CN102909048A - 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 good 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, have Hydrogenation and cracking performance, non-noble metal hydrocracking catalyst generally selects VI B and VIII family metal to make hydrogenation component, and cracking performance is mainly provided by acidic components, and acidic components can be selected crystal formation zeolite and/or amorphous aluminum silicide etc.Use amorphous aluminum silicide merely, although selectively higher, active low, operational flexibility is restricted, and all take the crystal formation zeolite as acidic components, or crystal formation zeolite and amorphous aluminum silicide are acidic components jointly in most of hydrocracking catalysts.
The middle oil type hydrocracking catalyst major part of using at present on the commercial plant is the catalyst that contains zeolite, and the zeolite component that adopts mainly is that y-type zeolite, β zeolite and two kinds of zeolites mix use, and catalyst all will carry out presulfurization before reaction, make metal component be converted into sulphided state, to improve the serviceability of catalyst.But use not only contaminated environment, harm operating personnel's health of the higher vulcanizing agent of sulfur content, 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 the β zeolite, and this patent thinks, in order to improve middle distillates oil selectivity and to reduce the hydrogen consumption, the silica/alumina molecular proportion of the zeolite component in the catalyst is 50:1 at least, general 100:1, even 200:1.The middle distillates oil selectivity that the variety classes zeolite is used for catalyst sequentially is: ZSM-20〉β〉the Y type, process Arabic VGO, in the situation that control 60v% transforms, middle distillates oil selectivity 45-65v%, wherein acidic components are the 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, purpose is to improve the middle distillates oil selectivity of catalyst, be characterized in being included in 676-788 ℃ of temperature hydrothermal treatment consists or the best 704 ℃ dry type heat treatment method that passes into inert gas by use, obtained a kind of low acidity Y zeolite, but because this zeolitic acid is spent low, reaction temperature is high when being used for catalytic component processing feedstock oil, generally more than 400 ℃, suppressed hydrogenation reaction, the thermal cracking performance trend of zeolite strengthens, make the middle distillates oil selectivity raising of catalyst 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, example embodies 50-185 °F of naphtha yield and improves obviously, and the use of β zeolite relatively only uses the catalyst activity of Y zeolite also high.Although this catalyst also can be used for oil type hydrocracking catalyst, because the characteristic of the β zeolite that uses, the content range of β zeolite generally is limited between the 2.5w%-10w% in middle oil type catalyst, and generally must be used in conjunction with a kind of γ of being dispersed in-Al
2O
3And so on the sial on the macroporous aluminium oxide matrix, the middle oil type catalyst that this patent relates to has to force down activity for guaranteeing middle distillates oil selectivity, makes reaction temperature higher, and is general more than 390 ℃, thereby caused relatively poor adaptability to raw material.
The hydrogenation component of above-mentioned hydrocracking catalyst is the metal component of sulphided state.In the hydrocracking catalyst, although provided by two kinds of components on hydrogenation activity and the cracking activity main body, but in catalyst, the effect of two kinds of components is not well-separated, but the interactional coordinated effect that influences each other, hydrocracking reaction is raw material collaborative reaction finishing in two kinds of activated centres.How to regulate in the hydrocracking catalyst, the correlation of hydrogenation activity component and cracking activity component is the important content that improves hydrocracking catalyst Integrated using performance.
Phosphorus component is one of usual component of hydrocracking catalyst, and in hydrocracking catalyst, phosphorus generally is present in the catalyst with two kinds of forms.A kind of mode is to introduce with the auxiliary agent form, and general consumption is less, loads on the catalyst with infusion process, is used for regulating the Acidity of catalyst, and the phosphorus in this catalyst generally exists with oxide form; Another kind of mode is phosphorous compound, such as phosphorous heteropoly acid (such as phosphotungstic acid), or phosphorus containing molecular sieve (such 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 the phosphotungstic acid cesium salt, hydrogenation component is nickel, this catalyst has improved the yield of hydrocracking product liquid take heteropoly acid hydrochlorate (phosphotungstic acid cesium salt) as acidic components.But heteropoly acid character is unstable, understands gradually decomposition and inversion under hot conditions, and the stability of catalyst is not enough.
CN200410071124.5 discloses a kind of hydrocracking catalyst that contains zeolite, formed by the carrier loaded group VIII and the group vib metal component that contain matrix and zeolite, wherein said zeolite is P-contained zeolite, in oxide and take described zeolite as benchmark, the content of phosphorus is the 0.1-15 % by weight.CN89100867.5 discloses a kind of hydrocracking catalyst that contains alumo-silicate molecular sieve, and its molecular sieve is the alumo-silicate molecular sieve SAPO of nonzeolite.Though contain phosphorus in the above-mentioned hydrocracking catalyst, the form of phosphorus in catalyst is different, and be also different to the performance impact of catalyst.The oxidized catalyst of preparation need be carried out normal vulcanizing treatment before use, and reactive 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 further to improve.
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 is produced intermediate oil.
Hydrocracking catalyst of the present invention comprises acidic components and active metal component compound, acidic components contain a kind of molecular sieve at least, the active metal component compound comprises the compound of Mo in the group VIB and/or W, and the compound of Ni and/or Co in the VIII family, under the hydrocracking reaction state, the active metal component compound is the phosphatization attitude of metal in the hydrocracking catalyst.
In the hydrocracking catalyst of the present invention, simultaneously can contain the refractory metal oxide, the refractory metal oxide is generally aluminium oxide, silica, silica-alumina (being amorphous aluminum silicide), silica-alumina and is scattered in wherein aluminium oxide (namely being dispersed in the amorphous aluminum silicide in the aluminium oxide), aluminium oxide, magnesia, zirconia, boron oxide and the titanium dioxide that silica is covered with paint, lacquer, colour wash, etc. one or more, is 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 the mesopore molecular sieve, is preferably Y molecular sieve and/or beta-molecular sieve.The modification that required molecular sieve can suit is such as hydrothermal treatment consists modification, acid treatment modification etc.
In the hydrocracking catalyst of the present invention, the composition and ratio of the phosphatization attitude of active metal component is generally: the mol ratio of P and VI B family metallic element is 1:1～2:1, and the mol ratio of P and group VIII metal element is 1:1～1:2.
In the hydrocracking catalyst of the present invention, in catalyst weight, the content of molecular sieve is generally 5%～45%, is preferably 10%～25%; Content is generally 10%-40% to the metal component of group VIB of phosphatization attitude (with WP and/or MoP weighing scale), better is 15%-35%, best 18%-28%, and the metal component of group VIII of phosphatization attitude is (with Ni
2P and/or Co
2The P weighing scale) content is generally 1%-10%, better is 2%-9%, preferably 4%-8%.Refractory inorganic oxides is surplus, and inorganic refractory oxide generally is preferably silica-alumina and/or aluminium oxide.
Hydrocracking catalyst specific surface of the present invention is 180-300m
2/ g, pore volume are 0.25-0.45ml/g, and infrared acidity is 0.25-0.55mmol/g.
The application of hydrocracking catalyst of the present invention in take vacuum distillate as the hydrocracking process of raw material inceasing output of jet fuel and diesel oil, reaction pressure is preferably in 6-20MPa, hydrogen to oil volume ratio 500:1-2000:1, raw material volume space velocity 0.5-2.0hr
-1, reaction temperature 350-410 ℃.Feedstock oil carried out hydrofinishing before carrying out hydrocracking, below organic nitrogen content to 100 μ g/g wherein, be preferably below the 50 μ g/g.
When hydrocracking catalyst of the present invention prepares, make catalyst carrier with molecular sieve and inorganic refractory oxide, then supported active metal component compound and phosphorus containg substances, under hydrogen existence and high temperature, the active metal component compound is converted into the phosphatization attitude, to improve the Integrated using performance of catalyst.The active metal component compound is converted into the phosphatization attitude can carry out in special equipment, also can carry out in reactor.
A kind of concrete preparation process of hydrocracking catalyst of the present invention is as follows: (1) preparation molecular sieve and porous, inorganic refractory oxide carrier and moulding; (2) supported active metal component compound on carrier; (3) dip phosphatizing compound; (4) under hydrogen atmosphere, obtain final catalyst by the hydrogen reducing reaction.
Hydrocracking catalyst of the present invention is owing to adding phosphorus-containing compound, with the common sulfidation cancellation of hydrocracking catalyst, adopt the hydrogen reducing mode that metal-containing compound and the catalyst that contains phosphorus component are carried out activation processing, so that metallic compound is converted into the phosphatization attitude.The phosphatization attitude of active metal component has desirable Hydrogenation on the one hand, and the phosphatization attitude of active metal component has produced certain effect to the acid centre of molecular sieve on the other hand.Show by analysis, the B acid site of reactive metal phosphatization attitude and molecular sieve interacts, significantly improved the acid strength on the zeolite and distributed, strong acid is reduced, middle intensity acid increases, the acid site number increases to some extent, and L acid site number reduces relatively, can reduce the fine melt function like this, increases the activity that moderate strength acid amount is conducive to improve catalyst, reduce reaction temperature, and improve the selective of intermediate oil (kerosene and diesel oil).Hydrocracking catalyst of the present invention can obviously improve the nitrogen resistance of catalyst simultaneously, and when using identical acidic components, the anti-nitrogen ability of catalyst of the present invention obviously improves.
The specific embodiment
A kind of concrete preparation process of hydrocracking catalyst of the present invention comprises:
(1) carrier material that catalyst of the present invention is related (comprising molecular sieve and inorganic refractory oxide) mixes in required ratio.
(2) add suitable amount of adhesive or directly add an amount of dilute acid soln kneading and become paste.
(3) with above-mentioned paste extruded moulding, obtain shaping carrier.
(4) carrier with above-mentioned moulding descended dry 4-12 hour at 80-150 ℃.
(5) carrier that drying is good is at 400-600 ℃ of lower roasting 2-6 hour, the shaping carrier that obtains activating.
(6) preparation contains the hydrogenation dipping solution of VI B family's metal and/or VIII family metallic compound.
(7) adopt saturated dipping or excess solution dipping method that above-mentioned dipping solution is carried on the carrier at the same time or separately, then descended dry 4-12 hour at 80-150 ℃.
(8) preparation phosphorus compound solution.
(9) adopt saturated dipping or excess solution dipping method that above-mentioned dipping solution is carried on the dry good carrier.
(10) carrier that above-mentioned dipping is good descended dry 4-12 hour at 80-150 ℃.
(11) carrier that above-mentioned dipping is good by the temperature programming activation, obtains final catalyst under hydrogen atmosphere.
Carrier material described in the 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 sieves are (such as Y, β, ZSM-5, SAPO-11, modenite, ZSM-22, ZSM-23 etc.), mesoporous molecular sieve is (such as MCM-41, Al-MCM-41, SBA-15, Al-SBA-15 etc.) etc. one or more in can specifically be selected according to the requirement of catalyst application.The auxiliary agent that can contain the catalyst needs in the porous, inorganic refractory oxide carrier, the type of auxiliary agent and content can specifically be selected by this area instructions for use.
Active metal component is group vib metal component or metal component of group VIII described in the step (6), and that the 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 is to support on the carrier by infusion process, can be incipient impregnation, and also excessive dipping can be step impregnation, and also total immersion is steeped, preferably the total immersion stain.Dipping method is that the technical staff is known.Dipping solution prepares by the compound with group VIB and VIII family metal, contain two or more components in molybdenum, tungsten, nickel, the cobalt, its solution concentration can be regulated by the dosage of each compound, thereby the catalyst of preparation specified activity constituent content, the compound method of solution is conventionally known to one of skill in the art.Catalyst according to the common application requirement.The method of supported active metal component comprises solution impregnation and dry run etc.
Phosphorus compound described in the step (8), as be in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) and the ammonium phosphate etc. one or more, be preferably ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) and ammonium phosphate.
Preparation hydrogen temperature programming activation method is in the step (11): with resulting intermediate products in the step (10) under nitrogen atmosphere, take heating rate as 2-10 ℃/min rises to 300-500 ℃ from room temperature, then take heating rate as 0.5-2 ℃/min, be warming up to 600-750 ℃, and intensification outlet temperature constant temperature 2-4 hour.
Hydrogen purity described in the step (11) is greater than the 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 the step (11) hydrogen phosphatization is the chemical reaction of WP such as phosphotungstate hydrogen reduction phosphatization:
2WPO
5.5·0.5H
2O→2WPO
5.5+0.5H
2O
2WPO
5.5+11H→2WP+11?H
2O
WPO wherein
5.50.5H
2After O is the metallic solution dipping, the presoma that in heating process, forms.The XRD spectra of the WP that generates is 21.04 °, 28.68 °, 31.10 °, 43.2 °, 44.6 °, 46.5 ° at 2 θ and locates all to occur stronger diffraction maximum, and is 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) the P presoma reduces, and generates Ni with Ni
12P
5(3) Ni
12P
5Further reduction generates Ni
2P.Be 40.7 °, 44.6 °, 54.2 ° and 54.9 ° at 2 θ and locate all to occur stronger diffraction maximum, be 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 generally in 250-600 ℃ of scope, in the 300-550 ℃ of scope of being everlasting, wherein the cut more than the 70w% is more than 350 ℃ for the boiling range of heavy hydrocarbon material.Have These characteristics feedstock oil such as gas oil, vacuum distillate, take off pitch prill oil, catalytic cracking recycle oil, shale oil, coal tar wet goods.Reaction condition generally under the hydrogen existence condition, reaction pressure 5-20MPa, hydrogen to oil volume ratio 100:1-5000:1, raw material volume space velocity 0.1-5.0hr
-1, reaction temperature 350-450 ℃.Hydrocracking process generally comprises the hydrofinishing of leading portion, be used for removing the most S of feedstock oil, N, and the saturated severity that reduces the operation of hydrocracking section of polycyclic aromatic hydrocarbon, but catalyst of the present invention can reduce the severity of refining stage operation, embodies preferably serviceability when high nitrogen-containing.
Following embodiment has illustrated the present invention, yet does not limit its scope.Reduction activation is to carry out under the normal pressure under the hydrogen atmosphere.
Comparative example 1
With 25.3 gram Y sieves (butt 95wt%), 71.4 gram amorphous aluminum silicide (SiO
2Content 50wt%, pore volume 0.85ml/g, specific area 370m
2/ g, butt 70wt%), 122.9 gram macroporous aluminium oxide (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 133.3 gram adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) put into the roller mixed grind, add water, be rolled into paste, extrusion is extruded bar 110 ℃ of dryings 4 hours, then 550 ℃ of roastings 4 hours, get carrier T-1, character sees Table 1.
Carrier is with the maceration extract room temperature dipping of Tungstenic compound and nickel compound (ammonium metatungstate and nickel nitrate, lower with) 2 hours, and 120 ℃ of dryings 4 hours 500 ℃ of roastings 4 hours, get catalyst B J-1, and catalyst property sees Table 2.Catalyst uses the common vulcanizing treatment of row of advancing, sulfidation for hydrogen sulfide containing hydrogen 230 ℃ of constant temperature 8 hours, 280 ℃ of constant temperature 8 hours, 320 ℃ of constant temperature 8 hours.
Embodiment 1
The carrier T-1 of comparative example 1 was flooded 2 hours with the maceration extract room temperature of Tungstenic compound and nickel compound, 120 ℃ of dryings 4 hours, prepare the ammonium dihydrogen phosphate that concentration is weight concentration 30%, the carrier that above-mentioned drying is good flooded 2 hours with the solution containing phosphate for preparing, 120 ℃ of dryings 4 hours, again carrier reduction activation under hydrogen atmosphere that above-mentioned dipping is good, the reduction activation program is for to rise to 500 ℃ with 5 ℃/min from room temperature, take heating rate as 2 ℃/min, rise to 750 ℃ from 500 ℃, and 750 ℃ of constant temperature 2 hours, be prepared into catalyst C-1 of the present invention.
Through XRD analysis (under the nitrogen protection condition), can find out to have tungsten phosphide (WP) and nickel phosphide (Ni in the catalyst of the present invention
2P) characteristic diffraction peak has formed the phosphatization attitude of reactive metal.
Comparative example 2
With 14.7 gram beta-molecular sieves (butt 95wt%), 151.4 gram amorphous aluminum silicide (SiO
2Content 50wt%, pore volume 0.85ml/g, specific area 370m
2/ g, butt 70wt%), 57.1 gram macroporous aluminium oxide (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 133.3 gram adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) put into the roller mixed grind, add water, be rolled into paste, extrusion is extruded bar 110 ℃ of dryings 4 hours, then 550 ℃ of roastings 4 hours, get carrier T-2, character sees Table 1.
Carrier is with the maceration extract room temperature dipping of tungstenic and nickel 2 hours, and 120 ℃ of dryings 4 hours 500 ℃ of roastings 4 hours, get catalyst B J-2, and catalyst property sees Table 2.Catalyst uses the common vulcanizing treatment of row of advancing, and sulfidation is identical with comparative example 1.
Embodiment 2
The carrier T-2 of comparative example 2 was flooded 2 hours with the maceration extract room temperature of tungstenic and nickel, 100 ℃ of dryings 6 hours, preparing concentration is the ammonium hydrogen phosphate solution of weight concentration 40%, the carrier that above-mentioned drying is good flooded 2 hours with the solution containing phosphate for preparing, 120 ℃ of dryings 5 hours, the carrier that above-mentioned dipping is good is under hydrogen atmosphere again, carry out the hydrogen activation, at first rise to 300 ℃ with 10 ℃/min from room temperature, take heating rate as 1 ℃/min, rise to 600 ℃ from 300 ℃, and 600 ℃ of constant temperature 4 hours, prepare phosphatization transition-metal catalyst C-2.
Comparative example 3
With 8.4 gram Y molecular sieves (butt 95wt%), 85.7 gram amorphous aluminum silicide (SiO
2Content 50wt%, pore volume 0.85ml/g, specific area 370m
2/ g, butt 70wt%), 131.42 gram macroporous aluminium oxide (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 133.3 gram adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) put into the roller mixed grind, add water, be rolled into paste, extrusion is extruded bar 110 ℃ of dryings 4 hours, then 550 ℃ of roastings 4 hours, get carrier T-3, character sees Table 1.
Carrier is with the maceration extract room temperature dipping of tungstenic and nickel 2 hours, and 120 ℃ of dryings 4 hours 500 ℃ of roastings 4 hours, get catalyst B J-3, and catalyst property sees Table 2.Catalyst uses the common vulcanizing treatment of row of advancing, and sulfidation is identical with comparative example 1.
Embodiment 3
The carrier T-3 of comparative example 3 was flooded 2 hours with the maceration extract room temperature of tungstenic and nickel, 110 ℃ of dryings 6 hours, prepare the ammonium dihydrogen phosphate that concentration is weight concentration 60%, the carrier that above-mentioned drying is good flooded 2 hours with the solution containing phosphate for preparing, 110 ℃ of dryings 5 hours, the carrier that above-mentioned dipping is good is under hydrogen atmosphere again, carry out activation processing, at first rise to 400 ℃ with 8 ℃/min from room temperature, take heating rate as 1 ℃/min, rise to 650 ℃ from 400 ℃, and 650 ℃ 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 forms 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 ℃), kg/m 3 | 920.6 |
| Boiling range, ℃ | ? |
| ? 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 catalyst comparative evaluation result of the present invention.
| Catalyst | BJ-1 | C-1 | BJ-2 | C-2 | BJ-3 | C-3 |
| The refined oil nitrogen content, μ g/g | 3 | 25 | 5 | 28 | 8 | 32 |
| Reaction temperature, ℃ | 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 |
| The 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
The present embodiment has been introduced by the catalyst of the present invention's preparation and the activity rating result of comparative example catalyst.Estimate at the fixed bed hydrogenation experimental rig, 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 is listed in table 3.The catalyst for preparing in above-mentioned each example is estimated under above-mentioned process conditions, and the evaluation result that obtains is listed in table 4.
As can be seen from Table 4, catalyst of the present invention is in the situation that the obvious raising of refined oil nitrogen content activity is higher, and product property is better.
Claims (10)
1. hydrocracking catalyst, comprise acidic components and active metal component compound, acidic components contain a kind of molecular sieve at least, the active metal component compound comprises the compound of Mo in the group VIB and/or W, and the compound of Ni and/or Co in the VIII family, it is characterized in that: under the hydrocracking reaction state, the active metal component compound is the phosphatization attitude of metal in the hydrocracking catalyst.
2. according to catalyst claimed in claim 1, it is characterized in that: in the hydrocracking catalyst, contain simultaneously the refractory metal oxide, the refractory metal oxide is that aluminium oxide, silica, silica-alumina, silica-alumina are scattered in one or more in wherein aluminium oxide, aluminium oxide, magnesia, zirconia, boron oxide and the titanium dioxide that silica is covered with paint, lacquer, colour wash, etc.
3. according to claim 1 or 2 described catalyst, 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 the mesopore molecular sieve.
4. according to catalyst claimed in claim 1, it is characterized in that: the composition and ratio of the phosphatization attitude of metal is: the mol ratio of P and VI B family metallic element is 1:1～2:1, and the mol ratio of P and group VIII metal element is 1:1～1:2.
5. according to claim 1 or 2 described catalyst, it is characterized in that: in catalyst weight, the content of molecular sieve is 5%～45%, is preferably 10%～25%; Take the metal component of group VIB content of WP and/or MoP weighing scale phosphatization attitude as 10%-40%, better be 15%-35%, best 18%-28%; With Ni
2P and/or Co
2The metal component of group VIII content of P weighing scale phosphatization attitude is 1%-10%, better is 2%-9%, preferably 4%-8%; Refractory inorganic oxides is surplus.
6. the application of the described catalyst of the arbitrary claim of claim 1 to 5 in take vacuum distillate as the hydrocracking process of raw material inceasing output of jet fuel and diesel oil, reaction pressure is preferably in 6-20MPa, hydrogen to oil volume ratio 500:1-2000:1, raw material volume space velocity 0.5-2.0hr
-1, reaction temperature 350-410 ℃, feedstock oil carried out hydrofinishing before carrying out hydrocracking, below organic nitrogen content to 100 μ g/g wherein.
7. the preparation method of the described catalyst of the arbitrary claim of claim 1 to 5 is characterized in that comprising following process: (1) preparation molecular sieve and inorganic refractory oxide carrier and moulding; (2) supported active metal component compound on carrier; (3) dip phosphatizing compound; (4) under hydrogen atmosphere, obtain final catalyst by the hydrogen reducing reaction.
8. in accordance with the method for claim 7, it is characterized in that: supported active metal component compound comprises dipping and drying steps on the carrier, carries out drying behind the dip phosphatizing compound.
9. it is characterized in that in accordance with the method for claim 7: phosphorus compound is one or more in phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) and the ammonium phosphate.
10. in accordance with the method for claim 7, it is characterized in that: the hydrogen reducing reaction method is under nitrogen atmosphere, take heating rate as 2-10 ℃/min rises to 300-500 ℃ from room temperature, then take heating rate as 0.5-2 ℃/min, be warming up to 600-750 ℃, and intensification outlet temperature constant temperature 2-4 hour.
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