After P1 mixed-forming, dry also roasting, obtained carrier has obvious bimodal pore distribution.Particularly exist
By the granule of 80-300 mesh therein, the granule of preferably 100-200 mesh mixes with the most thermally treated part
Molding, be dried and roasting after, obtained carrier bimodal in each unimodal pore size distribution concentrate especially.
Here, the granule of described 80-300 mesh, the granule of preferably 100-200 mesh refers to that described modifier is through sieving
(including step that is broken or that grind if desired), its screening thing (siftage) meets 80-300 purpose
Grain, the particulate matter of preferably 100-200 mesh accounts for the percent (by weight) of total amount and is not less than 60%, enters one
Step is preferably not less than 70%.
In being embodied as, described P2 conveniently can be obtained by following method:
(1) based on being dried to obtain P2, including by the hydrated alumina P1 containing boehmite according to a conventional method
During regular oxidation alumina supporter is prepared in molding, the tailing of drying by-product, such as: in extruded moulding,
Bar shaped article shaped is at dry, the tailing (being referred to as traditionally being dried waste material) of integer process by-product, by this tail
Material is milled, and sieves and obtains P2.
(2) obtain based on roasting, become according to a conventional method including by the hydrated alumina P1 containing boehmite
During regular oxidation alumina supporter prepared by type, the tailing (being referred to as roasting waste material traditionally) of fired by-product,
Such as, in roller forming, spheroidal particle is the tailing of by-product in roasting process, is ground by this tailing
Mill, sieves and obtains P2；Or directly P1 is dodged dry obtaining, when directly dodging dry by P1, flash-off time
Preferably 0.05-1 hour, more preferably 0.1-0.5 hour.
(3) two or more be mixed to get in the modifier P2 obtained based on preceding method.Mixed when using
When conjunction method obtains P2, the mixed proportion of the modifier P2 respectively obtaining aforementioned several method does not limit
System.
In the present invention, described introduce on carrier at least one selected from VIII race non-noble metal metal component and
At least one metal component selected from group vib and the method selected from phosphorus or the composite assistants component of phosphorus and magnesium can
To be arbitrary existing method, wherein preferably method is the method for dipping, and described dipping method is conventional
Method, such as, can be to use hole saturation dipping, excess immersion stain and spray impregnating.Wherein, described
VIIIth race, vib and the composite assistants component selected from phosphorus or phosphorus and magnesium can be introduced separately into, it is also possible to two
Two or selected from the non-noble metal metal component of VIII race with at least one is selected from the metal component of group vib and choosing
It is simultaneously introduced from the composite assistants component of phosphorus or phosphorus and magnesium.When using infusion process to introduce, including preparation dipping
Solution, such as, by the compound containing the described metal component selected from least one vib, containing at least one
Plant the compound of the metal component of the VIIIth race or the compound containing the composite assistants component selected from phosphorus or phosphorus and magnesium divides
Do not prepare dipping solution, and impregnate carrier respectively with these dipping solutions；Or be selected from least by containing described
The metal component of a kind of vib, the compound of the metal component containing at least one the VIIIth race and containing selected from phosphorus
Or two or three preparation hybrid infusion solution in the compound of the composite assistants component of phosphorus and magnesium, and use this
The method that a little dipping solutions impregnate carrier respectively.When described dipping is step impregnation, to described dipping solution
The order of dipping carrier does not limit.
In a detailed description of the invention, on carrier, first introduce magnesium adjuvant component, such as, preparation
The compound solution of magnesium-containing aid component, uses this solution impregnating carrier, is separately or concurrently introducing phosphorus choosing afterwards
From the non-noble metal metal component of VIII race and at least one selected from the metal component of group vib and selected from phosphorus or
The composite assistants component of phosphorus and magnesium.
Although optional, after dipping, preferably include the step being dried every time.Described drying condition bag
Include: baking temperature 100-210 DEG C, preferably 120-190 DEG C, 1-6 hour drying time, preferably 2-4
Hour.When the method using dipping is firstly introduced into magnesium, carry out roasting, described roasting the most after drying
Condition includes: temperature is 400-800 DEG C, preferably 500-700 DEG C, and the time is 1-6 hour, is preferably
2-4 hour.
The compound of the described non-noble metal components containing VIII race in their soluble-salt and complex one
Plant or several, such as, the one in the nitrate of VIII race's metal, chloride, acetate, subcarbonate
Or it is several, selected from cobalt nitrate, cobaltous acetate, basic cobaltous carbonate, cobaltous chloride and the solubility of cobalt as a example by cobalt salt
In one or more.
The described compound containing group vib metal component one or several in their soluble compound
Kind, such as, molybdenum oxide, molybdate (such as, ammonium molybdate, ammonium paramolybdate, ammonium phosphomolybdate), tungstates
One or more in (such as, ammonium tungstate, ammonium metatungstate, ammonium paratungstate, ethyl metatungstate).
The described compound containing magnesium, water soluble salt preferably wherein, such as magnesium nitrate.Described phosphorous chemical combination
Thing, the most phosphorous water soluble compound, such as phosphoric acid, Metaphosphoric acid or its esters.
The catalyst provided according to the present invention, wherein can provide catalyst containing any present invention that do not affects
The material of catalytic performance maybe can improve the material of the catalytic performance of the catalyst that the present invention provides.As contained
Boron and/or silicon, count and on the basis of catalyst by element, and the content of above-mentioned auxiliary agent is less than 10 weight %,
It is preferably 0.5-5 weight %.
When in described catalyst possibly together with during selected from the component such as boron and/or silicon, in the preparation method of described catalyst
Including the step of the introducing adjuvant component such as boron and/or silicon, introducing method can be arbitrary method, as permissible
It is by the compound containing described auxiliary agent and the non-noble metal slaine selected from VIII race and the gold selected from group vib
Belong to salt be configured to mixed solution after impregnate described carrier method introduce.
The catalyst that the present invention provides is before the use, it is usually preferred in presence of hydrogen, in 140-370 DEG C
At a temperature of carry out presulfurization with sulfur, hydrogen sulfide or sulfur-bearing raw material, this presulfurization can carry out also may be used outside device
In device In-situ sulphiding, be translated into sulfide type.
Compared with prior art, the catalyst that the present invention provides is adding for high sulfur content, high nitrogen-containing raw material
When hydrogen processes, hydrodesulfurization, denitrogenation and alkene saturated activity are high, are particularly suitable for mixing refining and blend coking
The hydroprocessing processes of the reformer charging of the raw material in gasoline stocks and other technique source.Described hydrogenation
Process reaction to realize in arbitrary fraction oil hydrogenation refining reaction unit, this present invention is limited the most especially
System.Such as, described selective hydrodesulfurization reaction uses one stage hydrofining, and its operating condition can be according to former
Material oil nature and the requirement to oil quality adjust in following ranges: reaction temperature 200～400 DEG C, volume
Air speed 4～15h-1, hydrogen dividing potential drop 0.8～6.0MPa, hydrogen-oil ratio 50～800:1(volume is (v)).
Detailed description of the invention
The present invention will be further described for the following examples, but should be therefore understands that be not the limit to the present invention
Fixed.Agents useful for same in example, except as expressly described, is chemically pure reagent.
The boehmite used below in an example includes:
(pore volume is 1.2 mls/g to the dry glue powder that P1-1: Chang Ling catalyst branch company produces, and specific surface is
280 meters2/ gram, can and bore dia 15.8nm.Butt is 73%, and wherein boehmite content is
68%, gibbsite content is 5 weight %, and surplus is amorphous alumina, DI value 15.8).
(pore volume is 1.1 mls/g to the dry glue powder that P1-2: Yantai Heng Hui Chemical Co., Ltd. produces, and compares table
Face is 260 meters2/ gram, can and bore dia 12nm.Butt is 71%, and wherein boehmite content is
67%, gibbsite content is 5 weight %, and surplus is amorphous alumina, DI value 17.2).
(pore volume is 0.85 ml/g to the dry glue powder that P1-3: Shandong Aluminium Industrial Corp produces, and specific surface is 180
Rice2/ gram, can and bore dia 7nm.Butt is 72%, and wherein boehmite content is 67%, three water aluminum
Stone content is 5 weight %, and surplus is amorphous alumina, DI value 19.5).
Modifier P2 and the preparation side thereof of the described P1 of carrier of the present invention is prepared in the explanation of embodiment 1-4
Method.
Embodiment 1
Weigh 1000 grams of P1-1, add afterwards containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product)
Aqueous solution 1440 milliliters, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is in 120
DEG C it is dried 4 hours, obtains dried strip, by dried strip shaping, sieve, by length less than the dried strip of 2mm
Material (commonly referred to as industrially drying bar waste material) is milled, and sieves, takes wherein 100～200 mesh sieve
Point, obtain the modifier P2A of P1-1.The k value of P2A is shown in Table 1.
Embodiment 2
Weigh 1000 grams of P1-1, dodge dry 6 minutes in 240 DEG C, obtain the modifier P2B of P1-1.P2B
K value be shown in Table 1.
Embodiment 3
The each 200 grams of uniform mixing of P2B that P2A embodiment 1 obtained and embodiment 2 obtain, obtain
The modifier P2C of P1-1.The k value of P2C is shown in Table 1.
Embodiment 4
Weigh 1000 grams of P1-2, add afterwards containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product)
Aqueous solution 1440 milliliters, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is in 120
DEG C it is dried 4 hours, 1200 DEG C of roastings 4 hours, obtains carrier, by carrier strip shaping, sieve, by length
Carrier strip material (commonly referred to as industry carrier waste material) less than 2mm is milled, and sieves, takes wherein
100～200 mesh sieves divide, and obtain the modifier P2D of P1-2.The k value of P2D is shown in Table 1.
Table 1
| Embodiment | Raw material | k |
| 1 | P2A | 0.5 |
| 2 | P2B | 0.4 |
| 3 | P2C | 0.4 |
| 4 | P2D | 0 |
The preparation method of carriers for catalysts of the present invention is prepared in the explanation of embodiment 5-10.The explanation of comparative example 1-4
The preparation method of conventional catalyst carrier.
Embodiment 5
Weighing 800 grams of P1-1, after the 200 grams of raw material P2A prepared with embodiment 1 uniformly mix, addition contains
The aqueous solution 1440 milliliters of 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), at double screw banded extruder
On be extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, should
900 DEG C of roastings of article shaped 3 hours, obtain carrier Z1.The character of carrier Z1 is listed in table 2.
Embodiment 6
Weighing 950 grams of P1-1, after the 50 grams of raw material P2B prepared with embodiment 2 uniformly mix, addition contains
Nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, on double screw banded extruder
It is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by this one-tenth
900 DEG C of roastings of type thing 3 hours, obtain carrier Z2.The character of carrier Z2 is listed in table 2.
Embodiment 7
Weighing 850 grams of P1-1, after the 150 grams of raw material P2C prepared with embodiment 3 uniformly mix, addition contains
Nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, on double screw banded extruder
It is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by this one-tenth
950 DEG C of roastings of type thing 3 hours, obtain carrier Z3.The character of carrier Z3 is listed in table 2.
Comparative example 1
Weigh 1000 grams of P1-1, add the product in nitric acid Tianjin chemical reagent three factory) aqueous solution of 10 milliliters
1440 milliliters, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried in 120 DEG C
4 hours, obtain article shaped, by 900 DEG C of roastings of this article shaped 3 hours, obtain carrier DZ1.Carrier DZ1
Character be listed in table 2.
Embodiment 8
Weighing 800 grams of P1-2, after the 200 grams of raw material P2A prepared with embodiment 1 uniformly mix, addition contains
The aqueous solution 1440 milliliters of 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), at double screw banded extruder
On be extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, should
1000 DEG C of roastings of article shaped 3 hours, obtain carrier Z4.The character of carrier Z4 is listed in table 2.
Embodiment 9
Weighing 850 grams of P1-2, after the 150 grams of raw material P2C prepared with embodiment 3 uniformly mix, addition contains
The aqueous solution 1440 milliliters of 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), at double screw banded extruder
On be extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, should
850 DEG C of roastings of article shaped 3 hours, obtain carrier Z5.The character of carrier Z5 is listed in table 2.
Comparative example 2
Weigh 1000 grams of P1-2, add and contain the water-soluble of 10 milliliters of nitric acid (Tianjin chemical reagent three factory product)
Liquid 1440 milliliters, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is done in 120 DEG C
Dry 4 hours, obtain article shaped, by 1000 DEG C of roastings of this article shaped 3 hours, obtain carrier DZ2.Carrier
The character of DZ2 is listed in table 2.
Comparative example 3
Weigh 1000 grams of P1-3, add and contain the water-soluble of 10 milliliters of nitric acid (Tianjin chemical reagent three factory product)
Liquid 1440 milliliters, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is done in 120 DEG C
Dry 4 hours, obtain article shaped, by 1000 DEG C of roastings of this article shaped 3 hours, obtain carrier DZ3.Carrier
The character of DZ3 is listed in table 2.
Embodiment 10
Weighing 900 grams of P1-3, after the 100 grams of raw material P2B prepared with embodiment 2 uniformly mix, addition contains
Nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, on double screw banded extruder
It is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by this one-tenth
1000 DEG C of roastings of type thing 3 hours, obtain carrier Z6.The character of carrier Z6 is listed in table 2.
Comparative example 4
The method provided according to patent CN1782031A embodiment 7, is extruded into external diameter on double screw banded extruder
The butterfly bar of φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by this article shaped 900 DEG C
Roasting 3 hours, obtains carrier DZ4.The character of carrier DZ4 is listed in table 2.
Table 2
By the result of table 2 it will be seen that compared with conventional method, provider's method of the present invention the oxidation prepared
Alumina supporter has obvious structure of double peak holes.
Embodiment 11-14 and comparative example 5-6 be described separately catalyst that the present invention provides and reference catalyst and
It is prepared.
Embodiment 11
Take 100 grams of carrier Z1.The method using step impregnation introduces molybdenum, nickel, cobalt at carrier Z1 and helps
Agent.First, weighing magnesium nitrate 8.4 grams, it is dissolved to clarification in deionized water thoroughly, total liquid 94ml, uses this
Solution impregnation 100g carrier Z1, is dried 4 hours in 120 DEG C, 600 DEG C of roastings 4 hours.Weigh phosphoric acid
7.6g, uses 70ml deionized water dissolving, and rear continuous heating, to solution temperature 60 DEG C, is slowly added into three oxidations
Molybdenum 21.0 grams, basic nickel carbonate 7.7 grams, basic cobaltous carbonate 0.36 gram, continues to be dissolved to total liquid 94 milli
Rise.Course of dissolution heats, and temperature is maintained at 60 DEG C, with this solution impregnation 100g carrier Z1, in 170 DEG C
It is dried 4 hours, obtains catalyst C1.In C1, nickel, cobalt, molybdenum oxide and auxiliary agent phosphorus, magnesium oxide contain
Amount is shown in Table 3.
Embodiment 12
Take 100 grams of carrier Z1.The method using step impregnation introduces molybdenum, nickel, cobalt at carrier Z1 and helps
Agent.First, weighing magnesium nitrate 8.2 grams, it is dissolved to clarification in deionized water thoroughly, total liquid 94ml, uses this
Solution impregnation 100g carrier Z1, is dried 4 hours in 120 DEG C, 600 DEG C of roastings 4 hours.Weigh phosphoric acid
6.2g, uses 70ml deionized water dissolving, and rear continuous heating, to solution temperature 60 DEG C, is slowly added into three oxidations
Molybdenum 17.9 grams, basic nickel carbonate 8.8 grams, basic cobaltous carbonate 0.26 gram, continues to be dissolved to total liquid 94 milli
Rise.Course of dissolution heats, and temperature is maintained at 60 DEG C, with this solution impregnation 100g carrier Z1, in 170 DEG C
It is dried 4 hours, obtains catalyst C2.In C2, nickel, cobalt, molybdenum oxide and auxiliary agent phosphorus, magnesium oxide contain
Amount is shown in Table 3.
Embodiment 13
Take 100 grams of carrier Z1.The method using step impregnation introduces molybdenum, nickel, cobalt at carrier Z1 and helps
Agent.First, weighing magnesium nitrate 6.3 grams, it is dissolved to clarification in deionized water thoroughly, total liquid 94ml, uses this
Solution impregnation 100g carrier Z1, is dried 4 hours in 120 DEG C, 600 DEG C of roastings 4 hours.Weigh phosphoric acid
6.2g, uses 70ml deionized water dissolving, and rear continuous heating, to solution temperature 60 DEG C, is slowly added into three oxidations
Molybdenum 15.5 grams, basic nickel carbonate 5.5 grams, basic cobaltous carbonate 0.33 gram, continues to be dissolved to total liquid 94 milli
Rise.Course of dissolution heats, and temperature is maintained at 60 DEG C, with this solution impregnation 100g carrier Z1, in 170 DEG C
It is dried 4 hours, obtains catalyst C3.In C3, nickel, cobalt, molybdenum oxide and auxiliary agent phosphorus, magnesium oxide contain
Amount is shown in Table 3.
Comparative example 5
Take 100 grams of carrier DZ4.The method using step impregnation introduces molybdenum, nickel, cobalt at carrier DZ4 and helps
Agent.First, weighing magnesium nitrate 8.4 grams, it is dissolved to clarification in deionized water thoroughly, total liquid 94ml, uses this
Solution impregnation 100g carrier Z1, is dried 4 hours in 120 DEG C, 600 DEG C of roastings 4 hours.Weigh phosphoric acid
7.6g, uses 70ml deionized water dissolving, and rear continuous heating, to solution temperature 60 DEG C, is slowly added into three oxidations
Molybdenum 21.0 grams, basic nickel carbonate 7.7 grams, basic cobaltous carbonate 0.36 gram, continues to be dissolved to total liquid 94 milli
Rise.Course of dissolution heats, and temperature is maintained at 60 DEG C, with this solution impregnation 100g carrier Z1, in 170 DEG C
It is dried 4 hours, obtains catalyst DB1.Nickel, cobalt, molybdenum oxide and auxiliary agent phosphorus, magnesium oxide in DB1
Content is shown in Table 3.
Comparative example 6
Take 100 grams of carrier DZ4.The method using co-impregnation introduces molybdenum, nickel and cobalt at carrier DZ4.First
First, weighing phosphoric acid 5.9g, use 70ml deionized water dissolving, rear continuous heating is to solution temperature 60 DEG C, slow
The slow molybdenum trioxide 14.1 grams that adds, basic nickel carbonate 6.7 grams, basic cobaltous carbonate 0.12 gram, continues to dissolve
To total liquid 94 milliliters.Course of dissolution heats, and temperature is maintained at 60 DEG C, with this solution impregnation 100g carrier
Z1, obtain catalyst DB2.In DB2, cobalt, molybdenum oxide content are shown in Table 3.
Table 3
Remarks: on metal, amount is catalyst XRF analysis result after 550 DEG C of roastings 4 hours.
Embodiment 14-16
This example is mixed v% Anqing coker gasoline with Zhenghai Chang Ding gasoline and catalyst C1-C3 is carried out activity rating.
Raw oil character is shown in Table 4.
Evaluating apparatus is 50ml fixed bed hydrogenation reactor, and hydrogen uses and once passes through.Before reaction, catalysis
First agent carries out presulfurization, and sulfurized oil is containing 2%CS2Zhenghai Chang Ding gasoline.Conditions of vulcanization is: pressure
1.6MPa, hydrogen to oil volume ratio 200:1, volume space velocity 2.0h-1, temperature be 290 DEG C, 3 hours time.Will
Charging switches to Zhenghai Chang Ding gasoline, after stablizing 30 hours, charging switches to raw oil reaction, instead
Condition is answered to include: reaction temperature 280 DEG C, liquid hourly space velocity (LHSV) (LHSV) 10h-1, reaction pressure 1.6MPa, hydrogen
Oil compares 100v/v.Sample analysis after reacting 24 hours, the results are shown in Table 5.
Comparative example 7-8
Evaluating comparative catalyst DB1, DB2 according to embodiment 14-16 same procedure, the results are shown in Table 5.
Table 4 raw oil character
| Test number | Raw material |
| Density (20 DEG C), g/cm3 | 0.7226 |
| Sulfur, ug/g | 1660 |
| Total nitrogen, ug/g | 16.8 |
| Bromine valency, gBr/100g | 5.8 |
| Diene value, gI2/100g | <0.2 |
| Colloid, mg/100ml | 4 |
| Race forms, v% | |
| Saturated hydrocarbons | 89.4 |
| Alkene | 3.7 |
| Aromatic hydrocarbons | 6.9 |
| Boiling range, DEG C | |
| Initial boiling point | 35 |
| 50% | 115 |
| Do | 164 |
Table 5
| Embodiment 14 | Embodiment 15 | Embodiment 16 | Comparative example 7 | Comparative example 8 | |
| Sulfur, ug/g | 1.9. | <0.5 | 5.3 | 63 | 170 |
| Nitrogen, ug/g | <0.5 | <0.5 | 0.7 | 3.7 | 6.6 |
Table 5 result shows, according to the present invention provide catalyst, high-speed, low hydrogen/gasoline ratio, low pressure and
Under lower temperature, hydrotreating high-sulfur, the raw oil of high nitrogen-containing, sulfur and nitrogen can be reduced to 0.5ppm
Hereinafter, catalytic reforming feedstock requirement is met.
Claims (22)
1. a catalyst for hydrorefining distillate oil, containing carrier, load on this carrier at least one is selected from the non-noble metal components of the VIIIth race, at least one is selected from the composite assistants component of the metal component of vib and phosphorus or phosphorus with magnesium, count and on the basis of catalyst by oxide, the mass fraction of described metal component of group VIII is 0.1-6%, the mass fraction of vib metals component is 1-40 weight %, the mass fraction of adjuvant component is 0.5-8%, described carrier is a kind of bimodal porous aluminum oxide, characterize with mercury injection method, the pore volume of described carrier is 0.9-1.2 ml/g, specific surface area is 50-300 rice2/ gram, the pore volume in a diameter of 10-30nm hole accounts for the 55-80% of total pore volume, and the pore volume in a diameter of 300-500nm hole accounts for the 10-35% of total pore volume.
Catalyst the most according to claim 1, it is characterized in that, count and on the basis of catalyst by oxide, the mass fraction of described metal component of group VIII is 1-6%, the mass fraction of vib metals component is 5-30%, and the mass fraction of adjuvant component is 1-6%.
Catalyst the most according to claim 2, it is characterized in that, count and on the basis of catalyst by oxide, the mass fraction of described metal component of group VIII is 1.5-5%, the mass fraction of vib metals component is 10-20%, and the mass fraction of adjuvant component is 1-5%.
4. according to the catalyst described in any one of claim 1,2 or 3, it is characterised in that the non-noble metal components of described VIIIth race is nickel and cobalt, and the metal component of described group vib is molybdenum, and described adjuvant component is phosphorus and magnesium.
Catalyst the most according to claim 4, it is characterised in that described nickel is 10-45 with the atomic ratio of cobalt, and the phosphorus counted with oxide and the mol ratio of magnesium are as 0.5-3.
Catalyst the most according to claim 5, it is characterised in that described nickel is 13-40 with the atomic ratio of cobalt, and the phosphorus counted with oxide and the mol ratio of magnesium are as 1-2.
Catalyst the most according to claim 1, it is characterised in that the pore volume of described carrier is 0.95-1.15 ml/g, specific surface area is 80-200 rice2/ gram, the pore volume in a diameter of 10-30nm hole accounts for the 60-75% of total pore volume, and the pore volume in a diameter of 300-500nm hole accounts for the 15-30% of total pore volume.
8. the preparation method of the catalyst for hydrorefining distillate oil described in a claim 1, it is included on carrier the composite assistants component of non-noble metal components, at least one metal component being selected from group vib and the phosphorus introducing at least one and being selected from VIII race or phosphorus and magnesium, it is dried afterwards, count and on the basis of described catalyst by oxide, the consumption of each component makes the mass fraction of metal component of group VIII in described catalyst be 0.1-6 weight %, the mass fraction of vib metals component is 1-40 weight %, and the mass fraction of adjuvant component is 0.5-8%；The preparation method of described carrier includes mixing the modifier P2 of hydrated alumina P1 and P1 containing boehmite, aftershaping, be dried and roasting, the pore volume of described P1 is 0.9-1.4 ml/g, and specific surface area is 100-350 rice2/ gram, most probable bore dia 8-30nm；Described P2 is the particulate matter of 80-300 mesh, the Mixing ratio by weight of described P1 and P2 be the κ value of 20-95:5-80, P2 be 0 to less than or equal to 0.9, described κ=DI2/DI1, DI1For the sour peptization index of the hydrated alumina P1 containing boehmite, DI2For the sour peptization index of the modifier P2 of the hydrated alumina P1 containing boehmite, described drying condition includes: temperature is 40-350 DEG C, and the time is 1-24 hour, and roasting condition includes: temperature is that the time is 1-8 hour to less than or equal to 1200 DEG C more than 500.
Method the most according to claim 8, it is characterized in that, count and on the basis of catalyst by oxide, the consumption of each component makes the mass fraction of metal component of group VIII in described catalyst be 1-6%, the mass fraction of vib metals component is 5-30%, and the mass fraction of adjuvant component is 1-6%.
Method the most according to claim 9, it is characterized in that, count and on the basis of catalyst by oxide, the consumption of each component makes the mass fraction of metal component of group VIII in described catalyst be 1.5-5%, the mass fraction of vib metals component is 10-20%, and the mass fraction of adjuvant component is 1-5%.
Method described in 11. according to Claim 8,9 or 10 any one, it is characterised in that the non-noble metal components of described VIIIth race is nickel and cobalt, the metal component of described group vib is molybdenum, and described adjuvant component is phosphorus and magnesium.
12. methods according to claim 11, it is characterised in that described nickel is 10-45 with the atomic ratio of cobalt, and the phosphorus counted with oxide and the mol ratio of magnesium are as 0.5-3.
13. methods according to claim 12, it is characterised in that described nickel is 13-40 with the atomic ratio of cobalt, and the phosphorus counted with oxide and the mol ratio of magnesium are as 1-2.
14. methods according to claim 8, it is characterised in that described drying condition includes: temperature is 100-210 DEG C, the time is 1-15 hour.
15. methods according to claim 14, it is characterised in that described drying condition includes: temperature 120-190 DEG C, drying time is 2-4 hour.
16. methods according to claim 8, it is characterised in that the Mixing ratio by weight of described P1 and P2 is 70-95:5-30, the κ value of described P2 is 0 to less than or equal to 0.6；Described drying condition includes: temperature is 100-200 DEG C, and the time is 2-12 hour, and roasting condition includes: temperature is that roasting time is 2-6 hour to less than or equal to 1000 DEG C more than 800.
17. methods according to claim 8, it is characterised in that the pore volume of described P1 is 0.95-1.3 ml/g, specific surface area is 120-300 rice2/ gram, most probable bore dia 10-25nm；Described P2 is the particulate matter of 100-200 mesh.
Method described in 18. according to Claim 8 or 16, it is characterized in that, one of P1 method being modified as P2 is by described hydrated alumina P1 molding containing boehmite, is dried, afterwards it is completely or partially ground, sieves, obtaining powder body thing is P2, described dry condition includes: temperature is 40-350 DEG C, and the time is 1-24 hour；The two of method are article shaped roastings method one obtained, and sintering temperature is that roasting time is 1-8 hour, it is completely or partially ground afterwards, sieves more than 350 to less than or equal to 1400 DEG C, and obtaining powder body thing is P2；The three of method are to dodge the hydrated alumina P1 containing boehmite to do, and dodging dry temperature is that flash-off time is 0.05-1 hour more than 150 to less than or equal to 1400 DEG C, and obtaining powder body thing is P2；The four of method are several in three modifiers obtained of one of method, the two of method and method to be mixed to get.
19. methods according to claim 18, it is characterised in that the condition being dried in described method one includes: temperature is 100-200 DEG C, and the time is 2-12 hour；Sudden strain of a muscle in the three of method is done temperature and is 200-1000 DEG C, and flash-off time is 0.1-0.5 hour.
Method described in 20. according to Claim 8 or 16 any one, it is characterised in that described P2 is the particulate matter of 80-300 mesh.
21. methods according to claim 20, it is characterised in that described P2 is the particulate matter of 100-200 mesh.
22. 1 kinds of distillate hydrogenation processing methods, including at hydrotreating reaction conditions, by raw oil and catalyst haptoreaction, it is characterised in that described catalyst is the catalyst described in claim 1-7 any one.
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