CN101210187A - Catalyst for cracking heavy oil - Google Patents
Catalyst for cracking heavy oil Download PDFInfo
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- CN101210187A CN101210187A CNA200610169674XA CN200610169674A CN101210187A CN 101210187 A CN101210187 A CN 101210187A CN A200610169674X A CNA200610169674X A CN A200610169674XA CN 200610169674 A CN200610169674 A CN 200610169674A CN 101210187 A CN101210187 A CN 101210187A
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Abstract
A catalyst for cracking heavy oil contains zeolite and clay. The catalyst is characterized in that the clay at least contains a rectorite containing an auxiliary agent and having a content of 5 to 100wt% with respect to the reference of the total weight of the clay; the rectorite containing the auxiliary agent contains 45 to 94.9wt% rectorite with the reference of the total weight of the rectorite containing the auxiliary agent, 5 to 50wt% (calculated by oxide) bonding agent component, and 0.1 to 20wt% (calculated by element) one or more auxiliary components selected from P, Mg, Re, Ti, B and Zr. The catalyst has the advantages of good coke selectivity, high transformation capacity of the heavy oil, high yield of the light oil, and good abrasion resistance.
Description
Technical field
The present invention relates to a kind of catalyst for cracking heavy oil, more particularly, the present invention designs a kind of catalyst for cracking heavy oil that contains rectorite.
Background technology
The change weight of stock oil and refinery require to improve the ability of cracking catalyst pressure fuel to the pursuit of economic benefit.The channel diameter of y-type zeolite is 0.75nm in the cracking catalyst, and the middle small molecule hydrocarbon in the stock oil can enter zeolite endoporus generation cracking reaction, and the macromole hydrocarbon is difficult to enter the zeolite endoporus.In order to improve cracking ability to heavy ends, usually the carrier of cracking catalyst has macropore and the certain acidity that the heavy oil macromole can enter, macromole in the heavy oil is cracked into earlier medium sized molecule in the macropore of carrier, medium sized then molecule enters acid stronger zeolite cavity again, further is cracked into less molecule.
Rectorite is a kind of aluminosilicate mineral, by nondistensible class mica unit layer and expandable class montmorillonite unit layer according to the mode interleaved of public adjacent 2: 1 clay seams, ordered arrangement and form.Rectorite has plate-column structure, two-dimensional channel, macropore opening, and its aperture is adjustable, acid amount is low, strong acid is few, heat and hydrothermal stability height, helps the macromole hydrocarbon cracking.
CN1031029A discloses a kind of clay molecular sieve with layer structure catalytic cracking catalyst, it is characterized in that: it contains the constitutional features of rule space layer clay mineral (1), basal spacing (d
001) be 17.0～50.0 * 10
-10Rice, interlamellar spacing is 0～33.0 * 10
-10Rice; (2) it is by 1～100: 0～99: active ingredient, monomer component and the binder component of 0～99 (the basic weight ratio of burning) constitute; (3) its active ingredient is the mixture that comprises clay molecular sieve with layer structure or this clay molecules sieve of the regular interbed mineral structure of having of cross-linked rectorite and comprise other molecular sieve of faujusite, the faujusite after various chemistry and/or stabilization treatment, ZSM series molecular sieve; (4) its carrier component is the various natural claies that comprise kaolin, rectorite leng, or comprises amorphous silicon aluminium, Al
2O
3, SiO
2Or contain among them the refractory oxide carrier of one or more mixture at interior various synthetic; (5) its binder component is aluminium colloidal sol, silicon sol, silicon-aluminum sol or the mixture that contains among them one or more.This Preparation of catalysts method comprises carries out crosslinking reaction, steps such as burin-in process, roasting with rectorite leng and inorganic metal hydroxy polymer.After calcination steps, can introduce tin, boron, silicon with the mode of dipping, to improve activity of such catalysts stability, to improve the coke selectivity of catalyzer.
CN 1031489A discloses a kind of complex carrier or Preparation of catalysts method that contains clay molecular sieve with layer structure, be each component raw material with this complex carrier or catalyzer: the laminated clay of smectite class or regular interbed mineral structure, zeolite molecular sieve, refractory oxide, clay are by required mixed moulding, introduce linking agent then and carry out crosslinking reaction, and steps such as warp is aging, roasting are made required carrier or catalyzer.
CN 1044414A discloses a kind of aluminium cross-linked clay seam column molecular sieve or has contained the method for modifying of the catalyzer of this molecular sieve, earlier natural calcium type clay is modified as the sodium type, again with polymerization aluminium chlorohydroxide solution crosslinking, and in the preparation process of this molecular sieve of layered crosslinking clay column, introduce 0.2～1.6% chromium, or at this molecular sieve of layered crosslinking clay column or contain in the catalyzer of this molecular sieve and introduce 0.5～2.0% tin.
CN 1353012A discloses a kind of preparation method of laminated clay column catalyst, it is characterized in that this method is after calcium type laminated clay is disperseed in water with a kind of dispersion agent, other each component raw material with catalyzer mixes again, and crosslinking reaction, aging and roasting are carried out in moulding then again.This method need not directly to adopt calcium type laminated clay prepared layer clay column catalyst through ion-exchange remodeling process.
CN 1160743A discloses a kind of laminated clay column catalyst of polyvinyl alcohol modification of producing in high-yield olefin, be the ancillary component that is selected from the supersiliceous zeolite, ZSM-5, β zeolite or the y-type zeolite that contain rare-earth five-membered ring structure by layer clay active ingredient 0～40 weight % of 20～90 weight % polyvinyl alcohol modifications, 0～50 weight % is selected from the carrier component of kaolin etc. and 10～40 weight % and is selected from by the friendship stick component of the inorganic oxides such as aluminum oxide of polyvinyl alcohol modification and forms.Its preparation method is: in the presence of polyvinyl alcohol, said components is mixed,, steps such as ammonification aging, drying, roasting dried through the making beating spray make.
CN 1107080A discloses a kind of layered molecular sieve catalyzer of producing in high-yield olefin, and its component and content are: the layered molecular sieve of (1) 10～50m%; (2) 4～30m% are selected from the ZSM-5 zeolite with H, Mg, RE, Zn, P modification; (3) 0～15m% are selected from a kind of zeolite among beta-zeolite, mordenite, the USY zeolite; The natural clay of (4) 10～70m%; The inorganic oxide of (5) 10～35m%.This Preparation of catalysts method is: carrier pulp is mixed making beating with layered molecular sieve and other molecular sieve, carry out moulding, drying then, promptly get product.This catalyzer also can make with the back cross-linking method.
CN 1211608A discloses a kind of laminar column clay microphere cracking catalyst for heavy oil that is used for voluminous gasoline and diesel oil, and this agent has following composition: the chemical ingredients of the layer clay of 20～90 weight %, 10～40 weight % is mainly the y-type zeolite of the binding agent of aluminum oxide, 0～40 weight % and kaolin group's clay of 0～70 weight %.
CN1175086C discloses a kind of cracking catalyst that contains laminated clay, this catalyzer is prepared by following method: swellable clay, adjuvant component, pseudo-boehmite and water are mixed making beating 0.1-10 hour, obtain a kind of slurries, under 50-85 ℃ temperature, wore out slurries 0.1-10 hour, drying and moulding, washing are worn out then, final drying and roasting, described adjuvant component be selected from the hydroxy polymer of silicon, aluminium, zirconium or titanium one or more or contain in one or more the material in the described hydroxy polymer one or more.
The existing catalytic cracking catalyst that contains rectorite is used for heavy oil fluid catalytic cracking, and coke selectivity is poor, and yield of light oil is not high enough or heavy oil conversion performance is strong inadequately.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of new catalyst for cracking heavy oil that contains rectorite, and this catalyst for cracking heavy oil heavy oil cracking ability is strong, and coke selectivity is good, can improve the yield of light oil of catalytic cracking.
Another technical problem that will solve of the present invention provides a kind of catalytic preparation method of heavy oil cracking who contains rectorite.
The invention provides a kind of catalyst for cracking heavy oil, contain the zeolite and the clay of significant quantity, it is characterized in that, contain a kind of rectorite that contains adjuvant component in the described clay at least, gross weight with clay is a benchmark, and the content that contains the rectorite of adjuvant component in the described clay is 5～100 weight %; Weight with the rectorite that contains adjuvant component is benchmark, the rectorite that contains 45～94.9 weight % in the described rectorite that contains adjuvant component, in the binder component of oxide compound 5～50 weight %, in one or more the adjuvant component among P, Mg, RE, Ti, B, the Zr of being selected from of element 0.1～20 weight %.
The invention provides a kind of preparation method of catalyst for cracking heavy oil, comprise clay is mixed making beating, spray-dired step with zeolite, it is characterized in that, contain a kind of rectorite that contains adjuvant component in the described clay at least; The described preparation method who contains the rectorite of adjuvant component comprises: the compound and the water of rectorite, binding agent, adjuvant component are mixed, stir and be not less than 10 minutes, obtain containing the rectorite slurries of adjuvant component; It is 10～60 weight % that the compound of rectorite, binding agent, adjuvant component and the consumption of water make the solid content of gained slurries, and the consumption of the compound of rectorite, binding agent, adjuvant component makes in the prepared thunder holder soil that contains adjuvant component, weight with the thunder holder soil that contains adjuvant component is benchmark, the rectorite that contains 45～94.9 weight %, in the binder component of oxide compound 5～50 weight %, in one or more the adjuvant component among P, Mg, RE, Ti, B, the Zr of being selected from of element 0.1～20 weight %.
Catalyst coke selectivity provided by the invention is good, and heavy oil conversion performance is strong, the yield of light oil height, and wear resisting property is good.The production of cracking catalyst that contains rectorite provided by the invention, technology is simple, does not need to filter and dispose waste liquid, and is easy to industrial implementation, can save the Preparation of Catalyst time, enhances productivity, and improves product performance.For example, (wherein the adjuvant component phosphorus content is 2.9 weight % to the rectorite that contains adjuvant component of the present invention's preparation, the adjuvant component Mg content is 2.9 weight %, the adjuvant component titanium content is 6.0 weight %, rectorite content is 58.8 weight %, the alumina bound agent content is 29.4 weight %,) content is 34.0 weight %, kaolin content 8.0 weight %, binder component content 20.0 weight % (calculating) with alumina content, y-type zeolite content is the catalyzer of 38.0 weight %, the fluidisation abrasion index is 2.0%, with heavy oil is raw material, estimate with fixed fluidized bed reaction unit, transformation efficiency is 75.33 weight %, yield of light oil is 70.02 weight %, coke selectivity is 0.0834, and the rectorite content of prior art for preparing is 20.0 weight %, and kaolin content is 14.0 weight %, and binder content is 28.0 weight % (calculating with alumina content), y-type zeolite content is the catalyzer of 38.0 weight %, the fluidisation abrasion index is 2.2%, estimates under similarity condition, and transformation efficiency is 73.33 weight %, yield of light oil is 67.61 weight %, and coke selectivity is 0.0965.
Embodiment
According to catalyzer provided by the invention, wherein, in element, the content of adjuvant component is 0.1～20 weight % in the described rectorite that contains adjuvant component, is preferably 0.5～15 weight %, more preferably 2～12 weight %.
Adjuvant component P, Mg, RE, Ti, B, Zr in the rectorite that contains adjuvant component of the present invention are derived from the compound that contains P, Mg, RE, Ti, B, Zr, can be inorganic or organic compound.For example, P contained compound can be selected from one or more of the phosphoric acid salt of phosphoric acid, tetra-sodium, phosphorous acid, ammonium, alkali-metal phosphoric acid salt, organic phosphoric acid, organic phosphorous acid or organic Hypophosporous Acid, 50; Magnesium-containing compound can be selected from one or more of halogenide, oxide compound, nitrate, vitriol, phosphoric acid salt, alkyl magnesium compound or alkoxyl magnesium compound of magnesium; One or more of muriate, nitrate, oxyhydroxide, oxide compound that contain the optional self-contained rare earth metal of compound of rare earth; Titaniferous compound can be selected from the organic compound of titanium or in the mineral compound one or more, for example alkoxy compound of the halogenide of titanium, oxide compound, titanate, titanium; The compound of boracic can be selected from one or more in oxide compound, halogenide, borine, boric acid, borate or the organic boride of boron; But one or more in the alkyl oxide of the oxide compound of zirconic compound selected among zirconium, halogenide, nitrate, phosphoric acid salt or zirconium.Described rare earth element is selected from one or more in group of the lanthanides and the actinium series rare earth metal, is preferably in lanthanum, cerium, lanthanum rich mischmetal or the cerium-rich mischmetal compound one or more.
According to catalyzer of the present invention, wherein, described binder component is derived from one or more in aluminium colloidal sol, silicon sol, sial complex sol, aluminum phosphate colloidal sol, the acidification pseudo-boehmite.Described binding agent can be by being purchased or preparing according to existing method, for example, acidification pseudo-boehmite can prepare according to the method that patent US4010116, US4206085 provide, acid is 0.12～0.18 with the mol ratio of pseudo-boehmite (in aluminum oxide) during preferred pseudo-boehmite acidifying, aluminum phosphate colloidal sol can prepare according to the method that patent CN1008974C, CN1083512A provide, and silicon sol can prepare according to the method that U.S. Pat 3957689, US3867308 provide.
According to catalyzer of the present invention, wherein, described rectorite is one or more in natural calcium type rectorite, sodium type, lithium type, rare-earth type or the ammonia type rectorite.Described sodium type, lithium type, rare-earth type or ammonia type rectorite can be made by calcium type rectorite remodeling.
The basal spacing of rectorite is generally 1.9～5.0nm, the preferred basal spacing d that contains the rectorite of adjuvant component of the present invention
001Value is 2.7～5.0nm, and preferably its specific surface area is 100～300m
2/ g.
According to catalyzer provided by the invention, contain clay, zeolite.Contain the described rectorite that contains adjuvant component in the described clay, also can contain other clay, when described clay is when containing the mixture of the rectorite of adjuvant component and other clay, described other clay is selected from one or several in kaolin, diatomite, polynite, wilkinite, the sepiolite, is preferably kaolin.The content that contains the rectorite of adjuvant component in the described clay is 5～100 weight %, is preferably 10～90 weight %.
According to catalyzer provided by the invention, wherein, described zeolite is selected from the zeolite that cracking catalyst is used always, for example, be selected from y-type zeolite, Beta zeolite, have in the zeolite of MFI structure one or more, described y-type zeolite can be one or more in the overstable gamma zeolite of the y-type zeolite, overstable gamma zeolite of phosphorous and/or rare earth, phosphorous and/or rare earth; The zeolite of the described MFI of having structure can be the zeolite with MFI structure of phosphorous and/or rare earth.
In the catalyzer of the present invention, preferably contain the clay of 5～90 weight %, the zeolite of 10～95 weight % more preferably contains the clay of 10～80 weight %, the zeolite of 20～90 weight %.
Also can contain binder component in the catalyzer of the present invention.Described binder component is derived from one or more in aluminium colloidal sol, silicon sol, sial complex sol, aluminum phosphate colloidal sol, the acidification pseudo-boehmite binding agent.Described binding agent can be by being purchased or preparing according to existing method, for example, acidification pseudo-boehmite can prepare according to the method that patent US4010116, US4206085 provide, acid is 0.12～0.18 with the mol ratio of pseudo-boehmite (in aluminum oxide) during preferred pseudo-boehmite acidifying, aluminum phosphate colloidal sol can prepare according to the method that patent CN1008974C, CN1083512A provide, and silicon sol can prepare according to the method that U.S. Pat 3957689, US3867308 provide.In the catalyzer of the present invention, preferably contain binder component, more preferably contain the binder component of 10～50 weight % in oxide compound 5～60 weight %.
Cracking catalyst provided by the invention can comprise clay, zeolite are mixed making beating, then with the spray-dired step of described slurries according to existing method preparation.If also contain binder component in the catalyzer, also should comprise the step of described binder component being mixed making beating with clay, zeolite.
In the clay of the present invention, the rectorite that contains adjuvant component, the described preparation method who contains the rectorite of adjuvant component comprises: the compound and the water of rectorite, binding agent, adjuvant component are mixed, stirring is not less than 10 minutes, the preferred stirring 10～180 minutes obtains containing the slurries of the rectorite of adjuvant component.Described slurries can be directly used in the preparation catalyzer, also can be used further to prepare catalyzer behind the first drying and moulding.It is 20～45 weight % that the consumption of preferred rectorite, binding agent, adjuvant component compound and water makes the content of solids in the slurries.When being used further to prepare catalyzer after with the described rectorite slurry dried moulding that contains adjuvant component, preferably, before the drying and moulding, with ammoniacal liquor the pH value of slurries is transferred to 2～7, then slurries were worn out 0.5～24 hour down in 15～75 ℃, dry again, moulding (for example spray drying forming), the concentration of described ammoniacal liquor is preferably 3～10 weight %, the thunder holder soil that contains adjuvant component behind the drying and moulding, can be directly used in the preparation catalyzer, or be used further to prepare catalyzer after 0.5～3 hour prior to 350～650 ℃ of following roastings.
Among the preparation method of the rectorite that contains adjuvant component provided by the invention, the order by merging of each material does not have particular requirement, after rectorite, binding agent and water can being mixed, again with the adjuvant component compound; After also rectorite, adjuvant component compound and water can being mixed, mix with binding agent again; Can also earlier adjuvant component compound and binding agent be mixed, mix with rectorite again.
Spraying drying is a prior art described in the Preparation of catalysts method of the present invention, and the exhaust temperature of preferably spray drying is 160～220 ℃.Spraying drying gained catalyzer also can carry out roasting, and the temperature of roasting is 350～800 ℃, is preferably 400～650 ℃, and the time of roasting is 0.5～6 hour, is preferably 1～4 hour; Described roasting can be carried out in any atmosphere, for example carries out in air.
Catalyzer provided by the invention can be used as the cracking hydrocarbon oil catalyzer, can also be as cocatalyst for cracking.When as promotor, the content of described catalyzer in the catalytic cracking catalyst mixture is 5～50 weight %.
The following examples will the invention will be further described, but not thereby limiting the invention.
Among the embodiment, rectorite derives from rectorite ore deposit, Zhongxiang City, Hubei, and its solid content is 86.7 weight %; Kaolin is produced by Suzhou kaolin company, and solid content is 76 weight %; In the rare earth chloride solution rare earth oxide mass content be 337 grams per liters (in the rare earth oxide, La
2O
3Content is 25.7 weight %, Ce
2O
3Content is 46.8 weight %, and other rare earth oxide content is 27.5 weight %); Alumina content in the aluminium colloidal sol is 21.5 weight %; The solid content 45.0 weight % of aluminum phosphate colloidal sol, the content of silicon oxide is 24.2 weight % in the silicon sol.The acidification pseudo-boehmite solid content is 12 weight %, and acid is 0.15 with the mol ratio of aluminum oxide during acidifying.Used overstable gamma zeolite is produced for the Shandong catalyst plant, and solid content 74.7%, lattice constant are 24.58
In weight percent content, Na
2O content is 0.44%, RE
2O
3Content is 10～12%.The concentration of ammoniacal liquor is 10 weight %, and all the other reagent are produced by Beijing dicyclo reagent company, and specification is analytical pure.
Physical and chemical performance is estimated: the fluidisation abrasion index, water droplet pore volume and the apparent bulk density that adopt RIPP standard method (seeing volumes such as " petrochemical complex analytical procedure " (RIPP test method) Yang Cuiding, Science Press, nineteen ninety publication) analytic sample.
Embodiment 1～8 explanation Catalysts and its preparation method provided by the invention.
Embodiment 1
(1) 313 gram decationized Y sieve water, 930 gram aluminium colloidal sols are mixed, add 580 gram rectorites under stirring, stir after 15 minutes, add 85.2 gram (NH again
4)
2HPO
4, continue to stir 30 minutes, obtain the slurries that solid content is 40 weight %.
(2) 4.8 kilograms of kaolin, 3.72 kilograms of aluminium colloidal sol, 8.3 kilograms acidification pseudo-boehmite will be added in step (1) the gained slurries, making beating, add 5.1 kilograms of y-type zeolites and 10.8 kilograms of slurries that the deionized waters mixing forms again, stirred 30 minutes, then with the slurries spray drying forming that obtains, 500 ℃ of roastings 1.5 hours obtain catalytic cracking catalyst C1.Composition and the physical and chemical performance of C1 are listed in table 1.
Embodiment 2
(1) 864 gram decationized Y sieve water, 826 gram silicon sol, 1150 gram rectorites are mixed, stir after 30 minutes, add 1255 gram MgCl
26H
2O continues to stir 60 minutes, makes the slurries that solid content is 35.0 weight %.
(2) 3.36 kilograms of kaolin, 3.31 kilograms of silicon sol, 12.5 kilograms acidification pseudo-boehmite will be added in the slurries of step (1) gained, making beating, the slurries of 5.1 kilograms of y-type zeolites and 10.8 kilograms of deionized water making beating formation are added in the resulting slurries, stirred 30 minutes, then with the slurries spray drying forming that obtains, 600 ℃ of following roastings 1 hour promptly obtain catalytic cracking catalyst C2.C2 forms and physical and chemical performance is listed in table 1.
Embodiment 3
(1) 5.17 kilograms of decationized Y sieve water, 1035 milliliters re chloride and 1.73 kilograms of rectorites are mixed, stirs after 30 minutes, add 667 gram aluminum phosphate colloidal sols, continue stirring 90 minutes, make the slurries that solid content is 25 weight %.
(2) 2.37 kilograms of kaolin, 2.23 kilograms of aluminum phosphate colloidal sol, 10.8 kilograms acidifying aluminium stone will be added in the slurries of step (1) gained, making beating, add 5.1 kilograms of y-type zeolites and 10.8 kilograms of slurries that deionized water forms again, stirred 30 minutes, again with the slurries spray drying forming that obtains, 400 ℃ of following roastings 3 hours obtain catalytic cracking catalyst C3.C3 forms and physical and chemical performance is listed in table 1.
Embodiment 4
(1) 1.9 kilograms of decationized Y sieve water, 1.86 kilograms of aluminium colloidal sols and 3.33 kilograms of acidification pseudo-boehmites are mixed, stir, add 2.31 kilograms of rectorites, stir after 20 minutes, add 707 gram ZrOCl
28H
2O stirred 40 minutes, was prepared into the slurries that solid content is 30 weight %.
(2) 1.71 kilograms of kaolin, 5.12 kilograms of aluminium colloidal sols, 6.67 kilograms of acidification pseudo-boehmites will be added in the slurries of step (1) gained, making beating, add 5.1 kilograms of y-type zeolites and 10.8 kilograms of slurries that deionized water forms again, restir 30 minutes, with the slurries spray drying forming that obtains, 450 ℃ of following roastings 2 hours obtain catalytic cracking catalyst C4.C4 forms and physical and chemical performance is listed in table 1.
Embodiment 5
(1) with 4.24 kilograms of decationized Y sieve water, 990 gram TiCl
4, 2.79 kilograms of aluminium colloidal sols mix and stir after 60 minutes, add 3.46 kilograms of rectorites, continue stirring 30 minutes, are prepared into the slurries that solid content is 35 weight %.
(2) 4.19 kilograms of aluminium colloidal sols, 12.08 kilograms acidification pseudo-boehmite will be added in the slurries of step (1) gained, making beating, add 5.1 kilograms of y-type zeolites and 10.8 kilograms of slurries that deionized water forms again, stirred 30 minutes, again with the slurries spray drying forming that obtains, 550 ℃ of following roastings 1 hour promptly obtain catalytic cracking catalyst C5.C5 forms and physical and chemical performance is listed in table 1.
Embodiment 6
(1) with 8.33 kilograms acidification pseudo-boehmite, 2131 gram tributyl borate (C
12H
27BO
3) mix, stirred 10 minutes, add 1.15 kilograms of rectorites, continue to stir 90 minutes, be prepared into the slurries that solid content is 20 weight %.
(2) 3.03 kilograms of kaolin, 3.72 kilograms of aluminium colloidal sol, 8.34 kilograms acidification pseudo-boehmite will be added in the slurries of step (1) gained, making beating, add 5.1 kilograms of y-type zeolites and 10.8 kilograms of slurries that the deionized water making beating obtains, restir 30 minutes, with the slurries spray drying forming that obtains, 550 ℃ of following roastings 1 hour promptly obtain catalytic cracking catalyst C6.C6 forms and physical and chemical performance is listed in table 1.
Embodiment 7
(1) with 0.58 kilogram of decationized Y sieve water, 4.65 kilograms of aluminium colloidal sol, 792 gram TiCl
4Mix with 2.31 kilograms of rectorites, stir after 35 minutes, add 426 gram (NH
4)
2HPO
4With 837 gram MgCl
26H
2Continue behind the O to stir 120 minutes, be prepared into the slurries that solid content is 40 weight %.
(2) 1.05 kilograms of kaolin, 16.67 kilograms acidification pseudo-boehmite will be added in the slurries of step (1) gained, making beating, slurries with 5.1 kilograms of y-type zeolites and 10.8 kilograms of deionized water making beating formation join in the above-mentioned slurries again, restir 30 minutes, with the slurries spray drying forming that obtains, 650 ℃ of following roastings 0.5 hour promptly obtain catalytic cracking catalyst C7.C7 forms and physical and chemical performance is listed in table 1.
Embodiment 8
(1) with 2.4 kilograms of decationized Y sieve water, 3.72 kilograms of aluminium colloidal sol, 354 gram ZrOCl
28H
2O and 4.04 kilograms of rectorites mix, and stir after 30 minutes, add 1.06 kilograms of (NH
4)
2HPO
4, 1.67 kilograms of MgCl
26H
2Continue behind the re chloride of O and 1.207 liters to stir 120 minutes, make the slurries that solid content is 40 weight %.
(2) with the acidification pseudo-boehmite that adds 8.33 kilograms in the slurries of step (1) gained, stir and add 5.1 kilograms of y-type zeolites and 10.8 kilograms of slurries that the deionized water making beating forms down, restir 30 minutes, with the slurries spray drying forming that obtains, 650 ℃ of following roastings 0.5 hour promptly obtain catalytic cracking catalyst C8.C8 forms and physical and chemical performance is listed in table 1.
Comparative Examples 1
The method that provides according to embodiment among the CN1175086C 1 prepares cracking catalyst, obtains contrast medium D1.D1 has following composition: with the total catalyst weight benchmark, and rectorite content 20.0 weight %, kaolin content 14.0 weight %, binder content 28.0 weight % (calculating) with alumina content, y-type zeolite content is 38.0 weight %.Its composition and physical and chemical performance are listed in table 1.
Comparative Examples 2
The method that provides according to embodiment among the CN1211608A 1 prepares cracking catalyst, obtains contrast medium D2.D2 has following composition: with the total catalyst weight benchmark, and rectorite content 20.0 weight %, kaolin content 14.0 weight %, binder content 28.0 weight % (calculating) with alumina content, y-type zeolite content is 38.0 weight %.Its composition and physical and chemical performance are listed in table 1.
Embodiment 9～16
Present embodiment illustrates the catalytic cracking performance of catalyst for cracking heavy oil provided by the invention.
Light oil microactivity is estimated: adopt the standard method of RIPP92-90 (to see volumes such as " petrochemical complex analytical procedure " (RIPP test method) Yang Cuiding, Science Press, the nineteen ninety publication) light oil microactivity of assess sample, the catalyzer loading amount is 5.0g, temperature of reaction is 460 ℃, stock oil is 235～337 ℃ of huge port solar oils of boiling range, and product is made up of gas chromatographic analysis, forms according to product to calculate light oil microactivity.
Light oil microactivity (MA)=(being lower than gasoline output+gas yield+coke output of 216 ℃ in the product)/charging total amount * 100%
Heavy oil cracking performance evaluation condition: catalyzer is earlier at 800 ℃, and 100% steam aging 8 hours is estimated on ACE (fixed fluidized bed) device then, and stock oil is military three heavy oil (character sees Table 2) that mix, 500 ℃ of temperature of reaction, and agent weight of oil ratio is 8.04.
Wherein, transformation efficiency=yield of gasoline+yield of liquefied gas+dry gas yield+coking yield
Yield of light oil=yield of gasoline+diesel yield
Coke selectivity=coke yield/transformation efficiency
Estimate the catalyzer C1～C8 of embodiment 1～8 preparation according to the method described above respectively, reaction result is listed in table 3.
Comparative Examples 3～4
The catalytic cracking performance of following Comparative Examples explanation contrast medium.
Adopt the method identical to estimate the catalytic cracking performance of comparative catalyst D1～D2 respectively, the results are shown in table 3 with embodiment 9.
From table 3 data as can be seen, compare with catalyzer D1, D2 that Comparative Examples provides, catalyst for cracking heavy oil provided by the invention has higher heavy oil conversion rate, higher gasoline yield and yield of light oil, and have coke selectivity preferably, coke yield obviously reduces.
Table 1
Table 2
| ACE estimates | |
| Stock oil | Military mixed three |
| Density (20 ℃), g/cm 3 | 0.9044 |
| Refractive power (70 ℃) | 1.5217(20℃) |
| Viscosity (100 ℃) mm 2/s | 9.96 |
| Zero pour, ℃ | 40 |
| Aniline point, ℃ | 95.8 |
| C m％ H m％ S m％ N m％ | 85.98 12.86 0.55 0.18 |
| Carbon residue m% | 3.0 |
| Boiling range, ℃ initial boiling point 5% 10% 30% 50% 70% 90% | 243 294 316 395 429 473 - |
Embodiment 17
Present embodiment explanation Catalysts and its preparation method of the present invention.
651.0 gram decationized Y sieve water, 883.7 gram aluminium colloidal sols are mixed, add 922.7 gram rectorites, stir after 15 minutes, add 42.6 gram (NH again
4)
2HPO
4, stirred 10 minutes, obtain the slurries that solid content is 40 weight %, the pH value with ammoniacal liquor adjusting slurries is 4.0 again, wears out 6 hours down in 25 ℃ then.With above-mentioned gained slurries spray drying forming,, obtain containing the rectorite of adjuvant component 600 ℃ of roastings 1 hour.Above-mentioned rectorite and 100 gram kaolin, the 555 gram decationized Y sieve water that contain adjuvant component of 270 grams are mixed making beating, add 2083 gram acidification pseudo-boehmites and 1086 gram REUSY6.0 molecular sieve (catalyzer Shandong branch office of China Petrochemical Industry product) slurries (slurry solid content is 35 weight %) making beating then, spray drying forming, obtain catalyzer CC1, composition, the rerum natura of catalyzer see Table 4.
Embodiment 18
Present embodiment explanation Catalysts and its preparation method of the present invention.
930.2 gram aluminium colloidal sols, 1541.7 gram acidification pseudo-boehmites, 692.0 gram rectorites are mixed, and making beating adds 125.5 gram MgCl
26H
2O stirred 30 minutes, obtained the slurries that solid content is 30.4 weight %.The pH value of regulating slurries with ammoniacal liquor is 5.0, wears out 12 hours down in 25 ℃ then.With above-mentioned slurries spray drying forming,, obtain containing the rectorite of adjuvant component 450 ℃ of roastings 3 hours.Above-mentioned rectorite and 100 gram kaolin, the 555 gram decationized Y sieve water that contain adjuvant component of 270 grams are mixed making beating, add 2083 gram acidification pseudo-boehmites and 1086 gram REUSY6.0 molecular sieve (catalyzer Shandong branch office of China Petrochemical Industry product) slurries (slurry solid content is 35 weight %) making beating then, spray drying forming, obtain catalyzer CC2, composition, the rerum natura of catalyzer see Table 4.
Embodiment 19
Present embodiment explanation Catalysts and its preparation method of the present invention.
1521.7 gram decationized Y sieve water, 103.5 milliliters of re chlorides and 922.7 gram rectorites are mixed, stirred 20 minutes, add 377.8 and restrain the aluminum phosphate colloidal sols, stirred 45 minutes, make the slurries that solid content is 35 weight %.The pH value of regulating slurries with ammoniacal liquor is 3.0, wears out 1 hour down in 40 ℃ then.With above-mentioned gained slurries spray drying forming,, obtain the rectorite that contains adjuvant component provided by the invention 500 ℃ of roastings 1.5 hours.Above-mentioned rectorite and 100 gram kaolin, the 555 gram decationized Y sieve water that contain adjuvant component of 270 grams are mixed making beating, add 2083 gram acidification pseudo-boehmites and 1086 gram REUSY6.0 molecular sieve (catalyzer Shandong branch office of China Petrochemical Industry product) slurries (slurry solid content is 35 weight %) making beating then, spray drying forming, obtain catalyzer CC3, composition, the rerum natura of catalyzer see Table 4.
Embodiment 20
Present embodiment explanation Catalysts and its preparation method of the present invention.
With 626.7 gram decationized Y sieve water, 586.8 gram silicon sol, 28.3 gram ZrOCl
28H
2O mixes, and stirs, and adds 980.4 gram rectorites, stirs 20 minutes, makes the slurries that solid content is 45 weight %.The pH value of regulating slurries with ammoniacal liquor is 3.5, wears out 3 hours down in 25 ℃ then.With above-mentioned gained slurries spray drying forming,, obtain the rectorite that contains adjuvant component provided by the invention 650 ℃ of roastings 0.5 hour.Above-mentioned rectorite and 100 gram kaolin, the 555 gram decationized Y sieve water that contain adjuvant component of 270 grams are mixed making beating, add 2083 gram acidification pseudo-boehmites and 1086 gram REUSY6.0 molecular sieve (catalyzer Shandong branch office of China Petrochemical Industry product) slurries (slurry solid content is 35 weight %) making beating then, spray drying forming, obtain catalyzer CC4, composition, the rerum natura of catalyzer see Table 4.
Embodiment 21
Present embodiment explanation Catalysts and its preparation method of the present invention.
With 973.5 gram decationized Y sieve water, 237.6 gram TiCl
4, 930.2 gram aluminium colloidal sols mix, and stir after 10 minutes, add 1166.7 gram acidification pseudo-boehmites and 692.0 and restrain rectorites, stirred 20 minutes, obtain the slurries that solid content is 25 weight %, the pH value of regulating slurries with ammoniacal liquor is 2.5, wears out 24 hours down in 25 ℃ then.With above-mentioned gained slurries spray drying forming,, obtain the rectorite that contains adjuvant component provided by the invention 500 ℃ of roastings 2 hours.Above-mentioned rectorite and 100 gram kaolin, the 555 gram decationized Y sieve water that contain adjuvant component of 270 grams are mixed making beating, add 2083 gram acidification pseudo-boehmites and 1086 gram REUSY6.0 molecular sieve (catalyzer Shandong branch office of China Petrochemical Industry product) slurries (slurry solid content is 35 weight %) making beating then, spray drying forming, obtain catalyzer CC5, composition, the rerum natura of catalyzer see Table 4.
Embodiment 22
Present embodiment explanation Catalysts and its preparation method of the present invention.
With 1013.0 gram decationized Y sieve water, 441.9 gram aluminium colloidal sols, 138.6 gram tributyl borate (C
12H
27BO
3) mix, stir, add 1038.1 gram rectorites, stirred 15 minutes, be prepared into the slurries that solid content is 38 weight %.The pH value of regulating slurries with ammoniacal liquor is 4.5, and is following aging 4 hours in 35 ℃ then.With above-mentioned gained slurries spray drying forming,, obtain the rectorite that contains adjuvant component provided by the invention 400 ℃ of roastings 3 hours.Above-mentioned rectorite and 100 gram kaolin, the 555 gram decationized Y sieve water that contain adjuvant component of 270 grams are mixed making beating, add 2083 gram acidification pseudo-boehmites and 1086 gram REUSY6.0 molecular sieve (catalyzer Shandong branch office of China Petrochemical Industry product) slurries (slurry solid content is 35 weight %) making beating then, spray drying forming, obtain catalyzer CC6, composition, the rerum natura of catalyzer see Table 4.
Embodiment 23
Present embodiment explanation Catalysts and its preparation method of the present invention.
With 977.0 gram decationized Y sieve water, 697.7 gram aluminium colloidal sols, 213.1 gram tributyl borate (C
12H
27BO
3), 51.7 milliliters of re chlorides mix, and stir to add 951.6 gram rectorites down, stir 25 minutes, are prepared into the slurries that solid content is 35 weight %.The pH value of regulating slurries with ammoniacal liquor is 4.5, and is following aging 8 hours in 25 ℃ then.With above-mentioned gained slurries spray drying forming,, obtain the rectorite that contains adjuvant component provided by the invention 500 ℃ of roastings 2.5 hours.Above-mentioned rectorite and 100 gram kaolin, the 555 gram decationized Y sieve water that contain adjuvant component of 270 grams are mixed making beating, add 2083 gram acidification pseudo-boehmites and 1086 gram REUSY6.0 molecular sieve (catalyzer Shandong branch office of China Petrochemical Industry product) slurries (slurry solid content is 35 weight %) making beating then, spray drying forming, obtain catalyzer CC7, composition, the rerum natura of catalyzer see Table 4.
Embodiment 24
Present embodiment explanation Catalysts and its preparation method of the present invention.
With 1395.3 gram aluminium colloidal sols, 167.4 gram MgCl26H2O, 85.4 gram (NH
4)
2HPO
4Mix with 120.7 milliliters of re chlorides, add 720.9 gram rectorites, stirred 40 minutes, be prepared into the slurries that solid content is 41 weight %.The pH value of regulating slurries with ammoniacal liquor is 4.0, wears out 12 hours in 25 ℃ then.With above-mentioned gained slurries spray drying forming,, obtain the rectorite that contains adjuvant component provided by the invention 650 ℃ of roastings 1 hour.Above-mentioned rectorite and 100 gram kaolin, the 555 gram decationized Y sieve water that contain adjuvant component of 270 grams are mixed making beating, add 2083 gram acidification pseudo-boehmites and 1086 gram REUSY6.0 molecular sieve (catalyzer Shandong branch office of China Petrochemical Industry product) slurries (slurry solid content is 35 weight %) making beating then, spray drying forming, obtain catalyzer CC8, composition, the rerum natura of catalyzer see Table 4.
Table 4
Embodiment 25～32
The catalytic cracking performance of embodiment 25～32 explanations cracking catalyst of the present invention.
With catalyzer CC1～CC8 respectively at 800 ℃, aging 8 hours of 100% water vapour atmosphere places ACE device (fixed fluidized bed reaction unit), and mixing three heavy oil (character sees Table 2) with force is raw material, 500 ℃ of temperature of reaction, the agent weight of oil is than being to estimate under 4.02 the condition.The results are shown in table 5.
Table 5
| The embodiment numbering | Embodiment 25 | Embodiment 26 | Embodiment 27 | Embodiment 28 | Embodiment 29 | Embodiment 30 | Embodiment 31 | Embodiment 32 |
| Catalyzer | CC1 | CC2 | CC3 | CC4 | CC5 | CC6 | CC7 | CC8 |
| Temperature of reaction, ℃ | 500 | 500 | 500 | 500 | 500 | 500 | 500 | 500 |
| Agent-oil ratio | 4.02 | 4.02 | 4.02 | 4.02 | 4.02 | 4.02 | 4.02 | 4.02 |
| Product distributes, w% | ||||||||
| Dry gas | 1.38 | 1.30 | 1.42 | 1.42 | 1.44 | 1.32 | 1.33 | 1.38 |
| Liquefied gas | 14.80 | 14.72 | 15.45 | 15.31 | 15.05 | 14.88 | 15.15 | 14.99 |
| Coke | 4.83 | 4.84 | 5.05 | 4.85 | 4.92 | 5.10 | 4.99 | 4.98 |
| Gasoline | 52.40 | 51.76 | 52.98 | 52.49 | 52.10 | 51.64 | 52.20 | 52.88 |
| Diesel oil | 17.62 | 17.73 | 16.85 | 16.67 | 17.65 | 17.66 | 17.59 | 17.66 |
| Heavy oil | 8.97 | 9.65 | 8.25 | 9.26 | 8.84 | 9.40 | 8.74 | 8.11 |
| Add up to | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Transformation efficiency, w% | 73.41 | 72.62 | 74.90 | 74.07 | 73.51 | 72.94 | 73.67 | 74.23 |
| Yield of light oil, w% | 70.02 | 69.49 | 69.83 | 69.16 | 69.75 | 69.30 | 69.79 | 70.54 |
| The light receipts *+ liquefied gas, w% | 84.82 | 84.21 | 85.28 | 84.47 | 84.80 | 84.18 | 84.94 | 85.53 |
| Coke/transformation efficiency | 0.0658 | 0.0666 | 0.0674 | 0.0655 | 0.0669 | 0.0699 | 0.0677 | 0.0671 |
*Annotate: " light receipts+liquefied gas " expression " yield of light oil+yield of liquefied gas "
Claims (14)
1. catalyst for cracking heavy oil, contain the zeolite and the clay of significant quantity, it is characterized in that, contain a kind of rectorite that contains adjuvant component in the described clay at least, gross weight with clay is a benchmark, and the content that contains the rectorite of adjuvant component in the described clay is 5～100 weight %; Weight with the rectorite that contains adjuvant component is benchmark, the rectorite that contains 45～94.9 weight % in the described rectorite that contains adjuvant component, in the binder component of oxide compound 5～50 weight %, in one or more the adjuvant component among P, Mg, RE, Ti, B, the Zr of being selected from of element 0.1～20 weight %.
2. according to the described catalyzer of claim 1, it is characterized in that the content of adjuvant component is 0.5～15 weight % in the described rectorite.
3. according to the described catalyzer of claim 2, it is characterized in that the content of adjuvant component is 2～12 weight % in the described rectorite.
4. according to the described catalyzer of claim 1, it is characterized in that, contain the rectorite that 10～90 weight % contain adjuvant component in the described clay.
5. according to the described catalyzer of claim 1, it is characterized in that described binder component is derived from one or more in aluminium colloidal sol, silicon sol, silica-alumina gel, sial complex sol, aluminum phosphate colloidal sol, the acidification pseudo-boehmite.
6. according to the described catalyzer of claim 1, it is characterized in that, contain the clay of 5～90 weight % in the described catalyst for cracking heavy oil, the zeolite of 10～95 weight %.
7. according to claim 1 or 6 described catalyzer, it is characterized in that, also contain the binder component of 5～60 weight % in the described catalyst for cracking heavy oil.
8. according to the described catalyzer of claim 1, it is characterized in that the described basal spacing d that contains the rectorite of adjuvant component
001Value is 2.7～5.0nm, and specific surface area is 100～300m
2/ g.
9. the preparation method of a catalytic cracking catalyst comprises clay is mixed making beating, spray-dired step with zeolite, it is characterized in that, contains a kind of rectorite that contains adjuvant component in the described clay at least; The described preparation method who contains the rectorite of adjuvant component comprises: the compound and the water of rectorite, binding agent, adjuvant component are mixed, stir and be not less than 10 minutes, obtain containing the rectorite slurries of adjuvant component; It is 10～60 weight % that the compound of rectorite, binding agent, adjuvant component and the consumption of water make the solid content of gained slurries, and the consumption of the compound of rectorite, binding agent, adjuvant component makes in the prepared thunder holder soil that contains adjuvant component, weight with the thunder holder soil that contains adjuvant component is benchmark, the rectorite that contains 45～94.9 weight %, in the binder component of oxide compound 5～50 weight %, in one or more the adjuvant component among P, Mg, RE, Ti, B, the Zr of being selected from of element 0.1～20 weight %.
10. in accordance with the method for claim 9, it is characterized in that among the preparation method of the described rectorite that contains adjuvant component, it is 20～45 weight % that the consumption of each material makes the solid content of resulting slurries, the churning time after each mixing of materials is 10～180 minutes.
11., it is characterized in that also comprise the step with the catalyzer roasting after the spraying drying in the described Preparation of catalysts method, the condition of roasting: maturing temperature is 350～800 ℃ according to claim 9 or 10 described methods, roasting time is 0.5～6 hour.
12. in accordance with the method for claim 11, it is characterized in that the condition of described roasting: maturing temperature is 400～650 ℃, and the time of roasting is 1～4 hour.
13. in accordance with the method for claim 9, it is characterized in that, also comprise with ammoniacal liquor among the described preparation method who contains the adjuvant component rectorite the described pH value that contains the rectorite slurries of adjuvant component is transferred to 2～7, then in 15～75 ℃ aging 0.5～24 hour down, drying and mouldings again.
14. in accordance with the method for claim 13, it is characterized in that, also comprise among the described preparation method who contains the adjuvant component rectorite drying and moulding gained is contained the rectorite of adjuvant component in 350～650 ℃ of following roastings 0.5～3 hour.
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