CN1017343B - Hydrocracking process - Google Patents
Hydrocracking processInfo
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- CN1017343B CN1017343B CN 87103714 CN87103714A CN1017343B CN 1017343 B CN1017343 B CN 1017343B CN 87103714 CN87103714 CN 87103714 CN 87103714 A CN87103714 A CN 87103714A CN 1017343 B CN1017343 B CN 1017343B
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Abstract
The present invention relates to an improved hydrocracking catalyst used for producing intermediate fractions, which comprises a mixture formed from a first modified Y zeolite ingredient, a second modified Y zeolite ingredient, a refractory inorganic oxide matrix and hydrogenation metal. The range of the average unit cell sizes of the first modified Y zeolite and the second modified Y zeolite is from 24.20 to 24.35 angstroms, and the difference of the respective average unit cell sizes of the first modified Y zeolite and the second modified Y zeolite is at least 0.1 angstrom.
Description
The present invention can be used for the catalyzed conversion field of hydrocarbon.The present invention relates to be used for the new catalyst of hydrocracking process.More precisely, the present invention relates to a kind of improved hydrocracking catalyst, when using from the hydrocracking process of heavy gas oil production middle runnings under hydrocracking condition, this catalyzer proof has beyond thought and unusual excellent activity, selectivity and anti-deactivation.
Modern a lot of refineries all are that the hydrocracking by the counterweight gas-oil feed comes production middle runnings product, as rocket engine fuel and diesel-fuel.The boiling range scope of charging is about 650-1050 ℃ F(343-566 ℃ usually) between.Improving temperature and pressure and having under the situation of hydrogen, heavy oil contacts with suitable hydrocracking catalyst can obtain the hydrocracking product.The boiling range scope of gained middle runnings is between 300-700F ° (149-371 ℃).The subject matter of modern refinery increases the output via hydrocracking process production middle runnings exactly.The performance of the catalyzer that improvement is used in hydrocracking process just can increase the output of middle runnings.
Activity, selectivity and stability are to estimate three main catalysis characteristicses of hydrocracking catalyst.Active normally measure like this, promptly be lower than under the situation identical with boiling point in that charging is identical to the transformation efficiency of the product of fixed temperature, when other hydrocracking condition is all constant, the use temperature of more used each catalyzer.Concerning given catalyzer, active temperature is lower, and then its activity for special process is also higher.The selectivity of hydrocracking catalyst is to measure the productive rate of desired product.Stability is to measure, and when handling given hydrocarbon charging, this catalyzer keeps it active and optionally good and bad in the time cycle that continues.Stability generally is that required rate of temperature change is measured every day to keep given transformation efficiency.
The target of hydrocracking catalyst provide have high as far as possible activity, selectivity and stability catalyzer.The catalyzer that uses in hydrocracking process comprises the VIII family metal component (promptly being selected from iron group and platinum metals) that combines with IV B family metal component (being chromium, molybdenum, tungsten) usually, they the two form uniform mixture with solid support material again.When using different carriers, activity of such catalysts, selectivity and stability also have very big variation.The carrier that becomes known for hydrocracking process comprises porous refractory inorganic oxide material, as unformed silica-alumina, aluminum oxide etc.; Also comprise the crystal type aluminosilicate zeolite, as the Y-zeolite.The main general activity of being made up of refractory oxide of solid support material is lower, but the selectivity height; Then general active higher by the solid support material that zeolite is formed, but selectivity is then lower.
Therefore, top priority of the present invention provides a kind of hydrocracking catalyst, and it has excellent catalytic performance to the hydrocracking of hydrocarbon.More precisely, the purpose of this invention is to provide a kind of catalyzer that is used for hydrocracking, it is compared with the catalyzer of prior art has excellent activity, selectivity and stability.Another object of the present invention provides a kind of hydrocracking catalyst, and it is used for that heavy gas oil is converted into the middle runnings product and has excellent catalytic performance.Another object of the present invention provides a kind of solid support material, and it can be used for hydrocracking process.A further object of the invention provides a kind of method for hydrogen cracking of excellence, and it is used for heavy gas oil is converted into the middle runnings product.These and other purpose of the present invention and advantage will clearly be reflected in following explanation of the present invention.
Some patents are open, contain the zeolite mixture cracking catalyst that is dispersed in the inorganic oxide matrix.
United States Patent (USP) 4,419, disclose a kind of hydrocracking catalyst that is used to produce intermediate oil for No. 271, it contains one or more hydrogenation component that are stated from the matrix, and this matrix contains crystal silicon-aluminate zeolite and the dispersion of silica-alumina in alumina substrate.The patentee points out: the mixture with one or more crystal aluminosilicates of cracking activity can be dispersed in the complex matrix.But the unexposed any concrete zeolite mixture of patentee.
United States Patent (USP) 4,287 discloses a kind of hydrocracking catalyst No. 048, and it contains a kind of overstable Y-type zeolite and aperture crystalline zeolite (as mordenite) in inorganic oxide matrix.
United States Patent (USP) 4,137 discloses a kind of cracking technology of using faujusite and mordenite mixture No. 152.
United States Patent (USP) 3,894 discloses a kind of catalyst cracking method of hydrocarbon No. 934, and this method is used large pore zeolite and the pore zeolite (as the ZSM-5 zeolite) that is dispersed in the general matrix.
United States Patent (USP) 3,702 is disclosed in for No. 886 in the catalytic cracking process of hydrocarbon and the ZSM-5 zeolite is used separately or use with other material (as zeolite or inert material).
United States Patent (USP) 3,804 discloses the hydroconversion process of a kind of X of use zeolite and Y zeolite mixture No. 747.
United States Patent (USP) 3,758 discloses a kind of catalytic cracking composition No. 403, and it contains large pore zeolite (as Y zeolite) and pore zeolite (as the ZSM-5 zeolite) in siliceous matrix.Matrix can be active or inert, as silica-alumina or aluminum oxide.Use the ZSM-5 zeolite can obtain high-octane gasoline.
United States Patent (USP) 3,769 discloses a kind of composite catalyst No. 202, and it contains the mixture of two kinds of different zeolites, and the one aperture is greater than 8 dusts, and another aperture is less than 7 dusts.Zeolite mixes with inorganic oxide matrix (as silica-alumina).Catalyzer is applicable to the cracking and the hydrocracking of hydrocarbon.
United States Patent (USP) 3,925, disclose a kind of cracking method No. 195, the catalyzer of use contains the mixture of the mordenite of rare earth-hydrogen-y-type zeolite and hydrogen or transition metal-exchange, the mixture of the A type zeolite of calcium-exchange or the erionite of hydrogen-exchange and amorphous matrix.
United States Patent (USP) 3,764 discloses a kind of catalyzer No. 520, and it contains the mixture of two kinds of different zeolites, and a kind of pore diameter range is at the 6-15 dust, and another kind of pore diameter range is less than 6 dusts, and this mixture and inorganic oxide carrier combine.Catalyzer is used for hydrocarbon conversion process, has higher selectivity.
United States Patent (USP) 4,477, disclose a kind of cracking catalyst composition No. 336, it contains and has unit cell and be of a size of non-dealuminzation hydrochlorate (nondealu minated) y-type zeolite of 24.6+/-0.1 dust and have the mixture of unit cell size less than dealuminzation hydrochlorate (dealuminated) y-type zeolite of 24.4 dusts.
According to the present invention, catalyst composition is provided, this composition contains at least the first kind of Y type crystal silicon-aluminate zeolite component and combines with second kind of Y type crystal silicon-aluminate zeolite component, and forms uniform mixture with the refractory inorganic oxide matrix.Wherein the average unit cell size of these first and second kinds of zeolites is being about 24.20 dusts in the scope that is about 24.35 dusts, and wherein the difference of these first and second kinds of average unit cell sizes of zeolite is at least 0.1 dust.
In another embodiment, the invention provides a kind of hydrocracking catalyst composition, this composition contains hydrogenation component, and at least the first kind of Y type crystal aluminosilicate component and second kind of Y type crystal aluminosilicate component combine, and form uniform mixture with the refractory inorganic oxide matrix.Wherein the average unit cell size of these first and second kinds of zeolites is being about 24.20 dusts in the scope that is about 24.35 dusts, and the difference of these first and second kinds of average unit cell sizes of zeolite is at least 0.1 dust.
In addition, the present invention also provides a kind of method of catalytic hydrocracking, uses any of above-mentioned two kinds of catalyst compositions, can produce the intermediate oil that boiling point is lower than 700 (371 ℃).
Catalyst composition of the present invention contains two kinds and inorganic matrix bonded y-type zeolite component at least.
Prior art has indicated from natural or synthetic zeolite all can prepare zeolite catalyst, and can be used for the conversion of hydrocarbon.Known zeolite comprises: natural zeolite, such as faujusite, mordenite, erionite and chabazite; And synthetic zeolite, as A, L, S, T, X and y-type zeolite.In general, zeolite is exactly the silico-aluminate with metal of crystalline texture, thereby all has sizable adsorption area in each crystalline inside.Zeolite is basically by being tetrahedral SiO
4And ALO
4Three-dimensional net structure form, share and to be tetrahedron crosslinked with Sauerstoffatom.Contain the positively charged ion institute balance that the tetrahedral electricity price of aluminium is comprised in the crystallization, these positively charged ions for example can be metal ion, ammonium ion, amine complex or hydrogen ion.Space in the hole can be occupied by water molecules or other adsorbed molecules.Common naturally occurring crystalline zeolite or the zeolite for preparing with alkali metal form, generally the catalytic cracking for hydrocarbon is a non-activity.
The present invention is conceived to have the zeolite component of cracking activity.In order to make the zeolite with cracking activity, basic metal will replace with the positively charged ion that contains polyvalent metal, hydrogen ion or hydrogen ion precursor (as ammonium ion) usually.This positively charged ion replaces realizes by ion-exchange that generally this is a known method in the prior art, and the zeolite of sodium type or other alkali metal form wherein and contains hydrogen ion, ammonium ion, alkene soil ion or other suitable cationic aqueous solution and contacts.Even replace the zeolite that a part of sodium ion also can produce the certain cracking activity of tool, but alkali metal content reduces to and is lower than 5%(weight), be preferably lower than 1%(weight), better be lower than 0.5%(weight) (calculating) with the alkalimetal oxide form, then can obtain having the material of remarkable cracking activity.
At United States Patent (USP) 3,130, y-type zeolite is generally disclosed in No. 007, this patent has been classified reference as.The crystal of y-type zeolite is the crosslinked SiO of tetrahedron that is shared by Sauerstoffatom basically
4And ALO
4Three-dimensional net structure.Each tetrahedral electricity price of closing aluminium is by the existence of forming positively charged ion (as alkalimetal ion) in the silico-aluminate network and balance.Pore space in the network is occupied by water molecules.
The chemical formula of the Y zeolite that shows with the oxide molar numerical table can be write as:
0.9±0.2Na
2O∶Al
2O
3∶WSiO
2∶XH
2O
In the formula, 3＜W＜～6 and X＜～9.
Y-type zeolite component used in the present invention can be with known technology modification in addition.Y-type zeolite is higher than under 500 ℃ in temperature, carries out water vapor thermal treatment.The steam heat treatment technology is at Dwyer, J., Zeolite Structure, Composition and Catalgsis, Chemistry and Industry, Issue No 7 April12, introduce in 1984, this document is also listed reference in.
No matter use which kind of y-type zeolite, the unit cell size of every kind of zeolite component must be in the scope that is about the 24.20-24.35 dust.In a preferred embodiment, this composition contains first and second kinds of zeolite component, and their unit cell size range is all within the 24.20-24.35 dust.The difference of the average unit cell size of these two kinds of zeolite component is at least 0.1 dust.First kind of weight ratio to second kind of zeolite component is about 0.1-10: 1, be preferably 1.0: 1.0.The content of first kind of zeolite component is about 1.0-20.0%(weight), be preferably 5.0%(weight).The content of second kind of zeolite component is about 1.0-20.0%(weight), be preferably 5.0%(weight).
Catalyst composition also contains the refractory inorganic oxide matrix.This composition contain between 2% and 98%(weight) between oxide matrix, preferably between 5% and 95%(weight) between.Matrix can contain any known refractory inorganic oxide, as aluminum oxide, magnesium oxide, silicon oxide, titanium oxide, zirconium white etc. and their combination.
Matrix comprises silica-alumina or aluminum oxide preferably.Better matrix is the mixture of silica-alumina and aluminum oxide, and wherein this silica-alumina content accounts for the 5-95%(weight of this matrix) between and always silica content account for the 1-75%(weight of this matrix) between.
The silica-alumina matrix is the composition of aluminum oxide and silicon oxide preferably.As particular instance, a kind of body material of satisfaction can contain equimolar aluminum oxide and silicon oxide or 63%(weight) aluminum oxide.In general, body material contains from about 10-90%(weight) aluminum oxide.Can with any in relevant prior art univocal various technology prepare matrix.These technology comprise: the acid treatment of natural clay, sand or soil, the co-precipitation of the water-sol or continuous precipitation.These technology usually combine with one or more activation treatment, and these activation treatment comprise: deep fat is aging, decatize, drying, oxidation, reduction, roasting etc.The general matrix of stipulating with surface-area, aperture, the more such parameters of pore volume or the pore texture of carrier, can be by following their concrete boundary of proper method expansion, these methods comprise: in room temperature or under heating up, and the aging water-sol and/or hydrogel under controlled acidity or alkaline condition; Or under critical pH, make the carrier gelling or handle carriers with various inorganic or organic reagents.The matrix that is applicable to the inventive method has following feature: surface-area is about 200-400 square metre of every gram, aperture and is about 200-300 dust, pore volume and is about every gram 0.10-0.80 milliliter and apparent bulk density in the scope that is about the 0.50-0.90 grams per milliliter.
The alumina substrate material can be the gel of any hydrated aluminum oxide or aluminum oxide, as the Alpha-alumina-hydrate of boehmite (boehmite) structure, the Alpha-alumina trihydrate of three water aluminium (gibbsite) structures, beta-alumina trihydrate of bayerite (bayerite) structure or the like.Particularly preferred aluminum oxide is referred to as the ziegler aluminum oxide.At United States Patent (USP) 3,852, introduced its feature in 190 and 4,012,313.As what narrated in the United States Patent (USP) 2,892,858 of Ziegler, it is a kind of byproduct as Ziegler higher alcohols building-up reactions.Be called the aluminum oxide preferably of " Catapal " recently by the another kind of commodity of the continent oil product Conoco of company Division of Chemistry supply.This material is ultra-pure Alpha-alumina-hydrate (boehmite structure), has proved that after high-temperature calcination, it can produce high-purity gama-alumina.
Should be appreciated that some accurate physics and/or chemical features of catalyzer of the present invention, should not regard limitation of the scope of the invention as.For example this catalyzer may exist with following various forms: ball shape, sheet, granular, shred, spherical or various specified shape, they are configured in the reaction zone with the form of fixed bed, charging may be with liquid phase, vapour phase or mixed phase by bed, and both can make progress also can flow downward.In addition, catalyzer also can be prepared into suitable form, is used for the moving bed reaction district, but wherein hydrocarbon charging and both also concurrent flows of reversible flow of catalyzer also can be used for fluidized solid process, and wherein the turbulence bed of particulate catalyzer is upwards passed through in charging; Or be used for suspension process, and wherein catalyzer is made pulpous state in feeding liquid, and the mixture of gained is sent into reaction zone.From reaction product and the catalyst separating that any aforementioned process obtains, reaction product is released to normal atmosphere and its each component of classification recovery.Hydrogen and unconverted materials can be carried out recirculation on demand.
Can prepare granules of catalyst with any known method in this area, these methods comprise that one-tenth drips a method and an extrusion molding in the oil of knowing.When in using oil, becoming to drip method, can at first be suspended in selected zeolite powder and prepare this granules of catalyst in the suitable solution.Active metal component also can mix in the solution.This collosol intermixture can droplet-like enter in the oil bath then, and oil bath remains on comparatively high temps, sol solutions is dropped in the oil bath keep, and forms the agglomerative bead up to them.These spherolites can be discharged from oil bath, then aging reasonable time in the suspension medium that heats up.Dry and calcine the oxide matrix of aluminum oxide if desired or silica-alumina spherolite then, then can press United States Patent (USP) 2,620 respectively, No. 314 or 3,003, to carry out becoming a method in the oil for No. 972, above-mentioned patent is also listed in the reference of the present invention.
Second of catalyst composition of the present invention suitable with preferred method for making, be with aluminum oxide and unformed silica-alumina blend mill (Co-mull) selected zeolite.Before the mixing, component to be mixed preferably all is ground into Powdered.Active metal component also can mix in the mixture.Behind the mix grinding, mixture is extruded by a mold with suitable perforate (as round hole), to obtain columniform extrudate.This extrudate can be cut into the segment of 1/2-1/4 inch, and is dry then and calcine in condition known in the art with under heating up.
Hydrogenation component except that in oil, become to drip method or extrusion molding carry out before or among the blending, also can form at selected zeolite and refractory inorganic oxide material, dry and calcine after, make it and catalyst mix with pickling process.Any currently known methods in the available this area of the dipping of hydrogenation component carries out, and these methods comprise: evaporation, dip-coating and vacuum impregnation technology.Generally be that drying contacts with one or more solution that contain required solubilised state hydrogenation component with the incinerating particle.Through after the contact of appropriate time,, just obtain the finished catalyst particle composition particle drying and calcining.
Selected hydrogenation component is the component with catalytic activity, and they are selected from VI B family and VIII family metal and compound thereof.The components contents of catalytic activity in finished catalyst is compared generally little with above-mentioned other blending ingredients.Usually the content of VIII family component in the finished catalyst composition is about 0.1-20%(weight), preferably be about 1-15%(weight) (is that benchmark calculates by element).The VI B family content of component in the finished catalyst composition is about 0.05-15%(weight), preferably be about 0.5-12%(weight) (is that benchmark calculates by element).Described hydrogenation component comprises metal component, and they are selected from molybdenum, tungsten, chromium, iron, cobalt, nickel, platinum, palladium, iridium, osmium, ruthenium, one group of metal of rhodium and their mixture.
When needs, also can in catalyzer, mix phosphorus component.Both mixing of phosphorus can make solid support material mix with P contained compound before particle forms, and also can add phosphoric acid in steeping fluid.Usually the content range of phosphorus in catalyzer is about 1-50%(weight) and be preferably 3-25%(weight) (press P
2O
5Calculate).
In addition, boron also can be added in the catalyst composition.Boron can any element or the form of compound, mixes in the composition with above-mentioned any method.That is to say that it can mix in particle forms, also can the boric acid form be present in the steeping fluid.Boron also can mix in the network of one or both selected zeolites.Under latter event, the y-type zeolite modification also generates silica-alumina-boron-zeolite.
If hydrogenation component exists, they calcines the most probable form in back in air be oxide compound, and the hydrogenation component of these forms when contacting with the reducing atmosphere that contains hydrogen sulfide, also can be converted into sulphided form in intensification if desired.Catalyzer contacts with sulfur feed stock at the scene can form sulfide, perhaps with before any charging contacts, just once having calcined this composition is exposed in the reducing atmosphere, also can form sulfide.
Aforesaid catalyzer is specially adapted to hydrocracking process, is the hydrocarbon feedstock conversion to have mean boiling point and the lower more value product of molecular-weight average.Preferable is that above-mentioned catalyzer is specially adapted to the middle runnings that the production boiling range is about 300-700 (149-371 ℃).In addition, above-mentioned catalyzer also is applicable to hydrogenation reaction, as the hydrodenitrification and the hydrogenating desulfurization of hydrocarbon.Can comprise all mineral oil and synthetic oil and their cut for the typical feed of processing.Therefore resemble straight run gas oil, vacuum gas oil, long residuum, diasphaltene vacuum residuum, coker distillate and catalytic cracking cut like this some chargings all at the row of consideration.Charging preferably comprises that the component that its boiling point is higher than 700 (371 ℃) accounts for 50%(weight) or higher gas oil.
Reaction conditions is to be used for the common reaction conditions in hydrocracking process field.Range of reaction temperature is preferably in 600-1200 °F (316-649 ℃) at 200-1500 °F (93-816 ℃).The reaction pressure scope is in normal pressure-Yue 3000Psig(0-20685 kPa gauge pressure), be preferably in 200-3000Psig(1379-20685 kPa of gauge pressure).Duration of contact, scope corresponding to liquid hourly space velocity degree (LHSV), was about 0.1-15 hour usually
-1, preferably be about 0.2-12 hour
-1The cycling rate scope of hydrogen is at 1000-50000 standard cubic foot (Scf)/every barrel of charging (178-8900 rice
3H
2/ every meter
3Charging), be preferably in every barrel of charging of 2000-30000Scf/ (356-5340 rice
3/ rice
3).
The embodiment that provides below is just for illustrating the present invention, and do not constitute limitation of the scope of the invention, found that catalyzer of the present invention has excellent catalytic performance, be converted in the technology of middle runnings product at Gas Oil Isomax, show excellent activity, selectivity and stability.
Embodiment 1
Under the temperature of normal pressure and 1000-1500 (538-816 ℃), decatize has the unit cell size and is about zeolite powder 0.5-24 hour of 24.56 dusts, can make the y-type zeolite of modification.Changing the decatize condition is the unit cell size of may command modified zeolite.The table I has been listed three kinds of modified zeolite of Y-type with different unit cell sizes, and they are to prepare with aforesaid method with under decatize condition separately.
The embodiment II
The modified zeolite of Y-type of embodiment I is mixed mutually with refractory oxide substrate mixture (being mixed by silica-alumina and aluminum oxide), and selected quantitative relation should make and contain 5%(weight in the extrudate that obtains) non-volatile zeolite and 95%(weight) oxide matrix.The mixture of gained obtains being approximately 1 * 16 inch * 1/2 inch segment right cylinder by extruding.Extrudate is dried and 650 ℃ of air calcination 2 hours.Then incinerating particle metatungstate and nickelous nitrate (Ni(NO
3)
26H
2O) aqueous solution evaporate floods altogether, and it is enough high that the content of these two kinds of salt is wanted, to contain 1.0%(weight in the assurance finished catalyst) elemental nickel and 10.0%(weight) elemental tungsten.Then the catalyzer of 343 ℃ of calcining dippings 45 minutes, and then 593 ℃ of calcinings 90 minutes.With three kinds of catalyst compositions of method for preparing, every kind of composition contains a kind of in three kinds of prepared in example I modified zeolite of Y-type.With containing 5%(weight respectively) zeolite A, B and the C and the 95%(weight of embodiment I) the carrier of oxide matrix, prepared catalyzer 1,2,3.With containing 10%(weight) the zeolite B and the 90%(weight of embodiment I) the preparing carriers catalyzer 4 of oxide matrix.The related properties of catalyzer 1-4 and their carrier are listed in the table II.
The embodiment III
At first weight such as the zeolite A of embodiment I and C are mixed and prepare catalyst composition of the present invention.Then zeolite mixture is mixed with refractory oxide mixture in the catalyzer 4, the quantitative relation of selection should satisfy in the carrier extrudate that obtains and contain 10%(weight) total zeolite and 90%(weight) oxide matrix.Then the mixture that obtains is extruded, calcined and flood according to the same procedure described in the embodiment II fully.The table II provides the catalyzer 5 of such preparation and the related properties of carrier thereof.Importantly be noted that because the zeolite A(24.25 atomic meter lattice of equivalent) and zeolite C(24.35 atomic meter lattice) the average unit cell that mixes this zeolite mixture of dying mutually is of a size of 24.30 dusts.
The embodiment IV
Test activity and the selectivity of aforesaid every kind of catalyzer as follows to being converted into middle runnings.
Pass through an adiabatic reactor for vacuum gas oil (its chemistry and physical properties the are listed in the table III) one way of preheating, this reactor contains the catalyst particle with 75 cubic centimetres of the quartzy sand facies blended of about 29 cubic centimetres 60-80 order (250-177 micron).Operating parameters is a 2000Psig(13790 kPa of gauge pressure), 1.0LHSV, purity is that the circulation velocity of the hydrogen of 90-95% is 10000 mark feet
3(1780 meters in/bucket
3/ rice
3) about 4 days of the cycle of operation.The conditioned reaction actuator temperature is to produce 70% transformation efficiency that boiling point is 700 (371 ℃) or lower product.Transformation efficiency is from liquid chromatography the boiling range analysis of product to be calculated.
Above-mentioned test-results is compiled in the table IV.Data show the average lattice dimensions of catalyzer 5(24.30 dust, 10%(weight) zeolite) and catalyzer 2(24.30 dust lattice dimensions, 5%(weight) zeolite) have identical productive rate, but unexpectedly activity exceeds 12 °F (6.6 ℃).With catalyzer 4(24.30 dust lattice dimensions, 10% zeolite) compares, catalyzer 5 is that activity also exceeds 6 °F (3.3 ℃) equally unexpectedly, and for required 300-700 (149-371 ℃) middle runnings product, its selectivity increases 1.9%(weight).
The table I
The zeolite unit cell size decatize condition time (hour) temperature ℃ pressure
A 24.25 12 788 normal pressures
B 24.30 2 788 ″
C 24.35 2 732 ″
The table II
Catalyzer numbers 12345
Carrier compositions
%(weight)
Zeolite 555 10 10
Oxide matrix 95 95 95 90 90
Catalyst composition
%(weight)
Ni 1.0 1.0 1.0 1.0 1.0
W 10.0 10.0 10.0 10.0 10.0
The zeolite characteristic
Zeolite (from the example I) A B C B A, C
The unit cell size, dust 24.25 24.30 24.35 24.30 24.30
(on average)
The table III
The character of vacuum gas oil
Proportion
60 (16 ℃) 0.9248 distillation ℃
Density ° API
60 (16 ℃) 21.5(924kg/m
3) initial boiling point (IPB) 280
Pour point, 80(27 ℃) 5/10% 340/372
Aniline point 167.0(75 ℃) 20,/30 398/419
Sulphur (LECO) %(weight) 2.24 40,/50 439/455
Nitrogen (Kjeldahl), ppm 1,100 60,/70 473/490
Carbon %(weight) 85.82 80,/90 514/544
Hydrogen %(weight) 11.64 full boiling points (EP) 582
Bromine number 5.0 rate of recovery (%Rec) 99.0
Viscosity,
210 (99 ℃) 6.954
The Kang Laxun carbon residue, %(weight) 0.42
The table IV
Catalyzer numbers 12345
Activity, F ° (℃) 794 782 774.5 776 770
（423.3）（416.6）（412.5）（413.3）（410）
300-700°F（149-
371 ℃) cut productive rate %(weight) 62.4 60.9 56.9 59.0 60.9
The unit cell size, dust 24.25 24.30 24.35 24.30 24.30
(on average)
Transformation efficiency %(weight) 70 70 70 70 70
Zeolite, %(weight) 555 10 10
Claims (3)
1, a kind of method of hydrocracking, it is included in optionally production boiling range under the condition of the hydrocracking that the middle runnings that is 149 to 371 ℃ is selected for use, the high boiling hydrocarbon charging is contacted with a kind of improved following catalyzer, wherein hydrogenation catalyst comprises the uniform mixture that the refractory inorganic oxide matrix of the hydrogenation component of at least 5% (weight) Y zeolite and catalytically effective amount and 5-95% (weight) forms, carrier contains the first modified Y zeolite component of 1.0-20.0% (weight), the said first modified Y zeolite component unit cell size range is between the 24.20-24.35 dust, its improvements are that adopting content in the uniform mixture that forms with this refractory inorganic oxide matrix is the second modified Y zeolite component of 1.0-20.0% (weight), the unit cell size range of this second modified Y zeolite component is between the 24.20-24.35 dust, wherein first and second unit cell size of improving the Y zeolite component is different, the difference of unit cell size be at least 0.1 dust and wherein first modified Y zeolite be 0.1: 1 to 10: 1 to the second weight ratio scope of improving Y zeolite.
2, according to the method for hydrogen cracking of claim 1, wherein the average unit cell size of first modified Y zeolite is about 24.25 dusts, and the average unit cell size of second modified Y zeolite is about 24.35 dusts.
3, according to the described method for hydrogen cracking of any one claim of claim 1-2, wherein this hydrocracking condition comprises temperature range at 93-815 ℃, and pressure range is about 0.1-15 hour in normal pressure-Yue 20685 kPas (gauge pressures) and liquid hourly space velocity degree scope.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90108134 CN1017059B (en) | 1987-04-27 | 1987-04-27 | Middle distillate producing hydrocracking catalyst |
| CN 87103714 CN1017343B (en) | 1986-07-07 | 1987-04-27 | Hydrocracking process |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/882,556 US4661239A (en) | 1985-07-02 | 1986-07-07 | Middle distillate producing hydrocracking process |
| CN 87103714 CN1017343B (en) | 1986-07-07 | 1987-04-27 | Hydrocracking process |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90108134 Division CN1017059B (en) | 1987-04-27 | 1987-04-27 | Middle distillate producing hydrocracking catalyst |
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| Publication Number | Publication Date |
|---|---|
| CN87103714A CN87103714A (en) | 1988-11-16 |
| CN1017343B true CN1017343B (en) | 1992-07-08 |
Family
ID=25742323
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87103714 Expired CN1017343B (en) | 1986-07-07 | 1987-04-27 | Hydrocracking process |
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|---|---|
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| CN109701595B (en) * | 2017-10-26 | 2022-02-08 | 中国石油化工股份有限公司 | Hydrocracking catalyst, preparation method thereof and heavy raw oil hydrocracking method |
-
1987
- 1987-04-27 CN CN 87103714 patent/CN1017343B/en not_active Expired
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| Publication number | Publication date |
|---|---|
| CN87103714A (en) | 1988-11-16 |
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