CN101285001B - Catalytic cracking catalyst - Google Patents
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- CN101285001B CN101285001B CN2007100653652A CN200710065365A CN101285001B CN 101285001 B CN101285001 B CN 101285001B CN 2007100653652 A CN2007100653652 A CN 2007100653652A CN 200710065365 A CN200710065365 A CN 200710065365A CN 101285001 B CN101285001 B CN 101285001B
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Abstract
The invention relates to cracking catalyst, containing rare earth ultrastable Y-type zeolite and stroma, wherein the stroma contains alumina with additive; the alumina with additive contains the following composition in percentage by weight: 60 to 99.5 percent of alumina and 0.5 to 40 percent of additive; the additive is selected from one or a plurality of compounds containing alkaline earth, lanthanide metal, silicon, gallium, boron or phosphorus elements; the rare earth ultrastable Y-type zeolite is obtained through a method comprising the following steps that: ultrastable Y-type zeolite and an acid solution with the equivalent concentration between 0.01 and 2 N are mixed with the liquid/solid weight ratio of 4 to 20 in the temperature range between 20 and 100 DEG C, stirred for 10 to 300 minutes, washed and filtered; rare earth salt solution is added in to exchange rare earth ions; the solution is washed and filtered after exchange. The catalyst is strong in heavy oil cracking capability, high in light oil yield and low in coke yield.
Description
Technical field
The present invention relates to a kind of hydrocarbon oil catalytic cracking catalyzer.
Background technology
Along with catalytically cracked stock become the strict day by day of heavy and environmental regulation day by day, require catalytic cracking catalyst to improve heavy oil conversion and preventing from heavy metal pollution ability, but low-carbon olefines high-output and low sulfur content stop bracket gasoline again simultaneously.The key that obtains high yield, stop bracket gasoline is that the catalyst activity component is that rare-earth type high-silicon gamma-zeolite can keep crystalline structure intact, has very high heat and hydrothermal stability, strongly-acid and low sour density.In order to obtain to have the rare earth high-silica zeolite of described performance, normally the NaY zeolite with synthetic carries out suitable ion-exchange and super steady modification processing, reduce the aluminium content in the y-type zeolite, reduce lattice constant, improve the silica alumina ratio of zeolite framework, thereby reduce sour density, improve thermostability and hydrothermal stability, improve gasoline selective.
The preparation method of overstable gamma zeolite mainly contains gas chemistry method, liquid phase villiaumite method, hydrothermal method and hydro-thermal/Chemical bond method.The gas chemistry method is that Beyer and Mankui at first reported in 1980.U.S. Pat 4273753, US4438178 disclose and have utilized SiCl
4The method of gas chemistry dealuminzation system ultrastable Y.The gas chemistry method prepares super steady zeolite, and to have a dealuminzation even, and it is timely to mend silicon, the characteristics that the duct is unimpeded, and made super steady crystallization of zeolites reservations degree height, the thermostability height, still, because problems such as equipment wait to solve, at present also promoting the use of industrial.
Liquid phase villiaumite method (US4503023) is with NH
4Y zeolite carries out the ammonium silicofluoride dealumination complement silicon, can significantly improve Si/Al thermostability when under the situation that keeps high-crystallinity, but this technology is on the one hand because the indissoluble thing AlF that forms in dealumination process
3Be difficult for removing fully with residual silicofluoride, influence the hydrothermal stability of zeolite, also have the serious environmental pollution problem on the other hand, make it can not widespread use.
Hydrothermal method is the present industrial method that ultrastable Y generally adopts for preparing, and still, hydrothermal method because silicon can not in time move, mends to go into to lack the aluminium room in dealumination process, causes lattice to subside, non-framework aluminum clogged with fragments duct.The obstruction in duct has not only influenced the accessibility of reaction molecular, has also hindered entering of rare earth ion.
The modified zeolite of Y-type that contains rare earth ion is a most frequently used active ingredient in current catalytic cracking and the hydrocracking reaction catalyzer, but the order of earth solution exchange, condition etc. have great role to the performance of rare earth ion exchanged effect and effect thereof.
People think for a long time all the time, make the catalyzer that contains the rare earth zeolite have higher heat and hydrothermal stability and must make sufficiently high content of rare earth is arranged in the zeolite.In order to improve the content of rare earth in the Hydrothermal Preparation high-silicon Y-Zeolite, employing at present repeatedly exchanges the method for repeatedly roasting, makes in the Hydrothermal Preparation type-Y high silicon zeolite with RE
2O
3The content of rare earth of meter can reach the heavy % of 2-3, but this does not still satisfy the requirement of deep processing to catalyzer.The duct obstruction that aluminium chips causes is the major cause that the intracrystalline content of rare earth of the super steady Y (as DASY-2.0) of present Hydrothermal Preparation is difficult to improve.
Among U.S. Pat 4584287 and the US4429053, the NaY zeolite is then carried out steam treatment with rare earth ion exchanged earlier, described method is because the shielding effect of rare earth ion and support make the aluminium of steam-treated process mesolite remove the comparison difficulty, the unit cell parameters of zeolite before steam-treated increases to 2.465-2.475nm, and handle the back is 2.420-2.464nm, reduces unit cell parameters temperature required higher (593-733 ℃).
In the method that U.S. Pat 5340957 and US5206194 provide, the SiO of raw material NaY zeolite
2/ Al
2O
3Than being 6.0, cost is higher.Described method also is after NaY is carried out rare earth exchanged, to carry out hydrothermal treatment consists again, has the shortcoming of aforesaid U.S. Patent US4584287 and US4429053 equally.
U.S. Pat 3493519 has been described the method for hydro-thermal and chemical association prepared overstable gamma zeolite, and this method is that NaY is exchanged through several, and roasting under the superheated vapor condition is then handled with mineral acid or complexing agent again.
Chinese patent CN1042558A discloses a kind of fluidized catalytic cracking catalyst that contains new-type high silicon Y zeolite, and described high-silicon Y-Zeolite combines by chemical dealuminization and hydrothermal treatment consists process and is used alternatingly the method preparation of handling the NaY zeolite.Two kinds of processes of chemical dealuminization and hydrothermal dealumination can be used alternatingly repeatedly arbitrarily.Chemical dealuminization can select for use some organic acids, organic and inorganic salt to do dealumination agent.In the chemical dealuminization process, carry out the ion-exchange of ammonium and sodium simultaneously.But this patent does not relate to further rare earth ion exchanged.
CN1436728A provides a kind of novel rare-earth ultrastable Y preparation method heavy oil fluid catalytic cracking, that contain anti-vanadium component that is used for, this method is to be raw material with the NaY zeolite, contain oxalic acid or oxalate and composition thereof in the chemical dealuminization complexing agent, introduce rare earth ion in the chemical dealuminization reaction later stage, form rare-earth precipitation, pass through hydrothermal treatment consists again, can realize the purpose of super stabilizing and introducing rare earth ion and independent phase oxidation rare earth, the precipitating rare earth precursor that this method forms comprises rare earth oxalate.This patent also is to introduce rare earth earlier, carries out hydrothermal treatment consists again, also has the shortcoming of aforesaid U.S. Patent US4584287 and US4429053.In addition, rare earth oxide can not play the effect of stablizing zeolite framework in the deposition of zeolite surface.
CN1296860A discloses the Preparation of catalysts method that contains small crystal grain Y-shaped molecular sieve, comprises with crystal grain being that the NaY molecular sieve of 200nm～800nm obtains little crystal grain USY, REY, REHY, HY molecular sieve through conventional modification procedure such as ion-exchange, roasting or super stabilizing processing; With one or more making beating of resulting molecular sieve, carry out modification with rare earth and magnesium salts and handle, and mix with binding agent and carrier then, spraying drying, washing, drying obtain catalyzer again.This patent does not relate to the content of rare earth problem that improves in the super stable molecular sieve.
CN1143666A discloses the catalyzer of a kind of voluminous isoparaffin and gasoline, and this catalyzer is made up of combined oxidation al binder, kaolin and mixed molecular sieve.Wherein contain y-type zeolite, described y-type zeolite content of rare earth is 0～5 heavy %, obtains through chemistry or physical method stabilization, the type-Y high silicon zeolite that comprises the ultrastable Y that obtains with hydrothermal method, obtains with liquid phase method or vapor phase process aluminium-eliminating and silicon-replenishing.
USP5258341 and USP5908547 disclose a kind of Y zeolite cracking catalyst that contains yttrium, and this catalyzer is to be active ingredient by the super-stable Y molecular sieves that contains yttrium, can reduce dry gas, increase gasoline yield.
CN1916116A has announced a kind of catalytic cracking catalyst, the molecular sieve and a kind of aluminum oxide that contains additive that contain significant quantity, with the described aluminum oxide that contains additive is benchmark, the described aluminum oxide that contains additive contains the aluminum oxide of 60-99.5 weight %, 0.5-40 the additive of weight %, described catalyzer is by the preparation of the method that may further comprise the steps: (1) with pseudo-boehmite be enough to that the water of its pulp and acid are under agitation mixed, wherein to make the weight ratio of aluminum oxide in described acid and the pseudo-boehmite be 0.01-0.5 to Suan consumption; (2) with the mixed serum of step (1) under the temperature of room temperature-90 ℃ aging 0-24 hour; (3) product with step (2) mixes with additive; (4) product with step (3) mix with molecular sieve, dry and roasting.
Because the ultra-steady Y molecular sieve intracrystalline content of rare earth in the catalytic cracking catalyst is low at present, its heavy oil conversion rate and yield of light oil are lower.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of lightweight oil productive rate height, coke yield is low, the catalytic cracking catalyst that heavy oil conversion performance is strong.
The invention provides a kind of cracking catalyst, contain rare earth superstable Y-type molecular sieve and matrix, described matrix contains a kind of aluminum oxide that contains additive; The aluminum oxide that contains 60 weight %-99.5 weight % in the described aluminum oxide that contains additive, 0.5 the additive of weight %-40 weight %, described additive is selected from one or more in the compound that contains alkaline-earth metal, lanthanide series metal, silicon, gallium, boron or phosphoric; Described hyperastable Y-type RE molecular sieve is obtained by the method that may further comprise the steps: with ultrastable Y and equivalent concentration is that the acid solution of 0.01N-2N mixes under 20 ℃-100 ℃ temperature range with the ratio of solvent and solute weight ratio 4-20, stir 10 minutes-300 minutes after scouring, filtration, add rare earths salt again and carry out rare earth ion exchanged, exchange after scouring, filtration.
Catalyzer of the present invention is used for heavy oil fluid catalytic cracking, lightweight oil productive rate height, and coke yield is low, and heavy oil cracking ability is strong.For example DASY2.0 introduces rare earth through method of the present invention, making hyperastable Y-type RE molecular sieve content is 38 weight %, clay content is 37 weight %, the alumina bound agent content is 20 weight %, the alumina content that contains additive is the catalyzer of 5 weight %, estimates with heavy oil on fixed fluidized bed evaluating apparatus, and coke yield is 5.86 weight %, yield of light oil is 73.44 weight %, and the heavy oil productive rate is 7.48 weight %; And DASY2.0 introduces rare earth through existing method, making hyperastable Y-type RE molecular sieve content is 38 weight %, clay content is 37 weight %, the alumina bound agent content is the catalyzer of 25 weight %, estimate under the same conditions, coke yield is 6.55 weight %, and yield of light oil is 70.34 weight %, and the heavy oil productive rate is 8.77 weight %.As seen, catalyzer of the present invention has higher yield of light oil, lower coke selectivity and the heavy oil conversion performance of Geng Gao.
Description of drawings
Fig. 1 does not contain one of rare earth to hand over the X-ray diffraction spectrogram of a roasting ultrastable Y sample with the inventive method modification front and back.
Embodiment
Of the present invention ultrastable Y is mixed with acid solution, mixing temperature is preferably 25 ℃-95 ℃, and the concentration of acid solution is preferably 0.05N-0.5N, and mixed churning time was preferably 20 minutes-60 minutes.
Raw material ultrastable Y of the present invention can be commercially available commodity, for example: DASY-0.0, DASY-2.0 (production of catalyzer Shandong branch office of China Petrochemical Industry), it also can be ultrastable Y through any method preparation, comprise ultrastable Y, preferably hand over the ultrastable Ys of two roastings or hand over the ultrastable Y of a roasting through one of the method preparation of hydrothermal dealumination through two of the method preparation of hydrothermal dealumination through the preparation of the method for hydrothermal dealumination.
Acid of the present invention is selected from one or more the mixture in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, citric acid, oxalic acid, acetic acid, the formic acid.The mixture of one or more in preferred hydrochloric acid, oxalic acid, the formic acid.
Rare-earth salts of the present invention is preferably rare earth chloride or rare earth nitrate compound.
The rare earth ion exchanged of zeolite molecular sieve of the present invention adopts conventional RE ion exchange method.
Described rare earth superstable Y-type molecular sieve content of rare earth is preferably 7 weight %～15 weight %, 7 weight %～12 weight % more preferably, and lattice constant is preferably 2.445nm～2.465nm.
Behind the overstable gamma zeolite exchanged rare earth of the present invention, wash, filter, the hyperastable Y-type RE molecular sieve that obtains after the filtration can be directly used in the preparation catalyzer, or after the drying, is used further to prepare catalyzer.Described washing, filtration, drying do not have particular requirement for existing method, and for example the exsiccant temperature is 100 ℃-300 ℃, uses deionized water wash.
In the catalyzer of the present invention, be benchmark, preferably contain the rare earth superstable Y-type molecular sieve of 10 weight %～50 weight %, the matrix of 50 weight %-90 weight % with the weight of catalyzer.
In the catalyzer of the present invention, containing the aluminum oxide of additive, is benchmark with the weight of catalyzer, and the described content that contains the aluminum oxide of additive is 2 weight %-40 weight %, is preferably 2 weight %-20 weight %.The described aluminum oxide that contains additive can be according to patent CN1915486A, CN1915485A, the described method preparation of CN1916116A.The aluminum oxide that contains 70 weight %-95 weight % in the preferred described aluminum oxide that contains additive, the additive of 5 weight %-30 weight %.Wherein said additive is preferably the compound of phosphorous and/or magnesium.
In the catalyst substrates of the present invention, preferably also containing alumina binder, is benchmark with the weight of catalyzer, and in aluminum oxide, the content of described alumina binder is no more than 32 weight %, is preferably 5 weight～32 weight %.Described alumina binder is selected from usually one or more in aluminum oxide, hydrated aluminum oxide and the aluminium colloidal sol of employed various forms of cracking catalyst, for example, be selected from gama-alumina, η-aluminum oxide, θ-aluminum oxide, x-aluminum oxide, pseudo-boehmite (Pseudoboemite), a diaspore (Boehmite), gibbsite (Gibbsite) or the bayerite (Bayerite) one or more, be preferably pseudo-boehmite and/or aluminium colloidal sol.
In the catalyzer of the present invention, preferred alumina binder is that 10 weight %-40 weight % and the content that contains the aluminum oxide of additive are 2 weight %-20 weight % with the total content that contains the aluminum oxide of additive.
Also can contain clay in the catalyst substrates of the present invention, be benchmark with the weight of catalyzer, and the content of described clay is no more than 70 weight %, is preferably 10 weight %-70 weight %.Described clay is selected from as in the clay of cracking catalyst component one or more, for example one or more in kaolin, halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the wilkinite.These clays are that those of ordinary skills are known.
Also can contain other molecular sieve in the catalyzer of the present invention, the molecular sieve of using always in described other molecular screening catalytic cracking catalyzer, for example have one or more of MFI structural zeolite, Beta zeolite, y-type zeolite, non-zeolite molecular sieve, preferably, weight with catalyzer is benchmark, and the content of other molecular sieve is no more than 20 weight %.
Method for preparing catalyst of the present invention is existing method, comprise rare-earth Y molecular sieve and matrix are mixed making beating, spraying drying and washing, filtration, exsiccant step, these preparation methods have detailed description in patent CN1916116A, CN1362472A, CN1727442A, CN1132898C, CN1727445A, CN1098130A, quote as a reference in the lump here.
Catalyzer of the present invention is applicable to hydrocarbon oil catalytic cracking, is particularly suited for heavy oil fluid catalytic cracking.Described hydrocarbon ils for example long residuum, vacuum residuum, vacuum gas oil, atmospheric gas oil, straight run gas oil, propane light/in heavy deasphalted oil and the coker gas oil one or more.
The following examples will be further specified the present invention, but not thereby limiting the invention.
Among the embodiment and in the Comparative Examples: hydro-thermal overstable gamma zeolite DASY0.0, DASY2.0, DY-0, provide by catalyzer Shandong branch office of China Petrochemical Industry, character sees Table 1, REY, ZRP-5, aluminium colloidal sol are provided by catalyzer Shandong branch office of China Petrochemical Industry, kaolin is Chinese Suzhou kaolin, and pseudo-boehmite is provided by Shandong Aluminum Plant.
In each Comparative Examples and embodiment, the lattice constant of zeolite, relative crystallinity are measured [referring to RIPP145-90, RIPP146-90 analytical procedure by x-ray powder diffraction (XRD), " petrochemical complex analytical procedure " (RIPP test method), Yang Cui waits volume surely, Science Press, nineteen ninety publishes]; Constituent content is by x-ray fluorescence spectrometry; Crystalline structure avalanche temperature is measured by differential thermal analysis (DTA).
Used chemical reagent does not indicate especially among Comparative Examples and the embodiment, is chemical pure.
Embodiment 1
1500 gram DASY2.0 (butt) are mixed with 15 liters of 0.2N oxalic acid aqueous solutions, stir it is mixed, be warming up to 95 ℃, keep 1 hour after-filtration, wash with water, the taking-up filter cake places 15 liters of decationized Y sieve water, adding 480ml RECl
3Solution (RE in the solution
2O
3Content is 319g/L), stir, be warming up to 92 ℃ and kept 1 hour, filter then, wash, filter cake promptly gets the extremely steady y-type zeolite of rare earth sample in 120 ℃ of dryings, is designated as A1, and its physical data sees Table 2.
Getting 524 gram alumina contents is that the pseudo-boehmite of 61 weight % joins in the 2606 gram decationized Y sieve water, under whipped state, add the chemical pure hydrochloric acid of 65ml (containing 31 weight %HCl), wore out 1 hour in 70 ℃, (Beijing Chemical Plant produces to add 55ml phosphoric acid afterwards, concentration 85%, analytical pure) and magnesium chloride hexahydrate (dicyclo chemical reagent work in Beijing produces, the analytical pure) aqueous solution 130 grams (wherein magnesium chloride hexahydrate 68 grams), making beating obtains containing the slurries of the aluminum oxide of additive.
Getting 1666 gram alumina contents is that under agitation adding 1951 gram solid contents then is the kaolin of 76 weight %, pulls an oar 60 minutes, obtains kaolin slurry in the aluminium colloidal sol adding 3650 gram decationized Y sieve water of 21 weight %.With 787 gram alumina contents is that the pseudo-boehmite of 61 weight % joins in the 3127 gram decationized Y sieve water, making beating, then under agitation to wherein adding 77ml chemical pure hydrochloric acid (containing 31 weight %HCl), the aging prepared kaolin slurry of adding after 60 minutes, the slurries that add the prepared aluminum oxide that contains additive again, making beating, add A1 molecular sieve 1200 grams (butt) and REY molecular sieve 200 grams (butt) then, making beating, again 650 ℃ of temperature ins, carry out spraying drying under 180 ℃ of the exhaust temperatures, use deionized water wash, oven dry obtains catalyzer, is designated as C1.
Embodiment 2
Get 1500 gram DASY2.0 (butt), join in 15 liters of 0.1N oxalic acid aqueous solutions to stir it is mixed, be warming up to 95 ℃, keeps filtering, washing with water after 1 hour, the taking-up filter cake places 15 liters of decationized Y sieve water and adds the RE (NO of 480ml
3)
3Solution (strength of solution: with RE
2O
3Count 319g/L), stir, be warming up to 92 ℃ and kept 1 hour, filter then, washing, filter cake be in 120 ℃ of dryings, promptly gets the extremely steady y-type zeolite of rare earth sample, is designated as A2, its physical data sees Table 2.
With 328 gram alumina contents is that the pseudo-boehmite of 61 weight % joins in the 1632 gram decationized Y sieve water, under agitation add the chemical pure hydrochloric acid of 41ml (containing 31 weight %HCl), wore out 1 hour in 70 ℃ then, (dicyclo chemical reagent work in Beijing produces to add magnesium chloride hexahydrate afterwards, analytical pure) aqueous solution 240 grams (wherein magnesium chloride hexahydrate 137 grams), making beating obtains containing the slurries of the aluminum oxide of additive.
The aluminium colloidal sol of getting 952 gram alumina contents and be 21 weight % adds in the 834 gram decationized Y sieve water, stirs that to add 1947 gram solid contents down be the kaolin of 76 weight %, pulls an oar 60 minutes, obtains kaolin slurry.With 983 gram alumina contents is that the pseudo-boehmite of 61 weight % joins in the 4897 gram decationized Y sieve water, under whipped state, add 107ml hydrochloric acid (chemical pure, concentration 31 weight %), the aging prepared kaolin slurry of adding after 60 minutes, making beating, the slurries that add the prepared aluminum oxide that contains additive again, making beating adds A2 molecular sieve 1520 grams (butt), making beating then, carry out spraying drying and carrying out washing treatment (with example 1) again, oven dry obtains catalyzer C2.
Embodiment 3
Get 1000 gram DASY2.0 (butt), join in 10 liters of 0.2N aqueous citric acid solutions, stir it is mixed, be warming up to 95 ℃ and keep filtering, wash with water, take out filter cake after 1 hour, place 10 liters of decationized Y sieve water and add the RECl of 320ml
3Solution (strength of solution: with RE
2O
3Count 319g/L), stir, be warming up to 93 ℃ and kept 1 hour, filter then, washing, filter cake be in 120 ℃ of dryings, promptly gets the extremely steady y-type zeolite of rare earth sample, is designated as A3, its physical data sees Table 2.
Getting 328 gram alumina contents is that the pseudo-boehmite of 61 weight % joins in the 1632 gram decationized Y sieve water, under agitation add the chemical pure hydrochloric acid of 41ml (HCl content is 31 weight %), wore out 1 hour at 70 ℃, (Beijing Chemical Plant produces to add 98ml phosphoric acid afterwards, concentration 85%, analytical pure), making beating obtains containing the slurries of the aluminum oxide of additive.
The aluminium colloidal sol of getting 952 gram alumina contents and be 21 weight % adds in the 1522 gram decationized Y sieve water, stirs that to add 1947 gram solid contents down be the kaolin of 76 weight %, pulls an oar 60 minutes, obtains kaolin slurry.Getting 1311 gram alumina contents is in the pseudo-boehmite adding 4243 gram decationized Y sieve water of 61 weight %, under whipped state, add the chemical pure hydrochloric acid of 142ml (concentration 31 weight %), the aging prepared kaolin slurry of adding after 60 minutes, making beating, the slurries that add the prepared aluminum oxide that contains additive again, making beating, add A3 molecular sieve 1000 grams (butt), REY molecular sieve 320 grams (butt) and ZRP-5 molecular sieve 200 grams (butt) then, making beating, carry out spraying drying and carrying out washing treatment (with example 1), oven dry obtains catalyzer, is designated as C3.
Embodiment 4
Get 1500 gram DASY0.0 samples (butt), join in 15 liters of 0.2N aqueous nitric acid to stir it is mixed, be warming up to 95 ℃ and keep filtering, wash with water, take out filter cake after 1 hour, place 15 liters of decationized Y sieve water and add the RECl of 480ml
3Solution (strength of solution: with RE
2O
3Count 319g/L), stir, be warming up to 90 ℃ and kept 1 hour, filter then, washing, filter cake be in 120 ℃ of dryings, promptly gets the extremely steady y-type zeolite of rare earth sample, is designated as A4, its physical data sees Table 2.
Getting 524 gram alumina contents is that the pseudo-boehmite of 61 weight % joins in the 2606 gram decationized Y sieve water, under agitation add the chemical pure hydrochloric acid of 65ml (containing 31 weight %HCl), wore out 1 hour in 70 ℃, (Beijing Chemical Plant produces to add 55ml phosphoric acid afterwards, concentration 85 weight %, analytical pure) and magnesium chloride hexahydrate (dicyclo chemical reagent work in Beijing produces, the analytical pure) aqueous solution 130 grams (wherein containing magnesium chloride hexahydrate 68 grams), making beating obtains containing the slurries of the aluminum oxide of additive.
Getting 1666 gram alumina contents is that the aluminium colloidal sol of 21 weight % joins in the 3650 gram decationized Y sieve water, making beating, and adding 1951 gram solid contents then is the kaolin of 76 weight %, pulls an oar 60 minutes, obtains kaolin slurry.Getting 787 gram alumina contents is in the pseudo-boehmite adding 3127 gram decationized Y sieve water of 61 weight %, under whipped state, add the chemical pure hydrochloric acid of 77ml (concentration is 31 weight %), the aging prepared kaolin slurry of adding after 60 minutes, the slurries that add the prepared aluminum oxide that contains additive afterwards again add A4 molecular sieve 1400 grams (butt), making beating then, carry out spraying drying and carrying out washing treatment (with example 1), oven dry obtains catalyzer, is designated as C4.
Embodiment 5
Get 2000 gram Y zeolite one and hand over a roasting sample DY-0 (butt), joining to stir in 20 liters of 0.15N aqueous hydrochloric acids mixes it, be warming up to 95 ℃ and keep filtering, wash with water, to take out filter cake after 1 hour, place 20 liters of decationized Y sieve water and add the RE (NO of 800ml
3)
3(strength of solution is with RE for solution
2O
3Count 255g/L), stir, be warming up to 90 ℃ and kept 1 hour, filter then, washing, filter cake be in 120 ℃ of dryings, promptly gets the extremely steady y-type zeolite of rare earth sample, is designated as A5, its physical data sees Table 2.
Getting 655 gram alumina contents is that the pseudo-boehmite of 61 weight % joins in the 3257 gram decationized Y sieve water, under agitation add the chemical pure hydrochloric acid of 81ml (HCl content is 31 weight %), wore out 1 hour in 70 ℃, (Beijing Chemical Plant produces to add 68ml phosphoric acid afterwards, concentration 85%, analytical pure) and magnesium chloride hexahydrate (dicyclo chemical reagent work in Beijing produces, the analytical pure) aqueous solution 150 grams (wherein magnesium chloride hexahydrate 85 grams), making beating obtains containing the slurries of the aluminum oxide of additive.
Getting 1332 gram alumina contents is in the aluminium colloidal sol adding 5060 gram decationized Y sieve water of 21 weight %, making beating, and adding 1579 gram solid contents are that the kaolin of 76 weight % was pulled an oar 60 minutes, obtain kaolin slurry.Getting 984 gram alumina contents is in the pseudo-boehmite adding 3222 gram decationized Y sieve water of 61 weight %, under agitation add the chemical pure hydrochloric acid of 71ml (concentration 31 weight %), the aging prepared kaolin slurry of adding after 60 minutes, making beating, the slurries that add the prepared aluminum oxide that contains additive again, making beating adds A5 molecular sieve 1520 grams (butt), making beating then, carry out spraying drying and carrying out washing treatment (with example 1), oven dry obtains catalyzer, is designated as C5.
Fig. 1 does not contain one of rare earth to hand over the X-ray diffraction spectrogram of a roasting ultrastable Y sample DY-0 with the inventive method modification front and back.Curve a is DY-0 shown (a 311) crystal face diffraction peak; Curve b adopts the inventive method to carry out (311) crystal face and (222) the crystal face diffraction peak that shows after the rare earth ion exchanged.(311) crystal face that does not contain the USY zeolite of rare earth can show very strong diffraction peak, as zeolite process RE
3+Exchange back (exchange degree is more than 60%) and without roasting, RE
3+When being in easily by anticommutative position (in the supercage), the diffraction peak of (311) crystal face is understood completely dissolve, demonstrates the diffraction peak of (222) crystal face, after the rare earth exchanged and through roasting, part RE
3+When moving in the little cage, the diffraction peak of (311) crystal face reappears.Therefore, zeolite is through RE
3+After the exchange, I (311)/I (222) value can be used to represent RE
3+Little cage and in supercage what of relative quantity.
By curve b as seen, after the inventive method modification, most RE
3+Enter into little cage, small portion is stayed in the supercage.The present invention is in the process of zeolite modification, and zeolite sample can prove the RE in the exchange through fully flushing
3+All enter into the intracrystalline cage of zeolite.
Comparative Examples 1
Get 2000 gram DASY2.0 samples (butt) and join in 20 liters of decationized Y sieve water, and in solution, add the RECl of 640ml
3Solution (strength of solution: with RE
2O
3Count 319g/L), stir, be warming up to 92 ℃ and kept 1 hour, filter then, wash with water, filter cake is in 120 ℃ of dryings, promptly gets and contrasts the extremely steady y-type zeolite of rare earth sample, is designated as B1, its physical data sees Table 2.
The aluminium colloidal sol of getting 952 gram alumina contents and be 21 weight % adds in the 834 gram decationized Y sieve water, opens and stirs, and adds 1947 gram solid contents and be the kaolin making beating 60 minutes of 76 weight %, obtains kaolin slurry.Getting 1311 gram alumina contents is in the pseudo-boehmite adding 6529 gram decationized Y sieve water of 61 weight %, under agitation add the chemical pure hydrochloric acid of 142ml (concentration 31 weight %), the aging prepared kaolin slurry of adding after 60 minutes, add B1 molecular sieve 1520 grams (butt) then, making beating, carry out spraying drying and carrying out washing treatment (with example 1), oven dry obtains catalyzer CC1.
Embodiment 6-10
C1～C5 catalyzer is estimated with fixed fluidized bed evaluating apparatus, estimated and to see Table 3 with stock oil character, 500 ℃ of temperature of reaction, the agent weight of oil is than 5.92, all wears out 8 hours under 800 ℃, 100% water vapour atmosphere before the evaluating catalyst, and evaluation result sees Table 4.
Comparative Examples 2
Method according to embodiment 6-10 is estimated the CC1 catalyzer, the results are shown in Table 4.
By table 4 as seen, compare with existing catalyzer, the heavy oil conversion performance of catalyzer of the present invention improves, and yield of light oil increases, and coke yield reduces.
Table 1
Table 2
Table 3
| Density (20 ℃), gram per centimeter 3 | 0.923 |
| Viscosity, millimeter 2/ second | 17.06(80℃) |
| 100℃ | 9.776 |
| Zero pour, ℃ | 28 |
| Carbon residue, weight % | 2.01 |
| Elementary composition, weight % | ? |
| C | 86.97 |
| H | 12.34 |
| S | 0.77 |
| N | 0.3 |
| Boiling range, ℃ | ? |
| Initial boiling point | 235 |
| 5％ | 330 |
| 10％ | 351 |
| 30％ | 389 |
| 50％ | 435 |
| 70％ | 478 |
| 90％ | ? |
Table 4
Claims (10)
1. a cracking catalyst contains rare earth superstable Y-type molecular sieve and matrix, and described matrix contains a kind of aluminum oxide that contains additive; The aluminum oxide that contains 60 weight %-99.5 weight % in the described aluminum oxide that contains additive, 0.5 the additive of weight %-40 weight %, described additive is selected from one or more in the compound that contains alkaline-earth metal, lanthanide series metal, silicon, gallium, boron or phosphoric; Described hyperastable Y-type RE molecular sieve is obtained by the method that may further comprise the steps: with ultrastable Y and equivalent concentration is that the acid solution of 0.01N-2N mixes under 20 ℃-100 ℃ temperature range with the ratio of solvent and solute weight ratio 4-20, stir 10 minutes-300 minutes after scouring, filtration, add rare earths salt again and carry out rare earth ion exchanged, exchange after scouring, filtration, described rare earth superstable Y-type molecular sieve middle-weight rare earths content is 7 weight %～15 weight %.
2. according to the described catalyzer of claim 1, it is characterized in that described acid is one or more the mixture in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, citric acid, oxalic acid, acetic acid, the formic acid.
3. according to the described catalyzer of claim 2, it is characterized in that described acid is one or more the mixture in hydrochloric acid, oxalic acid, the formic acid.
4. according to the described catalyzer of claim 1, it is characterized in that the equivalent concentration of described acid solution is 0.05N-0.5N, described temperature is 25 ℃-95 ℃, and churning time is 20 minutes-60 minutes.
5. according to the described catalyzer of claim 1, it is characterized in that described ultrastable Y is the ultrastable Y through the method preparation of hydrothermal dealumination.
6. according to the described catalyzer of claim 5, it is characterized in that described ultrastable Y is handed over the ultrastable Y or of two roastings for two of hydrothermal dealumination method preparation and handed over the ultrastable Y of a roasting.
7. according to the described catalyzer of claim 1, it is characterized in that described rare-earth salts is rare earth chloride or rare earth nitrate.
8. catalyzer according to claim 1 is characterized in that, described rare earth superstable Y-type molecular sieve content of rare earth is 7 weight %～12 weight %, and lattice constant is 2.445nm～2.465nm.
9. catalyzer according to claim 1, it is characterized in that described catalyzer contains in the aluminum oxide that contains additive of the rare earth superstable Y-type molecular sieve of butt 10 weight %～50 weight %, 2 weight %-40 weight %, in the clay of butt 10 weight %～70 weight %.
10. catalyzer according to claim 9 is characterized in that, described catalyzer contains the alumina binder of 5 weight %-32 weight %.
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| CN103157507B (en) | 2011-12-15 | 2015-05-13 | 中国石油天然气股份有限公司 | Heavy oil catalytic cracking catalyst and preparation method thereof |
| CN103159227B (en) | 2011-12-15 | 2015-05-13 | 中国石油天然气股份有限公司 | Magnesium modified ultrastable rare earth Y-type molecular sieve and preparation method thereof |
| CN103159228B (en) * | 2011-12-15 | 2016-07-13 | 中国石油天然气股份有限公司 | A kind of Ultra-stable rare earth Y-type molecular sieve and preparation method thereof |
| CN103447063B (en) | 2012-06-01 | 2016-02-10 | 中国石油天然气股份有限公司 | Heavy oil Efficient Conversion catalytic cracking catalyst and preparation method thereof |
| CN103449471B (en) | 2012-06-01 | 2017-07-14 | 中国石油天然气股份有限公司 | A kind of phosphorous Ultra-stable rare earth Y-type molecular sieve and preparation method |
| JP6232058B2 (en) | 2012-06-27 | 2017-11-15 | 中国石油化工股▲ふん▼有限公司 | Catalytic cracking catalyst containing modified Y-type zeolite and process for its preparation |
| TWI568495B (en) * | 2012-09-14 | 2017-02-01 | China Petrochemical Technology Co Ltd | Catalytic cracking catalyst with rare earth Y type molecular sieve and preparation method thereof |
| RU2770421C2 (en) * | 2017-02-21 | 2022-04-18 | Чайна Петролеум Энд Кемикал Корпорейшен | Magnesium-modified y-type molecular sieve, production thereof and catalyst containing same |
| CN108452835B (en) * | 2017-02-22 | 2020-03-24 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
| US11052381B2 (en) | 2017-02-21 | 2021-07-06 | China Petroleum & Chemical Corporation | Modified Y-type molecular sieve, preparation thereof and catalyst comprising the same |
| CN108452834B (en) * | 2017-02-22 | 2020-03-24 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
| RU2755891C2 (en) | 2017-02-22 | 2021-09-22 | Чайна Петролеум Энд Кемикал Корпорейшен | Catalytic cracking catalyst and its preparation |
| CN108452833B (en) * | 2017-02-22 | 2020-03-24 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
| CN108452836B (en) * | 2017-02-22 | 2020-05-19 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
| CN110833852B (en) * | 2018-08-17 | 2021-04-06 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation method and application thereof |
| CN112108173B (en) * | 2019-06-21 | 2023-06-30 | 中国石油天然气股份有限公司 | Catalyst preparation method for reducing diesel oil yield |
| CN112206809A (en) * | 2019-07-09 | 2021-01-12 | 中国石油化工股份有限公司 | Rare earth-containing Y-type molecular sieve and preparation method thereof |
| CN112808296B (en) * | 2019-11-18 | 2023-04-07 | 中国石油化工股份有限公司 | Catalyst containing Y-type molecular sieve and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030064881A1 (en) * | 2001-04-28 | 2003-04-03 | Jun Du | Rare earth zeolite Y and the preparation process thereof |
| CN1660495A (en) * | 2004-02-27 | 2005-08-31 | 中国石油化工股份有限公司 | Hydrocracking catalyst for hydrocarbon |
| CN1814705A (en) * | 2005-01-31 | 2006-08-09 | 中国石油化工股份有限公司 | Heavy-oil catalytic-cracking catalyst and preparing method |
-
2007
- 2007-04-12 CN CN2007100653652A patent/CN101285001B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030064881A1 (en) * | 2001-04-28 | 2003-04-03 | Jun Du | Rare earth zeolite Y and the preparation process thereof |
| CN1660495A (en) * | 2004-02-27 | 2005-08-31 | 中国石油化工股份有限公司 | Hydrocracking catalyst for hydrocarbon |
| CN1814705A (en) * | 2005-01-31 | 2006-08-09 | 中国石油化工股份有限公司 | Heavy-oil catalytic-cracking catalyst and preparing method |
Non-Patent Citations (1)
| Title |
|---|
| 孙书红等.稀土超稳Y型分子筛催化裂化催化剂的研究.《石油炼制与化工》.2001,第32卷(第6期),25-28. * |
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