CN1281310C

CN1281310C - Hydrocracking catalyst containing silicon oxide-alumina

Info

Publication number: CN1281310C
Application number: CN 200410037668
Authority: CN
Inventors: 毛以朝; 聂红; 石亚华; 李大东; 王奎; 张润强; 熊震霖; 胡志海
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2004-04-29
Filing date: 2004-04-29
Publication date: 2006-10-25
Anticipated expiration: 2024-04-29
Also published as: CN1690173A

Abstract

The present invention relates to a hydrocracking catalyst comprising silicon oxide-alumina. The catalyst comprises silicon oxide-alumina, beta-zeolite, at least one metal component selected from iron, cobalt and nickel in a VIII family, and at least one metal component selected from molybdenum or tungsten in a VIB family. The k value of the silicon oxide-alumina is from 0.4 to 15 A. (cm<2>. g)<-1>. When the catalyst is used as a reference, the content of the silicon oxide-alumina is from 10 to 90 wt 5, and the content of the beta-zeolite is from 1 to 50 wt%. Measured by oxides, the content of the metal component in a VIII family is from 1 to 10 wt%, and the content of the metal component in a VIB family is from 5 to 40 wt%. The catalyst has high hydrocracking activity, and simultaneously has favorable selectivity of middle distillate.

Description

A kind of monox-alumina containning hydrocracking catalyst

Technical field

The invention relates to a kind of hydrocracking catalyst, more specifically say so about a kind of monox-alumina containning hydrocracking catalyst.

Background technology

In recent years, crude oil heavy and poor qualityization tendency are obvious day by day in the world wide, meanwhile, demand to middle distillate and reformation, steam crack material but constantly increases, this impels the hydrocracking technology that turns to purpose with the high-quality of heavy distillate and lightweight to be developed rapidly, and hydrocracking catalyst is wherein important and one of The key factor.

Hydrocracking catalyst is a kind of bifunctional catalyst, and it has lytic activity and hydrogenation activity simultaneously, promptly contains acidic components and hydrogenation activity component simultaneously, and its acidity is mainly provided by heat-resistant inorganic oxide that constitutes carrier and/or various zeolite; The hydrogenation activity component generally is selected from metal, metal oxide and/or the metal sulfide of group vib and VIII family in the periodic table of elements.For reaching different requirements, need carry out adaptive modulation to acidic components in the catalyst and hydrogenation activity component to the hydrocracking product.

For example, molecular sieve is the main acidic components in the hydrocracking catalyst, by to the selection of molecular sieve type and the control of consumption, can reconcile and improve the distribution and the character of hydrocracking product.But the heat-resistant inorganic oxide that constitutes carrier also directly influences the character of catalyst.In the hydrocracking catalyst of forming by molecular sieve and alumina host, introduce silica-alumina, can remedy the active low defective of alumina host acid catalysis, activity of such catalysts and selectivity are improved.

CN 1315883 discloses a kind of hydrocracking catalyst that contains modification Beta zeolite, is benchmark with the percentage by weight of catalyst, comprising: (a) Beta zeolite 5%-40%; (b) large pore volume refractory oxide 10%-70%; (c) aperture aluminium oxide 0%-30%; (d) group vib metal oxide 10%-40%; (e) VIII metal oxide 1%-10%; Described Beta zeolite SiO2/Al2O3 mol ratio is 20-150, and the secondary pore pore volume of＞2nm accounts for more than 40% of total pore volume, specific surface 500-750m2/g, infrared acidity 0.05-0.5mmol/g, Na ₂O weight content＜0.2%, at 25 ℃, P/Po is 0.1 o'clock, and water adsorption amount is less than 5 heavy %, and n-butanol adsorption experiment residual value is less than 0.4, ion exchange capacity＜0.07.Said large pore volume refractory oxide is selected from the mixture of aluminium oxide, sial or aluminium oxide and silica.Adopt this catalyst to carry out hydrocracking, the diesel oil freezing point in the product is lower, can produce the long distillate low freezing point diesel fuel.

Though the monox-alumina containning hydrocracking catalyst that prior art provides can satisfy the requirement of some hydrocracking reactions, its hydrogenation cracking activity is still lower.

Summary of the invention

The objective of the invention is provides higher hydrocracking catalyst of a kind of activity and preparation method thereof at the existing lower shortcoming of catalyst hydrogenation cracking activity.

The present inventor finds that the Bronsted acid amount of contained silica-alumina is lower in the monox-alumina containning hydrocracking catalyst that prior art provides, and its k value is less than 0.4A (cm ²G) ^-1This is to cause the low major reason of this class catalyst hydrogenation cracking activity.

Catalyst provided by the invention contains a kind of silica-alumina, a kind of beta-zeolite, at least a iron, cobalt or nickel and at least a molybdenum or the tungsten metal component that is selected from group vib that is selected from group VIII, and the k value of wherein said silica-alumina is 0.4-15A (cm ²G) ^-1, be benchmark with the catalyst, the content of silica-alumina is 10-90 weight %, and the content of beta-zeolite is 1-50 weight %, and in oxide, the content of group VIII metal component is that the content of 1-10 weight %, group vib metal component is 5-40 weight %; Described k=B/M _SiO2, B is the Bronsted acid amount of silica-alumina, M _SiO2Molar fraction for silica in the silica-alumina.

The invention provides the Preparation of catalysts method comprises, a kind of silica-alumina and a kind of beta-zeolite are mixed iron, cobalt or nickel and at least a molybdenum or the tungsten metal component that is selected from group vib that is incorporated at least a group VIII of introducing in this mixture, and the k value of wherein said silica-alumina is 0.4-15A (cm ²G) ^-1Said k=B/M _SiO2, B is the Bronsted acid amount of silica-alumina, M _SiO2Molar fraction for silica in the silica-alumina.

Catalyst provided by the invention is compared with existing catalyst owing to adopted the high silica-alumina of Bronsted acid content, and its hydrogenation cracking activity improves.In addition, catalyst provided by the invention also has the selectivity of intermediate oil preferably.

For example, catalyst CH-2 provided by the invention is identical with Beta molecular sieve, tungsten oxide, nickel oxide content among the comparative catalyst X, and the k value of different the is contained silica-alumina of catalyst CH-2 is 2.1, and the k value of catalyst X is 0.36.Adopt same materials oil with identical reaction condition two kinds of different catalysts to be estimated, the product that relatively generates oil distributes, and the invention provides 370 ℃ of catalyst ⁺The comparison of distillate yield is than catalyst low 4.8%, illustrate that catalyst provided by the invention has higher hydrogenation cracking activity, the yield comparison of 65-370 ℃ of light oil that the invention provides catalyst is higher by 2.3% than catalyst, illustrates that catalyst provided by the invention has better intermediate oil selectivity.

Description of drawings

Fig. 1 is the contained silica-alumina of catalyst provided by the invention, the existing contained silica-alumina of hydrocracking catalyst and γ-Al ₂O ₃X-ray diffraction spectra.

The specific embodiment

According to catalyst provided by the invention, wherein said silica-alumina is that the k value is 0.4-15A (cm ²G) ^-1Silica-alumina, k=B/M wherein _SiO2, B is the Bronsted acid amount of silica-alumina, M _SiO2Molar fraction for silica in the silica-alumina.B adopts Bio-Rad IFS-3000 type determination of infrared spectroscopy.Concrete grammar is: be pressed into about 10mg/cm behind sample self porphyrize ²The self-supporting sheet, place the original position pond of infrared spectrometer, in 350 ℃, 10 ^-3Pa vacuum lower surface purified treatment 2 hours is reduced to room temperature and is introduced the pyridine saturated vapor, after the adsorption equilibrium 15 minutes, vacuumizes desorption 30 minutes under 200 ℃, reduces to room temperature and surveys absorption and decide the pyridine vibrational spectrum.Sweep limits is 1400cm ^-1-1700cm ^-1, with 1540 ± 5cm ^-1[the infrared Absorption value of unit are, unit mass sample is expressed as its Bronsted acid amount of ratio value defined of the infrared Absorption value of bands of a spectrum and sample strip weight and area: A (cm ²G) ^-1].M _SiO2Calculate after adopting X fluorescence method [Yang Cuiding etc., petrochemical industry analytical method (RIPP test method), Science Press, 1990, P380] working sample to form.

Described k value is 0.4-15A (cm ²G) ^-1Silica-alumina, can be commercially available or adopt any one prior art for preparing.The k value of preferred silica-alumina is 0.5-13A (cm ²G) ^-1, further preferred silica-alumina is that the k value is 0.5-13A (cm ²G) ^-1And silica-alumina with one or more X-ray diffraction spectrogram among γ, η, θ, δ and the x of feature.Several X-ray diffraction spectrograms that satisfy the silica-alumina with gama-alumina X-ray diffraction spectrogram of requirement of the present invention are seen a, b, c, d, the e among Fig. 1 respectively, h among Fig. 1 is the X-ray diffraction spectrogram of gama-alumina, with the catalyst is benchmark, the content of silica-alumina is 10-90 weight %, is preferably 15-70 weight %.

A kind of k value is 0.5-13A (cm ²G) ^-1And the silica-alumina with gama-alumina X-ray diffraction spectrogram of feature is the Siral series silica-alumina that German Condea company produces.

For example, the trade mark is that silica-alumina k value after high roasting of Siral40 is 0.58A (cm ²G) ^-1, X-ray diffraction spectrogram (seeing Fig. 1 d) is consistent with the X-ray diffraction spectrogram of gama-alumina.

A preferred preparation k value is 0.5-13A (cm ²G) ^-1And the method with silica-alumina of one or more aluminium oxide X-ray diffraction spectrogram among γ, η, θ, δ and the x of feature is: containing si molecular sieves or containing the composition that disordering contains si molecular sieves and mix the hydrate of aluminium oxide and at least a disordering, in 350-850 ℃ of roasting 2-8 hour, preferably in 450-650 ℃ of roasting 3-6 hour.The hydrate of described aluminium oxide is selected from one or more the mixture among hibbsite, monohydrate alumina and the amorphous hydroted alumina; Or one or more the mixture among one or more hibbsite, monohydrate alumina and the amorphous hydroted alumina in siliceous, the titanium, magnesium, boron, zirconium, thorium, niobium, rare earth; Can also be: will be selected from containing si molecular sieves or contain the composition that disordering contains si molecular sieves and directly mixing of the aluminium oxide of one or more crystal formations among γ, η, θ, δ and the x and at least a disordering.With the silica-alumina is benchmark, and the content of silica is 1-60 weight %, is preferably 1-45 weight %.

The condition that the disordering molecular sieve should satisfy is: when adopting XRD to characterize, be that 100% characteristic peak is a benchmark with original molecule sieve relative intensity, the relative intensity that disordering contains this characteristic peak of si molecular sieves is below 15%.

Described disordering molecular sieve comprises any one siliceous molecular sieve of disordering, for example silicon metal-the aluminate of disordering, silicon-phosphorus-aluminate, faujasite, ZSM series are boiled (as among ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35 and the ZSM-38 one or more), are preferably in the ZSM series zeolite of the faujasite of disordering and disordering one or more.

The hydrate of described aluminium oxide and disordering contain si molecular sieves or contain ratio that composition that disordering contains si molecular sieves mixes that should to make the silica content in the poriness silicon oxide-aluminium oxide that finally makes be 1-60 weight %, be preferably 1-45 weight %.

Described disordering contains si molecular sieves and can obtain by following two kinds of approach:

Article one, approach is to prepare the partially-crystallized si molecular sieves that contains.This partially-crystallized method can adopt in the prior art incomplete crystallization to prepare the method for low-crystallinity molecular sieve, for example C.P.Nicolaides is at ANovel Family of Solid Acid Catalysts:Substantially Amorphous orPartially Crystalline Zeolitic Materials, Applied Catalysis A:General 185,1999, reported among the 211-217.

The second approach is that the si molecular sieves that contains with complete crystallization carries out disordering and handles.For example to X type and Y zeolite, in the atmosphere of drying (as steam partial pressure less than 0.0069 MPa, preferably less than 0.00138 MPa) roasting down; And for example, at high temperature and V ₂O ₅Or MoO ₃Make the Y zeolite disordering under existing, this disordering trend increases (J.Thoret with the rising of temperature and/or the increase of metal oxide content, etc.Solid-State Interaction Between NaY Zeolite andVanadium Pentoxide, Molybdenum Trioxide, or Tungsten Trioxide, Zeolites, 13,1993,269-275); For another example, in the presence of water vapour, use V ₂O ₅Make Y zeolite disordering (Carlos A.Trujillo, etc.The Mechnism of Zeolite YDestruction by Steam in the Presence of Vanadium, Journal ofCatalysis 168,1-15,1997); Under certain condition, adopt halide to handle Y zeolite and can cause disordering (Kurt A.Becker equally, Catalytic Properties of SyntheticFaujasites Modified with Fluoride Anions, J, Chem.Soc., FaradayTrans.I, 1987,83,535-545), (Kurt A.Becker, etc., Modificationof HY-Zeolite with Trifluoromethane, React.Kinet.Catal.Lett., Vol.29, No.1,1-7,1985).

Beta-zeolite is the known zeolites of people, and its The Nomenclature Composition and Structure of Complexes is at U.S.Patent.No.3,308,069 and Re28341 in existing narration.According to catalyst provided by the invention, wherein suitable beta-zeolite can be commercially available commodity, also can adopt any one prior art for preparing.Preferred β zeolite is that silica (mol ratio) is at least 25, beta-zeolite as 30-500, more preferred β zeolite is that silica (mol ratio) is 30-200, EP164 is seen in description for this beta-zeolite, 939, U.S.Patent.No.4,923,690, U.S.Patent.No.5,164,169, patent such as CN 1108213A, CN1108214A, CN 1086792A.With the catalyst is benchmark, and the content of described beta-zeolite is the heavy % of 1-50, the heavy % of preferred 1-45.

According to catalyst provided by the invention, described iron, cobalt, the nickel that is selected from least a group VIII is preferably nickel, and the molybdenum in the VI family, tungsten are preferably tungsten.In oxide and with the catalyst is benchmark, the content of group VIII metal component is 1-10 weight %, be preferably 2-8 weight %, the content of group vib metal component is 5-40 weight %, be preferably 10-35 weight %, described metal component can be simple substance, oxide and/or sulfide and composition thereof.

The invention provides the Preparation of catalysts method comprises described silica-alumina is mixed with beta-zeolite, under the condition that is enough at least a iron, cobalt or the nickel that is selected from group VIII and at least a molybdenum that is selected from group vib or tungsten metal component be deposited on the mixture, mixture after the described roasting and the iron that contains at least a group VIII, cobalt or nickel are selected from the molybdenum of group vib or the solution of tungsten metallization compound contacts with at least a, for example by methods such as ion-exchange, dipping, co-precipitation, preferred infusion process.

Iron in the said group VIII, cobalt, nickel metallic compound are selected from one or more in the soluble compound of these metals, can be in the nitrate, acetate, soluble carbon hydrochlorate, chloride, soluble complexes of these metals one or more as them.

Molybdenum in the said group vib, tungsten metallization compound are selected from one or more in the soluble compound of these metals, can be in molybdate, paramolybdate, tungstates, metatungstate, the ethyl metatungstate one or more as them.

According to catalyst provided by the invention, look the article shaped that various objectives or requirement can be made into various easy operatings, for example microballoon, sphere, tablet or bar shaped etc.Moulding can be carried out according to a conventional method, all can as methods such as compressing tablet, spin, extrusions.

In the embodiment preferred, method for preparing catalyst comprises that with described k value be 0.4-15A (cm ²G) ^-1Silica-alumina mix with a kind of beta-zeolite, moulding and at 400-650 ℃ of roasting 2-8 hour; With the iron that contains at least a group VIII, cobalt or nickel and at least a described article shaped of solution impregnation that is selected from the molybdenum or the tungsten metallization compound of group vib.

According to the conventional method in this area, catalyst provided by the invention is before using, usually can be in the presence of hydrogen, under 140-370 ℃ temperature, carry out presulfurization with sulphur, hydrogen sulfide or sulfur-bearing raw material, this presulfurization can be carried out also can original position vulcanizing in device outside device, is translated into sulfide type.

Catalyst provided by the invention is applicable to hydrocarbon raw material carried out hydrocracking, has hydrocarbon fraction than low boiling and lower molecular weight with production.Described hydrocarbon raw material can be various heavy mineral oils or artificial oil or their mixed fraction oil, as straight run gas oil (straight run gas oil), vacuum gas oil (VGO) (vacuum gas oil), metal removal oil (demetallized oils), reduced crude (atmosphericresidue), depitching decompression residuum (deasphalted vacuum residue), coker distillate (coker distillates), catalytic cracking distillate oil (cat craker distillates), shale oil (shale oil), asphalt sand oil (tar sand oil), liquefied coal coil (coal liquid) etc.The hydrocracking that catalyst provided by the invention is specially adapted to heavy and inferior distillate oil is 149-371 ℃ to produce boiling range, and especially boiling range is the hydrocracking process of 180-370 ℃ of intermediate oil.

When catalyst provided by the invention is used for distillate hydrocracking, can under the hydrocracking process condition of routine, use, as reaction temperature 200-510 ℃, preferred 300-450 ℃, reaction pressure 3-24 MPa, preferred 4-15 MPa, liquid hourly space velocity (LHSV) 0.1-10 hour ^-1Preferred 0.2-5 hour ^-1, hydrogen to oil volume ratio 100-5000, preferred 200-1000.

To the present invention be described by example below.

Agents useful for same in the example except that specifying, is chemically pure reagent.

The hydrogenation activity constituent content adopts x-ray fluorescence spectrometry [Yang Cuiding etc., petrochemical industry analytical method (RIPP test method), Science Press, 1990, P380].

The X-ray diffraction experiment carries out on SIMENS D5005 type X-ray diffractometer, CuK α radiation, and 44KV, 40mA, sweep speed is 2 °/minute.

Example 1-5 has described and has been applicable to silica-alumina of the present invention and preparation method thereof.

Example 1

With 800 gram NaY type molecular sieve (SiO ₂/ Al ₂O ₃=4.8, degree of crystallinity is defined as 100%, Chang Ling refinery product) placing 4000 milliliters, concentration is ammonium chloride (Beijing Chemical Plant's product of 1.0 moles, analyze pure) in the aqueous solution, exchange is 1 hour under 90 ℃ of stirrings, filters, and spends deionised water and does not detect to there being chlorion, 120 ℃ of oven dry, 550 ℃ of roastings 4 hours.Repeat the Y zeolite A that said process obtains sodium content (in sodium oxide molybdena) 0.35 weight % (flame atomic absorption spectrometry mensuration) for twice, recording sample degree of crystallinity with x-ray diffraction method is 76%, getting Y zeolite A 200 gram, to place 1000 milliliters, concentration be ammonium fluoride (Beijing Chemical Plant's product of 0.2 mole, analyze pure) in the aqueous solution, filter after 1 hour in stirring at normal temperature, 120 ℃ of oven dry, 600 ℃ of roastings 4 hours obtain disordering Y zeolite B (the X ray diffracting characteristic peak of B disappears); Getting 1.5 liters of concentration is 60 gram Al ₂O ₃/ liter sodium aluminate solution, place one 2 liters one-tenth glue jar, 60 ℃ of initial temperatures feed CO from the bottom that becomes the glue jar ₂Content is carbon dioxide and the Air mixing gas of 90 body %, and the flow of gaseous mixture is 1.5 meters ³/ hour, reaction is 15 minutes, and pH drops to 8.8, and this moment, reaction temperature was 73 ℃, stopped into the glue reaction, added sodium carbonate rapidly, made slurries pH rise to 11.0.Be warming up to 90 ℃ and wore out 4 hours, filter, wash 4 times, filter and obtain wet cake C with 20 times of 90 ℃ of deionized waters to solid content; Get disordering Y zeolite B 80 grams and mix making beating with C, filter back 120 ℃ of oven dry, obtain the precursor Si-1 (butt 73 heavy %) of poriness silicon oxide-aluminium oxide, with Si-1 in 550 ℃ of roastings 4 hours, its x-ray diffraction spectra is seen Fig. 1 a, and silica content and k value see Table 1.

Example 2

Taking by weighing 12 gram example 1 disordering Y zeolite B and 100 gram SB powder (diaspore that German Condea company produces) mixes, obtain the precursor Si-2 (butt 74 weight %) of silica-alumina, with Si-2 in 550 ℃ of roastings 4 hours, its x-ray diffraction spectra is seen Fig. 1 b, and silica content and k value see Table 1

Example 3

Contain the rare-earth five-membered ring structure zeolite by example among the CN1020269C 12 is synthetic, obtain containing rare-earth five-membered ring structure zeolite D; According to identical condition is that crystallization temperature is 90 ℃ and synthetic obtains the partially-crystallized rare-earth five-membered ring structure zeolite E that contains.Contain rare-earth five-membered ring structure zeolite E silica content 93.3 weight %, alumina content 4.5 weight %, RE ₂O ₃1.5 weight % (RE ₂O ₃Represent rare earth oxide, wherein lanthana accounts for 26 weight % of total amount of the rare earth oxide, and oxidation Cerium accounts for 51 weight % of rare earth oxide gross weight, and other rare earth oxide accounts for 23 weight % of rare earth oxide gross weight).To contain rare-earth five-membered ring structure zeolite D is that the degree of crystallinity that benchmark is measured part crystallization ZSM-5-5 molecular sieve E is 6%.

Getting boehmite powder (Shandong Aluminum Plant's production) 150 grams respectively mixes with partially-crystallized rare-earth five-membered ring structure zeolite E 38 grams that contain, in mixture, add 300 milliliters of deionized waters, normal temperature stirred 30 minutes down, filter, 150 ℃ of dryings 6 hours obtain silica-alumina precursor Si-3 (butt 73 weight %), with Si-3 in 550 ℃ of roastings 4 hours, its x-ray diffraction spectra is seen Fig. 1 c, and silica content and k value see Table 1.

Example 4

This example silica-alumina is through 550 ℃ of roastings 4 hours, and the commodity Siral40 of its X-ray diffracting spectrum such as Fig. 1 d (German Codea company product, silica content 40 weight %) is numbered Si-4, and silica content and k value see Table 1.

Example 5

Precursor Si-4 104 gram, SB powder (diaspore that German Condea company produces) 26 grams of getting silica-alumina mix, and obtain Si-4/SB, and in 550 ℃ of roastings 4 hours, its x-ray diffraction spectra was seen Fig. 1 e with Si-4/SB, and silica content and k value see Table 1.

Silica-alumina that Comparative Examples 1-2 explanation preparation reference catalyst is used and preparation method thereof.

Comparative Examples 1

Synthetic silica-aluminium oxide in accordance with the following methods: get 90 gram Al ₂O ₃/ liter 934 milliliters of aluminum trichloride solutions, place one 2 liters one-tenth glue jar, stir a following concentration and be 22% ammoniacal liquor to pH6.0, intensification degree to 60 ℃, constant temperature splashes into the sodium silicate solution that 162.5 ml concns are 6 gram silica/100 milliliter after one hour, with concentration is that 25 heavy % sulfuric acid are reconciled pH to 8.5, reacted 1 hour, filter, wash 120 ℃ of oven dry 4 times with 20 times of 90 ℃ of deionized waters to solid content, obtain the precursor Q (butt 76 weight %) of silica-alumina, in 550 ℃ of roastings 4 hours, its x-ray diffraction spectra was seen Fig. 1 f with Q, and silica content and k value see Table 1.

Comparative Examples 2

Precursor Q 202.4 grams that prepare silica-alumina according to 1 method of Comparative Examples and SB powder (diaspore that German Condea company produces) 63.3 restrains and mixes, obtain Q/SB, in 550 ℃ of roastings 4 hours, its x-ray diffraction spectra was seen Fig. 1 g with Q/SB, and silica content and k value see Table 1;

Table 1

Example	1	2	3	4	5	Comparative Examples 1	Comparative Examples 2
Example	1	2	3	4	5	Comparative Examples 1	Comparative Examples 2	Numbering	Si-1	Si-2	Si-3	Si-4	Si-4/SB	Q	Q/SB
SiO ₂(weight %)	32.5	6.8	25.0	40.0	32.5	32.5	25.0	Numbering	Si-1	Si-2	Si-3	Si-4	Si-4/SB	Q	Q/SB
SiO ₂(weight %)	32.5	6.8	25.0	40.0	32.5	32.5	25.0	M _SiO2	0.45	0.11	0.36	0.5	0.45	0.45	0.36
B[A·(cm ²·g) ^-1]	5.4	0.7	0.76	0.3	0.26	0.15	0.13	M _SiO2	0.45	0.11	0.36	0.5	0.45	0.45	0.36
B[A·(cm ²·g) ^-1]	5.4	0.7	0.76	0.3	0.26	0.15	0.13	K[A·(cm ²·g) ^-1]	12.1	6.4	2.1	0.6	0.58	0.33	0.36

Example 6-11 illustrates catalyst provided by the invention and preparation process thereof.

Example 6

Precursor Si-2 (butt) and 147.2 gram β zeolite (Chang Ling oil plant catalyst plant products with 93.9 gram silica-aluminas, silica alumina ratio 28, butt 80 heavy %) mix, be extruded into circumscribed circle diameter and be 1.8 millimeters trilobal bar, 120 ℃ of oven dry, programming rate with 2 ℃/minute under air atmosphere is warming up to 500 ℃, constant temperature 4 hours, get 180 grams with containing ammonium metatungstate (Sichuan Zigong Hard Alloy Foundry product after being cooled to room temperature, tungsten oxide content is 82 weight %) 79.8 grams, nickel nitrate (the new Photochemical agents in Beijing factory product, nickel oxide content is 27.85 weight %) 59.2 aqueous solution dippings that restrain, 120 ℃ of oven dry 480 ℃ of roastings 4 hours, obtain catalyst CH-1, with the catalyst is benchmark, wherein molecular sieve, nickel oxide, the content of tungsten oxide sees Table 2.

Example 7

The precursor Si-3 that gets 194.2 gram silica-aluminas mixes with 20 gram β zeolites (with example 6), be extruded into circumscribed circle diameter and be 1.8 millimeters trilobal bar, 120 ℃ of oven dry, programming rate with 2 ℃/minute under air atmosphere is warming up to 580 ℃, constant temperature 4 hours, get 230 grams with containing ammonium metatungstate (with example 6) 116.4 grams after being cooled to room temperature, the aqueous solution dipping of nickel nitrate (with example 6) 47.09 grams, 120 ℃ of oven dry, 480 ℃ of roastings 4 hours, obtain catalyst CH-2, with the catalyst is benchmark, wherein molecular sieve, nickel oxide, the content of tungsten oxide sees Table 2.

Comparative Examples 3

This Comparative Examples explanation reference catalyst and preparation thereof.

The precursor Q/SB that gets 194.2 gram silica-aluminas mixes with 20 gram β zeolites (with example 6), be extruded into circumscribed circle diameter and be 1.8 millimeters trilobal bar, 120 ℃ of oven dry, programming rate with 2 ℃/minute under air atmosphere is warming up to 580 ℃, constant temperature 4 hours, get 230 grams with containing the aqueous solution dipping that ammonium metatungstate (with example 6) 116.4 restrains, nickel nitrate (with example 6) 47.09 restrains after being cooled to room temperature, 120 ℃ of oven dry, 480 ℃ of roastings 4 hours, obtain catalyst X, with the catalyst is benchmark, and wherein the content of molecular sieve, nickel oxide, tungsten oxide sees Table 2.

Example 8

With 150 gram Si-3 silica-alumina precursor and 25.7 gram β zeolite (Chang Ling oil plant catalyst plant products, silica alumina ratio 110, butt 86 heavy %) mix, be extruded into circumscribed circle diameter and be 1.8 millimeters trilobal bar, 120 ℃ of oven dry, programming rate with 2 ℃/minute under air atmosphere is warming up to 450 ℃, constant temperature 4 hours, get 110 grams with containing ammonium metatungstate (with example 6) 49.51 grams after being cooled to room temperature, the aqueous solution dipping of nickel nitrate (with example 6) 27.76 grams, 120 ℃ of oven dry 480 ℃ of roastings 4 hours, obtain catalyst CH-3, with the catalyst is benchmark, wherein molecular sieve, nickel oxide, the content of tungsten oxide sees Table 2.

Example 9

150 gram Si-1 are mixed with 185.9 gram β zeolites (with example 6), be extruded into circumscribed circle diameter and be 1.8 millimeters trilobal bar, 120 ℃ of oven dry, programming rate with 2 ℃/minute under air atmosphere is warming up to 450 ℃, constant temperature 4 hours, get 310 grams with containing the aqueous solution dipping that ammonium metatungstate (with example 6) 118.78 restrains, nickel nitrate (with example 6) 99.2 restrains after being cooled to room temperature, 120 ℃ of oven dry, 480 ℃ of roastings 4 hours, obtain catalyst CH-4, with the catalyst is benchmark, and wherein the content of molecular sieve, nickel oxide, tungsten oxide sees Table 2.

Comparative Examples 4

This Comparative Examples explanation reference catalyst and preparation thereof

The precursor Q that gets 150 gram silica-aluminas mixes with 185.9 gram β zeolites (with example 6), be extruded into circumscribed circle diameter and be 1.8 millimeters trilobal bar, 120 ℃ of oven dry, programming rate with 2 ℃/minute under air atmosphere is warming up to 450 ℃, constant temperature 4 hours, get 310 grams with containing the aqueous solution dipping that ammonium metatungstate (with example 6) 118.78 restrains, nickel nitrate (with example 6) 99.2 restrains after being cooled to room temperature, 120 ℃ of oven dry, 480 ℃ of roastings 4 hours, obtain catalyst W, with the catalyst is benchmark, and wherein the content of molecular sieve, nickel oxide, tungsten oxide sees Table 2.

Example 10

150 gram Si-4/SB are mixed with 185.91 gram β zeolites (with example 6), be extruded into circumscribed circle diameter and be 1.8 millimeters trilobal bar, 120 ℃ of oven dry, programming rate with 2 ℃/minute under air atmosphere is warming up to 580 ℃, constant temperature 4 hours, get 280 grams with containing the aqueous solution dipping that ammonium metatungstate (with example 6) 118.78 restrains, nickel nitrate (with example 6) 99.2 restrains after being cooled to room temperature, 120 ℃ of oven dry, 480 ℃ of roastings 4 hours, obtain catalyst CH-5, with the catalyst is benchmark, and wherein the content of molecular sieve, nickel oxide, tungsten oxide sees Table 2.

Example 11

150 gram Siral40 are mixed with 44.51 gram β zeolites (with example 6), be extruded into circumscribed circle diameter and be 1.8 millimeters trilobal bar, 120 ℃ of oven dry, programming rate with 2 ℃/minute under air atmosphere is warming up to 450 ℃, constant temperature 4 hours, get 118 grams with containing the aqueous solution dipping that ammonium metatungstate (with example 6) 63.8 restrains, nickel nitrate (with example 6) 23.0 restrains after being cooled to room temperature, 120 ℃ of oven dry, 480 ℃ of roastings 4 hours, obtain catalyst CH-6, with the catalyst is benchmark, and wherein the content of molecular sieve, nickel oxide, tungsten oxide sees Table 2.

Table 2

Example 12-13

The hydrocracking performance of this example explanation catalyst of the present invention.

With the n-decane is raw material, the hydrogenation cracking activity of evaluate catalysts CH-4, CH-5 on the small fixed hydrocracking unit, the catalyst loading amount is 0.2 milliliter, the catalyst granules diameter is the 0.3-0.45 millimeter, 390 ℃ of reaction temperatures, reaction pressure 4.0 MPas, hydrogen-oil ratio (volume ratio) is 25, liquid hourly space velocity (LHSV) is 60 hours ^-1, the n-decane percentage that transforms in forming with product is represented the conversion ratio of catalyst, and evaluation result sees Table 3.

Comparative Examples 5

The evaluation method of catalyst W is with example 12, and the results are shown in Table 3 for gained.

Table 3

	Example 12	Example 13	Comparative Examples 3
	Example 12	Example 13	Comparative Examples 3	Catalyst	CH-4	CH-5	W
Conversion ratio, %	68.9	66.7	62.5	Catalyst	CH-4	CH-5	W

Catalyst CH-5 is identical with the composition of comparative catalyst W, and the k value of different the is contained silica-alumina of catalyst CH-5 is 0.58, and the k value of the contained silica-alumina of comparative catalyst W is 0.33.But from the result of table 3 as can be seen, improved 4.2 percentage points, illustrated that catalyst of the present invention has better hydrocracking performance with respect to the conversion ratio of comparative catalyst W catalyst CH-5 provided by the invention.

Example 14

Raw materials used oil is Iraq's vacuum gas oil (VGO), and its physico-chemical property sees Table 4.

Catalyst CH-2 is broken into the particle of diameter 0.5-1.0 millimeter, in 30 milliliters of small stationary bed bioreactors, pack into 30 milliliters of this catalyst, under nitrogen atmosphere, use earlier before the reaction and contain the kerosene of 2 heavy % carbon disulfide 300 ℃ of following presulfurizations 25 hours, switch reaction raw materials then, estimate at 360 ℃, 6.4 MPas, the results are shown in Table 5.

Comparative Examples 6

The evaluation method of catalyst X is with example 14, and the results are shown in Table 5 for gained.

Table 4

	Feedstock oil
	Feedstock oil	Density (20 ℃), grams per milliliter	0.9017
S, heavy %	2.38	Density (20 ℃), grams per milliliter	0.9017
S, heavy %	2.38	N, mg/litre	1080
Simulation distil (ASTM D-2887)		N, mg/litre	1080
Simulation distil (ASTM D-2887)		IBP	243
50	437	IBP	243
50	437	90	497

Table 5

Catalyst	Example 14	Comparative Examples 6
Catalyst	Example 14	Comparative Examples 6	Simulation distil (ASTM D-2887)	CH-2	X
65℃ ^-，％	6.1	5.6	Simulation distil (ASTM D-2887)	CH-2	X
65℃ ^-，％	6.1	5.6	65-370℃，％	77.5	75.2
370℃ ⁺，％	16.4	21.2	65-370℃，％	77.5	75.2

As can be seen from Table 5, under identical reaction condition, in the generation oil of example 14,370 ℃ ⁺Cut is lower by 4.8% than Comparative Examples 6, and the yield of 65-370 ℃ of intermediate oil exceeds 2.3% than Comparative Examples 6, and this illustrates that catalyst provided by the invention has comparison than higher hydrogenation cracking activity of catalyst and intermediate oil selectivity preferably.

Claims

1, a kind of monox-alumina containning hydrocracking catalyst, this catalyst contains a kind of silica-alumina, a kind of beta-zeolite, at least a iron, cobalt or nickel and at least a molybdenum or the tungsten metal component that is selected from group vib that is selected from group VIII, it is characterized in that the k value of described silica-alumina is 0.4-15A (cm ²G) ^-1, be benchmark with the catalyst, the content of silica-alumina is 10-90 weight %, and the content of beta-zeolite is 1-50 weight %, and in oxide, the content of group VIII metal component is that the content of 1-10 weight %, group vib metal component is 5-40 weight %; Said k=B/M _SiO2, B is the Bronsted acid amount of silica-alumina, M _SiO2Molar fraction for silica in the silica-alumina.

According to the described catalyst of claim 1, it is characterized in that 2, the k value of described silica-alumina is 0.5-13A (cm ²G) ^-1, be benchmark with the silica-alumina, the content of silica is 1-60 weight %.

According to the described catalyst of claim 2, it is characterized in that 3, described silica-alumina has the X-ray diffraction peak that is selected from one or more aluminium oxide among γ, η, θ, δ and the χ of feature, the content of silica is 1-45 weight %.

According to the described catalyst of claim 3, it is characterized in that 4, described silica-alumina has the X-ray diffraction peak of the gama-alumina of feature.

5, according to the described catalyst of claim 1, it is characterized in that, with the catalyst is benchmark, the content of silica-alumina is 15-70 weight %, the content of beta-zeolite is 1-45 weight %, in oxide, the content of group VIII metal component is that the content of 2-8 weight %, group vib metal component is 10-35 weight %.

6, the described Preparation of catalysts method of claim 1, this method comprises mixes iron, cobalt or nickel and at least a molybdenum or the tungsten metal component that is selected from group vib that is incorporated at least a group VIII of introducing in this mixture with a kind of silica-alumina and a kind of beta-zeolite, it is characterized in that the k value of described silica-alumina is 0.4-15A (cm ²G) ^-1Said k=B/M _SiO2, B is the Bronsted acid amount of silica-alumina, M _SiO2Molar fraction for silica in the silica-alumina.

7, in accordance with the method for claim 6, it is characterized in that the k value of described silica-alumina is 0.5-13A (cm ²G) ^-1, be benchmark with the silica-alumina, silica content is 1-60 weight %.

8, in accordance with the method for claim 7, it is characterized in that described silica-alumina has the X-ray diffraction peak that is selected from one or more aluminium oxide among γ, η, θ, δ and the χ of feature, the content of silica is 1-45 weight %.

9, in accordance with the method for claim 8, it is characterized in that, described silica-alumina is by having containing si molecular sieves or contain composition that disordering contains si molecular sieves and directly mixing and obtain of the aluminium oxide that is selected from one or more crystal formations among γ, η, θ, δ and the χ and at least a disordering.

10, in accordance with the method for claim 8, it is characterized in that, described silica-alumina is mixed by containing si molecular sieves or containing the composition that disordering contains si molecular sieves of the hydrate of aluminium oxide and at least a disordering, obtains in 350-850 ℃ of roasting 2-8 hour.

11, in accordance with the method for claim 10, it is characterized in that the hydrate of described aluminium oxide is selected from one or more the mixture among hibbsite, monohydrate alumina and the amorphous hydroted alumina; Or one or more the mixture among one or more hibbsite, monohydrate alumina and the amorphous hydroted alumina in siliceous, the titanium, magnesium, boron, zirconium, thorium, niobium, rare earth.

According to claim 10 or 11 described methods, it is characterized in that 12, described disordering contains one or more in the ZSM series zeolite of faujasite that si molecular sieves is a disordering and disordering.

According to claim 10 or 11 described methods, it is characterized in that 13, it is by preparing partially-crystallized molecular sieve or the si molecular sieves that contains of complete crystallization being carried out disordering and handles and to obtain that described disordering contains si molecular sieves.