CN102909048B - Hydrocracking catalyst, and preparation method and application thereof - Google Patents
Hydrocracking catalyst, and preparation method and application thereof Download PDFInfo
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Abstract
The invention describes a hydrocracking catalyst, and a preparation method and an application thereof. The hydrocracking catalyst comprises an acid component and an active metal component compound, wherein the acid component comprises at least one molecular sieve; the active metal component compound comprises a compound of Mo and/or W in a VIB group and a compound of Ni and /Co in a VIII group; and in a hydrocracking reaction state, the active metal component compound in the hydrocracking catalyst is in a metal phosphatizing state. The catalyst has excellent usage performance, good catalyst activity and high selectivity for medium oil under the condition of high nitrogen content in raw oil, is suitable for hydrocracking processes for increasing jet fuels and clean diesel oil, has stronger adaptability for nitrogen, and can reduce burden of a refining catalyst.
Description
Technical field
The present invention relates to a kind of hydrocracking catalyst and its preparation method and application, this catalyst has excellent hydrocracking performance and Hydrodewaxing performance, and middle distillates oil selectivity is high, inceasing output of jet fuel and diesel oil.
Background technology
Hydrocracking catalyst is a kind of bifunctional catalyst, there is Hydrogenation and cracking performance, non-noble metal hydrocracking catalyst generally selects VI B and VIII race's metal to make hydrogenation component, and cracking performance provides primarily of acidic components, and acidic components can select crystal formation zeolite and/or amorphous aluminum silicide etc.Simple amorphous aluminum silicide, although selective higher, active low, operational flexibility is restricted, in most of hydrocracking catalyst all with crystal formation zeolite for acidic components, or crystal formation zeolite and amorphous aluminum silicide are acidic components jointly.
The middle oil type hydrocracking catalyst major part that commercial plant uses at present is the catalyst containing zeolite, and the zeolite component adopted mainly y-type zeolite, β zeolite and two kinds of zeolites are used in combination, and catalyst all will carry out presulfurization before reactions, metal component is made to be converted into sulphided state, to improve the serviceability of catalyst.But use the health of the higher vulcanizing agent of sulfur content not only contaminated environment, harm operating personnel, and sulfidation is numerous and diverse, needs to drop into a lot of manpower and materials.
US4820402 discloses a kind of hydrocracking catalyst, has used β zeolite, and this patent is thought, in order to improve middle distillates oil selectivity and reduce hydrogen consumption, the silica/alumina molecular proportion at least 50:1 of the zeolite component in catalyst, general 100:1, even 200:1.The middle distillates oil selectivity order that variety classes zeolite is used for catalyst is: ZSM-20> β >Y type, process Arabic VGO, when control 60v% transforms, middle distillates oil selectivity 45-65v%, wherein acidic components are β zeolite, during conversion ratio 60v%, the catalyst middle distillates oil selectivity that this patent relates to is no more than 70v%.
US4894142 discloses a kind of hydrocracking catalyst, object is the middle distillates oil selectivity improving catalyst, be characterized in by using the dry type heat treatment method passing into inert gas being included in 676-788 DEG C of temperature water heat treatment or best 704 DEG C, obtain a kind of low acidity Y zeolite, but because this zeolitic acid is spent low, high for reaction temperature during catalytic component process feedstock oil, general more than 400 DEG C, inhibit hydrogenation reaction, the thermal cracking performance trend of zeolite strengthens, the middle distillates oil selectivity of catalyst is improved not obvious, middle distillates oil selectivity is no more than 70%.
US5447623 discloses hydrocracking catalyst and the technique thereof of a kind of compound β zeolite and Y zeolite, but this catalyst is mainly used in light oil type hydrogen cracking catalyst, embodiment 50-185 °F of naphtha yield improves obviously, and the use of β zeolite relatively only uses the catalyst activity of Y zeolite also high.Although this catalyst also may be used for middle oil type hydrocracking catalyst, due to the characteristic of used β zeolite, in middle oil type catalyst, the content range of β zeolite is generally limited between 2.5w%-10w%, and generally must be dispersed in γ-Al with the use of one
2o
3and so on the sial on macroporous aluminium oxide matrix, the middle oil type catalyst that this patent relates to is for ensureing middle distillates oil selectivity, and activity of having to force down, makes reaction temperature higher, general more than 390 DEG C, thus result in poor adaptability to raw material.
The hydrogenation component of above-mentioned hydrocracking catalyst is the metal component of sulphided state.In hydrocracking catalyst, although hydrogenation activity and cracking activity main body are provided by two kinds of components, but in the catalyst, the effect of two kinds of components is not well-separated, but the interactional coordinated effect that influences each other, hydrocracking reaction is the reaction that raw material has been worked in coordination with on two kinds of activated centres.How regulating in hydrocracking catalyst, the correlation of hydrogenation active component and cracking active component, is the important content improving the comprehensive serviceability of hydrocracking catalyst.
Phosphorus component is one of usual component of hydrocracking catalyst, and in hydrocracking catalyst, phosphorus is generally present in catalyst in two forms.A kind of mode introduces with auxiliary agent form, and general consumption is less, loads on catalyst with infusion process, and for regulating the Acidity of catalyst, the phosphorus in this catalyst generally exists in the form of an oxide; Another kind of mode is phosphorous compound, as phosphorous heteropoly acid (as phosphotungstic acid), or phosphorus containing molecular sieve (as phosphorus modified molecular sieves or skeleton phosphorus containing molecular sieve etc.).
CN200910112036.8 discloses a kind of hydrocracking catalyst and preparation method thereof, hydrocracking catalyst comprises acidic components and hydrogenation component, acidic components are phosphotungstic acid cesium salt, hydrogenation component is nickel, this catalyst for acidic components, improves the yield of hydrocracking product liquid with heteropoly acid hydrochlorate (phosphotungstic acid cesium salt).But heteropoly acid character is unstable, under the high temperature conditions can decomposition and inversion gradually, the stability of catalyst is not enough.
CN200410071124.5 discloses a kind of hydrocracking catalyst containing zeolite, be made up of the carrier loaded group VIII containing matrix and zeolite and group vib metal component, wherein said zeolite is P-contained zeolite, with oxide basis and with described zeolite for benchmark, the content of phosphorus is 0.1-15 % by weight.CN89100867.5 discloses a kind of hydrocracking catalyst containing alumo-silicate molecular sieve, and its molecular sieve is the alumo-silicate molecular sieve SAPO of nonzeolite.Though containing phosphorus in above-mentioned hydrocracking catalyst, phosphorus form is in the catalyst different, also different to the performance impact of catalyst.The oxidized catalyst of preparation needs to carry out normal vulcanizing treatment before use, and active metal is converted into sulphided state, and phosphorus is generally oxidation state or exists with the form of heteropoly acid or phosphorus containing molecular sieve, and the serviceability of catalyst needs to improve further.
Summary of the invention
The object of the invention is to obtain a kind of hydrocracking catalyst and its preparation method and application, for the treatment of heavy hydrocarbon material, maximum produces intermediate oil.
Hydrocracking catalyst of the present invention comprises acidic components and active metal component compound, acidic components are at least containing a kind of molecular sieve, active metal component compound comprises the compound of Mo and/or W in group VIB, and the VIIIth compound of Ni and/or Co in race, under hydrocracking reaction state, in hydrocracking catalyst, active metal component compound is the phosphatization state of metal.
In hydrocracking catalyst of the present invention, Refractory metal oxides can be contained simultaneously, one or more in Refractory metal oxides is generally aluminium oxide, silica, silica-alumina (i.e. amorphous aluminum silicide), silica-alumina are scattered in aluminium oxide (being namely dispersed in the amorphous aluminum silicide in aluminium oxide) wherein, silica is covered with paint, lacquer, colour wash, etc. aluminium oxide, magnesia, zirconia, boron oxide and titanium dioxide, are preferably amorphous aluminum silicide and/or alumina component.Molecular sieve is generally one or more in Y molecular sieve, beta-molecular sieve, ZSM-5 molecular sieve, SAPO-11 molecular sieve, modenite, ZSM-22 molecular sieve, ZSM-23 molecular screen and mesopore molecular sieve, is preferably Y molecular sieve and/or beta-molecular sieve.Required molecular sieve can carry out the modification be suitable for, as hydrothermal treatment consists modification, acid treatment modification etc.
In hydrocracking catalyst of the present invention, the composition and ratio of the phosphatization state of active metal component is generally: the mol ratio of P and VI B race metallic element is the mol ratio of 1:1 ~ 2:1, P and group VIII metal element is 1:1 ~ 1:2.
In hydrocracking catalyst of the present invention, with catalyst weight, the content of molecular sieve is generally 5% ~ 45%, is preferably 10% ~ 25%; Metal component of group VIB (with WP and/or the MoP weighing scale) content of phosphatization state is generally 10%-40%, and be better 15%-35%, best 18%-28%, the metal component of group VIII of phosphatization state is (with Ni
2p and/or Co
2p weighing scale) content is generally 1%-10%, is better 2%-9%, preferably 4%-8%.Refractory inorganic oxides is surplus, and inorganic refractory oxide is generally preferably silica-alumina and/or aluminium oxide.
Hydrocracking catalyst specific surface of the present invention is 180-300m
2/ g, pore volume is 0.25-0.45ml/g, and infrared acidity is 0.25-0.55mmol/g.
The application of hydrocracking catalyst of the present invention in the hydrocracking process taking vacuum distillate as raw material inceasing output of jet fuel and diesel oil, reaction pressure preferably at 6-20MPa, hydrogen to oil volume ratio 500:1-2000:1, raw material volume air speed 0.5-2.0hr
-1, reaction temperature 350-410 DEG C.Feedstock oil, before carrying out hydrocracking, carries out hydrofinishing, and organic nitrogen content is wherein reduced to 100 below μ g/g, is preferably 50 below μ g/g.
Time prepared by hydrocracking catalyst of the present invention, catalyst carrier is made with molecular sieve and inorganic refractory oxide, then supported active metals component composition and phosphorus containg substances, under hydrogen existence and high temperature, be phosphatization state by active metal component converting compounds, to improve the comprehensive serviceability of catalyst.Active metal component converting compounds is that phosphatization state can be carried out in special equipment, also can carry out in the reactor.
The concrete preparation process of one of hydrocracking catalyst of the present invention is as follows: (1) prepares molecular sieve and porous, inorganic refractory oxide carrier and shaping; (2) at supported on carriers active metal component compound; (3) dip phosphatizing compound; (4) in a hydrogen atmosphere, final catalyst is obtained by reacting by hydrogen reducing.
Hydrocracking catalyst of the present invention is owing to adding phosphorus-containing compound, common for hydrocracking catalyst sulfidation is cancelled, adopt hydrogen reducing mode to carry out activation process to metal-containing compound with containing the catalyst of phosphorus component, make metallic compound be converted into phosphatization state.The phosphatization state of active metal component has desirable Hydrogenation on the one hand, and the acid centre of phosphatization state to molecular sieve of active metal component creates certain effect on the other hand.Show by analysis, the B acid site of active metal phosphatization state and molecular sieve interacts, significantly improve the acid strength distribution on zeolite, strong acid is reduced, middle intensity acid increases, acid site number increases to some extent, and L acid site number reduces relatively, can reduce fine melt function like this, increase the activity that moderate strength acid amount is conducive to improving catalyst, reduce reaction temperature, and improve the selective of intermediate oil (kerosene and diesel oil).Hydrocracking catalyst of the present invention can significantly improve the nitrogen resistance of catalyst simultaneously, and when using identical acidic components, the resistance to nitrogen ability of catalyst of the present invention significantly improves.
Detailed description of the invention
The concrete preparation process of one of hydrocracking catalyst of the present invention comprises:
(1) carrier material (comprising molecular sieve and inorganic refractory oxide) involved by catalyst of the present invention is mixed in required ratio.
(2) add suitable amount of adhesive or directly add appropriate dilute acid soln kneading and become paste.
(3) by above-mentioned paste extruded moulding, shaping carrier is obtained.
(4) by above-mentioned shaping carrier dry 4-12 hour at 80-150 DEG C.
(5) by dried carrier roasting 2-6 hour at 400-600 DEG C, the shaping carrier activated is obtained.
(6) preparation contains the hydrogenation dipping solution of VI B race metal and/or VIII race's metallic compound.
(7) saturated dipping or excess solution impregnation method is adopted to be carried at the same time or separately on carrier by above-mentioned dipping solution, then dry 4-12 hour at 80-150 DEG C.
(8) phosphorus compound solution is prepared.
(9) saturated dipping or excess solution impregnation method is adopted to be carried on dried carrier by above-mentioned dipping solution.
(10) by carrier good for above-mentioned dipping dry 4-12 hour at 80-150 DEG C.
(11) by carrier good for above-mentioned dipping in a hydrogen atmosphere, activated by temperature programming, obtain final catalyst.
Carrier material described in step (1) is porous, inorganic refractory oxide carrier, comprise aluminium oxide, silica, silica-alumina, silica-alumina is scattered in aluminium oxide wherein, the aluminium oxide that silica is covered with paint, lacquer, colour wash, etc., magnesia, zirconia, boron oxide, titanium dioxide, various molecular sieve is (as Y, β, ZSM-5, SAPO-11, modenite, ZSM-22, ZSM-23 etc.), mesoporous molecular sieve is (as MCM-41, Al-MCM-41, SBA-15, Al-SBA-15 etc.) etc. in one or more, specifically can select according to the requirement in catalyst application field.The auxiliary agent that can need containing catalyst in porous, inorganic refractory oxide carrier, the type of auxiliary agent and content specifically can be selected by this area instructions for use.
Described in step (6), active metal component is group vib metal component or metal component of group VIII, and that group vib metal component is the most frequently used is Mo and/or W, and that metal component of group VIII is the most frequently used is Co and/or Ni.The solution of group VIB and metal component of group VIII supports on carrier by infusion process, can be incipient impregnation, may also be excessive dipping, can be step impregnation, may also be total immersion stain, preferably total immersion stain.Dipping method is known by technical staff.Dipping solution is by preparing with the compound of group VIB and VIII race's metal, containing two or more components in molybdenum, tungsten, nickel, cobalt, its solution concentration regulates by the dosage of each compound, thus prepare the catalyst of specified activity constituent content, the compound method of solution is conventionally known to one of skill in the art.According to the catalyst that common application requires.The method of supported active metals component comprises solution impregnation and dry run etc.
Phosphorus compound described in step (8), as being one or more in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) and ammonium phosphate etc., is preferably ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) and ammonium phosphate.
Prepare in step (11) hydrogen temperature programming activation method for: by the intermediate products that obtain in step (10) under a hydrogen atmosphere, be that 2-10 DEG C/min rises to 300-500 DEG C from room temperature with heating rate, then be 0.5-2 DEG C/min with heating rate, be warming up to 600-750 DEG C, and at intensification outlet temperature constant temperature 2-4 hour.
Hydrogen purity described in step (11) is greater than 95%(volume), hydrogen gas space velocity is 50-1000h
-1, pressure can be normal pressure to 1MPa, be preferably normal pressure.
The course of reaction of the hydrogen reduction of activation procedure generation slaine described in step (11) hydrogen phosphatization, if phosphotungstate hydrogen reduction phosphatization is the chemical reaction of WP:
2WPO
5.5·0.5H
2O→2WPO
5.5+0.5H
2O
2WPO
5.5+11H→2WP+11 H
2O
Wherein WPO
5.50.5H
2o is after metallic solution dipping, the presoma formed in heating process.The XRD spectra of the WP generated is that stronger diffraction maximum all appears in 21.04 °, 28.68 °, 31.10 °, 43.2 °, 44.6 °, 46.5 ° places at 2 θ, identical with the standard spectrogram (PDF-29-1364) of WP.
The H of the phosphide of Ni
2reduction process: (1) Ni
2p
2o
7→ Ni; (2) P presoma reduction, and generate Ni with Ni
12p
5; (3) Ni
12p
5further reduction generates Ni
2p.Being that stronger diffraction maximum all appears in 40.7 °, 44.6 °, 54.2 ° and 54.9 ° of places at 2 θ, is Ni
2the diffraction maximum of P.
Hydrocracking catalyst of the present invention is applicable to hydrocracking process, is particularly suitable for treatment of heavy hydrocarbon material, and the boiling range of heavy hydrocarbon material is generally within the scope of 250-600 DEG C, and through being everlasting within the scope of 300-550 DEG C, wherein the cut of more than 70w% is more than 350 DEG C.There is the feedstock oil of These characteristics as gas oil, vacuum distillate, de-pitch prill oil, catalytic cracking recycle oil, shale oil, coal tar wet goods.Reaction condition generally under hydrogen existence condition, reaction pressure 5-20MPa, hydrogen to oil volume ratio 100:1-5000:1, raw material volume air speed 0.1-5.0hr
-1, reaction temperature 350-450 DEG C.Hydrocracking process generally comprises the hydrofinishing of leading portion, for removing most S, N in feedstock oil, and the saturated severity reducing the operation of hydrocracking section of polycyclic aromatic hydrocarbon, but catalyst of the present invention can reduce the severity of refining stage operation, embodies good serviceability when high nitrogen-containing.
Following embodiment describes the present invention, but does not limit its scope.Under hydrogen atmosphere, reduction activation is carry out under normal pressure.
Comparative example 1
By 25.3 grams of Y sieves (butt 95wt%), 71.4 grams of amorphous aluminum silicide (SiO
2content 50wt%, pore volume 0.85ml/g, specific area 370m
2/ g, butt 70wt%), 122.9 grams of macroporous aluminium oxides (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier T-1, character is in table 1.
The maceration extract room temperature immersion of carrier Tungstenic compound and nickel compound (ammonium metatungstate and nickel nitrate, lower with) 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 hours, obtain catalyst B J-1, catalyst property was in table 2.Catalyst uses the common vulcanizing treatment of row of advancing, and sulfidation is with hydrogen sulfide containing hydrogen 230 DEG C of constant temperature 8 hours, 280 DEG C of constant temperature 8 hours, 320 DEG C of constant temperature 8 hours.
Embodiment 1
By the maceration extract room temperature immersion 2 hours of the carrier T-1 Tungstenic compound of comparative example 1 and nickel compound, 120 DEG C of dryings 4 hours, prepare the ammonium dihydrogen phosphate that concentration is weight concentration 30%, the above-mentioned dried carrier solution containing phosphate prepared is flooded 2 hours, 120 DEG C of dryings 4 hours, again by carrier reduction activation in a hydrogen atmosphere good for above-mentioned dipping, reduction activation program is for rise to 500 DEG C with 5 DEG C/min from room temperature, be 2 DEG C/min with heating rate, 750 DEG C are risen to from 500 DEG C, and 750 DEG C of constant temperature 2 hours, be prepared into catalyst C-1 of the present invention.
Through XRD analysis (under nitrogen protection condition), can find out, there is in catalyst of the present invention tungsten phosphide (WP) and nickel phosphide (Ni
2p) characteristic diffraction peak, defines the phosphatization state of active metal.
Comparative example 2
By 14.7 grams of beta-molecular sieves (butt 95wt%), 151.4 grams of amorphous aluminum silicide (SiO
2content 50wt%, pore volume 0.85ml/g, specific area 370m
2/ g, butt 70wt%), 57.1 grams of macroporous aluminium oxides (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier T-2, character is in table 1.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 hours, obtain catalyst B J-2, catalyst property was in table 2.Catalyst uses the common vulcanizing treatment of row of advancing, and sulfidation is identical with comparative example 1.
Embodiment 2
By the maceration extract room temperature immersion 2 hours of the carrier T-2 tungstenic of comparative example 2 and nickel, 100 DEG C of dryings 6 hours, prepare the ammonium hydrogen phosphate solution that concentration is weight concentration 40%, the above-mentioned dried carrier solution containing phosphate prepared is flooded 2 hours, 120 DEG C of dryings 5 hours, again by carrier good for above-mentioned dipping in a hydrogen atmosphere, carry out Hydrogen activation, first 300 DEG C are risen to 10 DEG C/min from room temperature, be 1 DEG C/min with heating rate, rise to 600 DEG C from 300 DEG C, and 600 DEG C of constant temperature 4 hours, prepare phosphatization transition-metal catalyst C-2.
Comparative example 3
By 8.4 grams of Y molecular sieves (butt 95wt%), 85.7 grams of amorphous aluminum silicide (SiO
2content 50wt%, pore volume 0.85ml/g, specific area 370m
2/ g, butt 70wt%), 131.42 grams of macroporous aluminium oxides (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier T-3, character is in table 1.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 hours, obtain catalyst B J-3, catalyst property was in table 2.Catalyst uses the common vulcanizing treatment of row of advancing, and sulfidation is identical with comparative example 1.
Embodiment 3
By the maceration extract room temperature immersion 2 hours of the carrier T-3 tungstenic of comparative example 3 and nickel, 110 DEG C of dryings 6 hours, prepare the ammonium dihydrogen phosphate that concentration is weight concentration 60%, the above-mentioned dried carrier solution containing phosphate prepared is flooded 2 hours, 110 DEG C of dryings 5 hours, again by carrier good for above-mentioned dipping in a hydrogen atmosphere, carry out activation process, first 400 DEG C are risen to 8 DEG C/min from room temperature, be 1 DEG C/min with heating rate, rise to 650 DEG C from 400 DEG C, and 650 DEG C of constant temperature 4 hours, prepare phosphatization transition-metal catalyst C-3.
the physico-chemical property of table 1 catalyst carrier.
| Numbering | T-1 | T-2 | T-3 |
| Molecular sieve, wt% | 12.0 | 7.0 | 4.0 |
| Amorphous aluminum silicide, wt% | 25.0 | 53.0 | 30.0 |
| Macroporous aluminium oxide, wt% | 43.0 | 20.0 | 46.0 |
| Adhesive, wt% | 20.0 | 20.0 | 20.0 |
| Pore volume, ml/g | 0.73 | 0.76 | 0.78 |
| Specific area, m 2/g | 425 | 392 | 383 |
table 2 catalyst composition and character.
| Numbering | BJ-1 | C-1 | BJ-2 | C-2 | BJ-3 | C-3 |
| WO 3，wt% | 16.58 | - | 22.82 | - | 23.27 | - |
| WP，wt% | - | 15.76 | - | 22.6 | - | 23.18 |
| NiO，wt% | 4.36 | - | 5.73 | - | 5.81 | - |
| Ni 2P，wt% | - | 3.63 | - | 5.02 | - | 5.55 |
| Pore volume, ml/g | 0.56 | 0.54 | 0.53 | 0.55 | 0.55 | 0.56 |
| Specific area, m 2/g | 324 | 330 | 279 | 285 | 281 | 292 |
table 3 feedstock oil main character.
| Feedstock oil | Vacuum distillate |
| Density (20 DEG C), kg/m 3 | 920.6 |
| Boiling range, DEG C | |
| IBP/10% | 328/413 |
| 30%/50% | 450/471 |
| 70%/90% | 493/522 |
| 95%/EBP | 534/545 |
| Nitrogen, μ g/g | 1575 |
| Carbon, wt% | 85.25 |
| Hydrogen, wt% | 11.96 |
| Carbon residue, wt% | 0.35 |
table 4 COMPARATIVE CATALYST's evaluation result of the present invention.
| Catalyst | BJ-1 | C-1 | BJ-2 | C-2 | BJ-3 | C-3 |
| Refined oil nitrogen content, μ g/g | 3 | 25 | 5 | 28 | 8 | 32 |
| Reaction temperature, DEG C | 383 | 369 | 390 | 373 | 393 | 376 |
| Product yield and character | ||||||
| Heavy naphtha | ||||||
| Yield, wt% | 9 | 8.7 | 8.9 | 6.5 | 9.7 | 9.8 |
| Virtue is dived, wt% | 61.9 | 62.6 | 62.8 | 63.2 | 60.8 | 61.3 |
| Jet fuel | ||||||
| Yield, wt% | 25.3 | 23.3 | 23.8 | 22.6 | 22.6 | 22.7 |
| Smoke point, mm | 24 | 27 | 23 | 27 | 22 | 28 |
| Aromatic hydrocarbons, volume % | 8.9 | 7.8 | 10 | 8.1 | 12.4 | 10.8 |
| Diesel oil | ||||||
| Yield, wt% | 36.5 | 35.6 | 35.9 | 38.6 | 32.6 | 33 |
| Cetane number | 58.2 | 62.3 | 56.4 | 60.3 | 55.5 | 60.1 |
| Tail oil | ||||||
| Yield, wt% | 24.2 | 28.7 | 28.5 | 29.4 | 28.6 | 28.2 |
| BMCI value | 9.8 | 8.1 | 10 | 8.6 | 11 | 9 |
| Chemical hydrogen consumption, wt% | 2.21 | 2.09 | 2.18 | 2.07 | 2.26 | 2.10 |
| Middle distillates oil selectivity, wt % | 83.7 | 84.9 | 85.6 | 88.8 | 80.2 | 80.6 |
Embodiment 4
This embodiment describes the Activity evaluation of catalyst and the comparative example catalyst prepared by the present invention.Fixed bed hydrogenation experimental rig is evaluated, and appreciation condition is: reaction stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200, feedstock oil volume space velocity 1.0h
-1, use vacuum distillate (VGO) as feedstock oil, feedstock oil character lists in table 3.Evaluated under above-mentioned process conditions by the catalyst prepared in above-mentioned each example, the evaluation result obtained lists in table 4.
As can be seen from Table 4, catalyst of the present invention activity when refined oil nitrogen content significantly improves is higher, and product property is better.
Claims (10)
1. a hydrocracking catalyst, comprise acidic components and active metal component compound, acidic components are at least containing a kind of molecular sieve, active metal component compound comprises the compound of Mo and/or W in group VIB, and the VIIIth compound of Ni and/or Co in race, it is characterized in that: under hydrocracking reaction state, in hydrocracking catalyst, active metal component compound is the phosphatization state of metal, the mol ratio of P and VI B race metallic element is 1:1 ~ 2:1, the mol ratio of P and group VIII metal element is 1:1 ~ 1:2, with catalyst weight, the content of molecular sieve is 5% ~ 45%, with the metal component of group VIB content of WP and/or MoP weighing scale phosphatization state for 10%-40%, with Ni
2p and/or Co
2the metal component of group VIII content of P weighing scale phosphatization state is 1%-10%, refractory inorganic oxides is surplus.
2. according to catalyst according to claim 1, it is characterized in that: in hydrocracking catalyst, simultaneously containing Refractory metal oxides, Refractory metal oxides is aluminium oxide, silica, amorphous aluminum silicide, be dispersed in aluminium oxide amorphous aluminum silicide in one or more.
3. according to the catalyst described in claim 1 or 2, it is characterized in that: molecular sieve is one or more in Y molecular sieve, beta-molecular sieve, ZSM-5 molecular sieve, SAPO-11 molecular sieve, modenite, ZSM-22 molecular sieve, ZSM-23 molecular screen and mesopore molecular sieve.
4. according to the catalyst described in claim 1 or 2, it is characterized in that: with catalyst weight, the content of molecular sieve is for being 10% ~ 25%; With the metal component of group VIB content of WP and/or MoP weighing scale phosphatization state for 15%-35%; With Ni
2p and/or Co
2the metal component of group VIII content of P weighing scale phosphatization state is 2%-9%; Refractory inorganic oxides is surplus.
5. according to catalyst according to claim 4, it is characterized in that: with the metal component of group VIB content of WP and/or MoP weighing scale phosphatization state for 18%-28%; With Ni
2p and/or Co
2the metal component of group VIII content of P weighing scale phosphatization state is 4%-8%.
6. the application of the catalyst described in the arbitrary claim of claim 1 to 5 in the hydrocracking process taking vacuum distillate as raw material inceasing output of jet fuel and diesel oil, reaction pressure is at 6-20MPa, hydrogen to oil volume ratio 500:1-2000:1, raw material volume air speed 0.5-2.0hr
-1, reaction temperature 350-410 DEG C, feedstock oil, before carrying out hydrocracking, carries out hydrofinishing, and organic nitrogen content is wherein reduced to 100 below μ g/g.
7. a preparation method for catalyst described in the arbitrary claim of claim 1 to 5, is characterized in that comprising following process: (1) prepares molecular sieve and inorganic refractory oxide carrier and shaping; (2) at supported on carriers active metal component compound; (3) dip phosphatizing compound; (4) in a hydrogen atmosphere, final catalyst is obtained by reacting by hydrogen reducing.
8. in accordance with the method for claim 7, it is characterized in that: supported on carriers active metal component compound comprises dipping and drying steps, carries out drying after dip phosphatizing compound.
9. in accordance with the method for claim 7, it is characterized in that: phosphorus compound is one or more in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) and ammonium phosphate.
10. in accordance with the method for claim 7, it is characterized in that: hydrogen reducing reaction method is under a hydrogen atmosphere, be that 2-10 DEG C/min rises to 300-500 DEG C from room temperature with heating rate, then be 0.5-2 DEG C/min with heating rate, be warming up to 600-750 DEG C, and at intensification outlet temperature constant temperature 2-4 hour.
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|---|---|---|---|
| CN201110217547.3A CN102909048B (en) | 2011-08-01 | 2011-08-01 | Hydrocracking catalyst, and preparation method and application thereof |
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| CN103949280B (en) * | 2014-05-14 | 2016-04-13 | 武汉凯迪工程技术研究总院有限公司 | Be suitable for the Catalysts and its preparation method that living beings Fischer-Tropsch synthesis oil produces aviation kerosine |
| CN105312071A (en) * | 2014-07-28 | 2016-02-10 | 南京大学 | Method for preparing composite oxide supported Ni2P catalyst |
| CN105435837B (en) * | 2014-08-29 | 2019-01-08 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and its preparation and application |
| CN104258888A (en) * | 2014-09-25 | 2015-01-07 | 中国科学院山西煤炭化学研究所 | Hydrocracking catalyst capable of reducing polycyclic aromatic hydrocarbon compounds in coal tar and application thereof |
| CN106140251B (en) * | 2015-03-27 | 2018-07-20 | 中国石油化工股份有限公司 | Carrier of hydrocracking catalyst and preparation method thereof |
| CN106140287B (en) * | 2015-03-27 | 2018-06-19 | 中国石油化工股份有限公司 | The preparation method of hydrocracking catalyst |
| CN106582782A (en) * | 2015-10-15 | 2017-04-26 | 中国石油化工股份有限公司 | High-nitrogen-resistance hydrocracking catalyst and preparation method thereof |
| CN106582781B (en) * | 2015-10-15 | 2020-03-31 | 中国石油化工股份有限公司 | High-sulfur-resistance hydrocracking catalyst and preparation method thereof |
| CN106582778A (en) * | 2015-10-15 | 2017-04-26 | 中国石油化工股份有限公司 | Light cycle oil hydrocracking catalyst and preparation method thereof |
| CN107008487B (en) * | 2017-05-08 | 2020-11-06 | 武汉凯迪工程技术研究总院有限公司 | Hydrocracking catalyst for diesel oil and jet fuel production and preparation method thereof |
| CN110090660B (en) * | 2018-01-30 | 2022-01-04 | 中国石油化工股份有限公司 | Composite material containing Y-type molecular sieve and preparation method thereof |
| CN109529926A (en) * | 2018-12-06 | 2019-03-29 | 中国科学院山西煤炭化学研究所 | A kind of naphthalene is hydrocracked the catalyst and preparation method and application of light aromatics processed |
| US11130119B2 (en) * | 2019-07-03 | 2021-09-28 | Saudi Arabian Oil Company | Methods for producing multifunctional catalysts for upgrading pyrolysis oil |
| CN114433208B (en) * | 2020-10-19 | 2024-01-12 | 中国石油化工股份有限公司 | Method for producing middle distillate by hydrocracking |
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