CN100537029C - Catalytic cracking catalyst - Google Patents
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- CN100537029C CN100537029C CNB2006101132357A CN200610113235A CN100537029C CN 100537029 C CN100537029 C CN 100537029C CN B2006101132357 A CNB2006101132357 A CN B2006101132357A CN 200610113235 A CN200610113235 A CN 200610113235A CN 100537029 C CN100537029 C CN 100537029C
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Abstract
The present invention relates to a cracking catalyst. Its composition contains (by wt%) 10%-50% of high rare earth ultrastable Y-type molecular sieve, 10%-40% of aluminium oxide adhesive and 10%-70% of clay. The preparation method of described high rare earth ultrastable Y-type molecular sieve includes the following steps: fully mixing ultrastable Y-type zeolite and acid solution whose equivalent concentration is 0.01N-2N according to the solid-liquid ratio of 20:4 at temperature range of 20deg.C-100deg.C, stirring them for 10min-300min, then washing, filtering, adding rare earth salt solution to make rare earth ion exchange, after the exchange washing, filtering and drying so as to obtain the high rare earth ultrastable Y-type molecutar sieve.
Description
Technical field
The present invention relates to a kind of hydrocarbon oil catalytic cracking catalyst.
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 transformation and preventing from heavy metal pollution ability, but low-carbon olefines high-output and low sulfur content high-knock rating gasoline again simultaneously.The key that obtains high yield, high-knock rating gasoline is that the catalyst activity component is that rare-earth type high-silicon gamma-zeolite can keep crystal structure intact, has very high heat and hydrothermal stability, highly acid and low sour density.In order to obtain to have the rare earth high-silica zeolite of described performance, normally the NaY zeolite that will manually synthesize 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 zeolitic frameworks, thereby reduce sour density, improve heat endurance and hydrothermal stability, improve gasoline selective.
The preparation method of overstable gamma zeolite mainly contains gas chemistry method, liquid phase villiaumite method, hydro-thermal 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.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 heat endurance 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
4The Y zeolite carries out the ammonium fluosilicate dealumination complement silicon, can significantly improve Si/Al heat endurance 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 fluosilicate, influence the hydrothermal stability of zeolite, also have the serious environmental pollution problem on the other hand, make it can not extensive use.
Hydro-thermal method is the present industrial method that ultrastable generally adopts for preparing, and still, hydro-thermal 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 component in current catalytic cracking and the hydrocracking reaction catalyst, 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, making the catalyst that contains the rare earth zeolite have higher heat and hydrothermal stability 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 Y-type high-Si zeolite with RE
2O
3The content of rare earth of meter can reach 2～3 weight %, but this does not still satisfy the requirement of deep processing to catalyst.The duct obstruction that aluminium chips causes is the main 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 action of rare earth ion and support make the aluminium of steam treatment process mesolite remove the comparison difficulty, the cell parameter of zeolite before steam treatment increases to 2.465～2.475nm, and be 2.420～2.464nm after handling, reduce cell parameter 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 that hydro-thermal and chemical combination technology prepare overstable gamma zeolite, this method be with NaY through exchange for several times, roasting under the superheated vapor condition is then handled with inorganic acid or network and 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 salts to do dealumination agent.In the chemical dealuminization process, carry out the ion-exchange of ammonium and sodium simultaneously.Prepared high-silicon Y-Zeolite has framework aluminum and is evenly distributed, characteristics such as secondary pore prosperity.Described zeolite has very high heat endurance and hydrothermal stability.But this patent does not relate to further rare earth ion exchanged, and provides a kind of Cracking catalyst that contains prepared ultrastable.
CN1436728A provides a kind of novel rare-earth ultrastable preparation method RFCC, that contain anti-vanadium component that is used for, this method is to be raw material with the NaY zeolite, contain oxalic acid or oxalates 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 zeolitic frameworks in the deposition of zeolite surface.
CN1296860A discloses the Preparation of catalysts that contains small crystal grain Y-shaped molecular sieve, comprises that with crystal grain be little crystal grain USY, REY, REHY, the HY molecular sieve that the NaY molecular sieve of 200nm～800nm obtains 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, spray-drying, washing, drying obtain catalyst again.The liquefied gas yield of this catalyst, gasoline yield, heavy oil transformation rate are improved.This patent does not relate to the content of rare earth problem that how to improve in the super stable molecular sieve.
CN1143666A discloses the catalyst of a kind of voluminous isoparaffin and gasoline, and this catalyst 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 weight %, through chemistry or physical method stabilisation and obtain, and the Y-type high-Si zeolite that comprises the ultrastable that obtains with hydro-thermal method, obtains with liquid phase method or vapor phase method aluminium-eliminating and silicon-replenishing.
USP5258341 and USP5908547 disclose a kind of Y zeolite Cracking catalyst that contains yttrium, and this catalyst is to be active component by the super-stable Y molecular sieves that contains yttrium, can reduce dry gas, increase gasoline yield.
Because the ultra-steady Y molecular sieve intracrystalline content of rare earth in the catalytic cracking catalyst is low at present, its heavy oil transformation rate and yield of gasoline are lower.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of gasoline yield height, catalytic cracking catalyst that heavy oil conversion performance is strong, and this catalyst contains the ultrastable of high rare-earth content.
The invention provides a kind of catalytic cracking catalyst, contain high rare earth superstable Y-type molecular sieve, in the alumina binder of aluminium oxide 10 weight～40 weight % with in the clay of butt 10 weight～70 weight % in butt 10 weight %～50 weight %; Described high rare earth superstable Y-type molecular sieve is obtained by the step that comprises following method: with raw material ultrastable and equivalent concentration is ratio under 20 ℃～100 ℃ temperature range the fully mixing of the acid solution of 0.01N～2N with solvent and solute weight ratio 4～20, stir washing after 10 minutes～300 minutes, filter, add rare earths salt again and carry out rare earth ion exchanged, exchange back washing, filtration, drying.
Catalyst of the present invention is used for RFCC, has higher gasoline yield, strong heavy oil cracking ability.After for example DASY2.0 is treated as high hyperastable Y-type RE through method of the present invention, making high hyperastable Y-type RE molecular sieve content is 38.0 weight %, clay content is 37 weight %, the alumina bound agent content is the catalyst of 25 weight %, on fixed fluidized bed evaluating apparatus, estimate with heavy oil, the heavy oil transformation rate is 76.49 weight %, yield of gasoline is 53.82 weight %, and DASY2.0 is through the identical catalyst of constituent content of existing method Processing of Preparation, estimate under the same conditions, the heavy oil transformation rate is 72.67 weight %, and yield of gasoline is 51.17 weight %.As seen, catalyst of the present invention has higher heavy oil conversion performance and yield of gasoline.
Description of drawings
Accompanying drawing 1 is not contain one of rare earth to hand over the X-ray diffraction spectrogram of a roasting ultrastable sample with the inventive method modification front and back.
The specific embodiment
Of the present invention ultrastable 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 mixing time is preferably 20 minutes～and 60 minutes.
Raw material ultrastable of the present invention can be commercially available commodity, for example: DASY-0.0, DASY-2.0 (production of catalyst Shandong branch company of China Petrochemical Industry), it also can be ultrastable through any method preparation, comprise ultrastable, preferably hand over the ultrastables of two roastings or hand over the ultrastable 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 nitric acid rare earth compound.
The rare earth ion exchanged of zeolite of the present invention adopts conventional RE ion exchange method.
Described high rare earth superstable Y-type molecular sieve content of rare earth is preferably 7 weight～15 weight % weight, and lattice constant is preferably 2.445nm～2.465nm.
Fig. 1 does not contain one of rare earth to hand over the X-ray diffraction spectrogram of a roasting ultrastable sample DY-0 with the inventive method modification front and back.Curve a is DY-0 shown (a 311) crystal face diffraction maximum; Curve b adopts the inventive method to carry out (311) crystal face and (222) the crystal face diffraction maximum 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 maximum, 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 maximum of (311) crystal face is understood complete obiteration, demonstrates the diffraction maximum of (222) crystal face, after the rare earth exchanged and through roasting, part RE
3+When moving in the little cage, the diffraction maximum 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, fraction is stayed in the supercage.In the modifying process of the present invention, zeolite sample is fully washed, and can prove the RE in the exchange
3+All enter into the intracrystalline cage of zeolite.
The present invention also can contain other molecular sieve, and commonly used molecular sieve in described other molecular screening catalytic cracking catalyst for example has one or more of MFI structural zeolite, Beta zeolite, y-type zeolite, non-zeolite molecular sieve.
Described clay is selected from as in the clay of Cracking catalyst component one or more, for example one or more in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the bentonite.These clays are that those of ordinary skills are known.
Alumina binder of the present invention is selected from usually one or more in aluminium oxide, hydrated alumina and the aluminium colloidal sol of employed various forms of Cracking catalyst.For example, be selected from gama-alumina, η-aluminium oxide, θ-aluminium oxide, χ-aluminium oxide, boehmite (Pseudoboemite), a diaspore (Boehmite), gibbsite (Gibbsite) or the bayerite (Bayerite) one or more, preferred boehmite and aluminium colloidal sol.
Method for preparing catalyst of the present invention is existing method, comprise clay, molecular sieve, alumina binder are mixed making beating, the step of spray-drying and washing, filtration, drying, these methods all have detailed description in patent CN1098130A, CN1362472A, CN1727442A, CN1132898C, CN1727445A, quote as a reference in the lump here.
Spray-drying, washing, drying are prior art, and the present invention does not have specific (special) requirements.
The following examples will be further specified the present invention, but not thereby limiting the invention.
In an embodiment with Comparative Examples in:
Hydro-thermal overstable gamma zeolite DASY0.0, DASY2.0, DY-0, provided by catalyst Shandong branch company of China Petrochemical Industry, character sees Table 1, and REY, ZRP-5, aluminium colloidal sol are provided by catalyst Shandong branch company of China Petrochemical Industry, kaolin is Chinese Suzhou kaolin, and boehmite is provided by Shandong Aluminum Plant.
In each Comparative Examples and embodiment, the lattice constant of zeolite, relative crystallinity adopt the RIPP145-90 standard method (to see volumes such as " petrochemical industry analytical method " (RIPP test method) Yang Cuiding by x-ray powder diffraction (XRD), Science Press, nineteen ninety publishes) measure; Constituent content is by x-ray fluorescence spectrometry.Crystal structure avalanche temperature is measured by differential thermal analysis (DTA).
Used chemical reagent does not indicate especially among Comparative Examples and the embodiment, and its specification is a chemical pure.
Embodiment 1
Get 1500 gram DASY2.0 (butt), join in 15 liters of 0.2N oxalic acid aqueous solutions to stir it is mixed, be warming up to 90～100 ℃ and keep filtering after 1 hour, washing, take out filter cake with water, place 15 liters of decationized Y sieve water, the RECl of adding 480ml
3Solution (RE in the solution
2O
3Content is 319g/L), stir, be warming up to 90～95 ℃ 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 A1, its physical data sees Table 2.
The aluminium colloidal sol of getting 952 gram alumina contents and be 21 weight % adds in the 2086 gram decationized Y sieve water, opens and stirs, and adds 2105 gram solid contents and be the kaolin making beating 60 minutes of 76 weight %.Getting 1311 gram alumina contents is in the boehmite adding 5212 gram decationized Y sieve water of 61 weight %, under stirring, add the chemical pure hydrochloric acid of 128ml (31 weight %HCl), acidifying adds the good kaolin slurry of making beating after 60 minutes, add levigate A1 molecular sieve 1200 grams (butt) and REY molecular sieve 200 grams (butt) then, after stirring, 650 ℃ of inlet temperatures, carry out spray-drying under 180 ℃ of the exhaust temperatures, wash with water, oven dry obtains catalyst, 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 90～100 ℃ and keep filtering, wash with water, take out filter cake after 1 hour, place 15 liters of decationized Y sieve water and add the RE (NO of 480ml
3)
3Solution (solution concentration: with RE
2O
3Count 319g/L), stir, be warming up to 90～95 ℃ 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.
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 %.Getting 1311 gram alumina contents is in the boehmite adding 6529 gram decationized Y sieve water of 61 weight %, under stirring, add the chemical pure hydrochloric acid of 142ml (concentration 31 weight %), acidifying adds the good kaolin slurry of making beating after 60 minutes, add levigate A2 molecular sieve 1520 grams (butt) then, after stirring, carry out spray-drying and carrying out washing treatment (with example 1), oven dry obtains catalyst C2.
Embodiment 3
Get 1000 gram DASY2.0 (butt), join in 10 liters of 0.2N aqueous citric acid solutions to stir it is mixed, be warming up to 90～100 ℃ 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 (solution concentration: with RE
2O
3Count 319g/L), stir, be warming up to 90～95 ℃ 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.
The aluminium colloidal sol of getting 952 gram alumina contents and be 21 weight % adds in the 1522 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 %.Getting 1311 gram alumina contents is in the boehmite adding 4243 gram decationized Y sieve water of 61 weight %, under stirring, add the chemical pure hydrochloric acid of 142ml (concentration 31 weight %), acidifying adds the good kaolin slurry of making beating after 60 minutes, add levigate A3 molecular sieve 1000 grams (butt), REY molecular sieve 320 grams (butt) and ZRP-5 molecular sieve 200 grams (butt) then, after stirring, carry out spray-drying and carrying out washing treatment (with example 1), oven dry is designated as C3.
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 (solution concentration: with RE
2O
3Count 319g/L), stir, be warming up to 90 ℃ 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.
Method according to embodiment 2 prepares catalyst, and A2 molecular sieve 1520 grams (butt) are replaced with B1 molecular sieve 1520 grams (butt), and oven dry is designated as CC1.
Embodiment 4
Get 1500 gram DASY0.0 samples (butt), join in 15 liters of 0.2N aqueous solution of nitric acid to stir it is mixed, be warming up to 90～100 ℃ 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 (solution concentration: 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.
The aluminium colloidal sol of getting 952 gram alumina contents and be 21 weight % adds in the 870 gram decationized Y sieve water, opens and stirs, and adds 2000 gram solid contents and be the kaolin making beating 60 minutes of 76 weight %.Getting 1311 gram alumina contents is in the boehmite adding 4243 gram decationized Y sieve water of 61 weight %, under stirring, add the chemical pure hydrochloric acid of 142ml (concentration 31 weight %), acidifying adds the good kaolin slurry of making beating after 60 minutes, add levigate A4 molecular sieve 1400 grams (butt) then, after stirring, carry out spray-drying and carrying out washing treatment (with example 1), oven dry is designated as C4.
Embodiment 5
Get one of 1500 gram Hydrothermal Preparation and hand over a roasting sample DY-0 (butt), joining to stir in 15 liters of 0.15N aqueous formic acids mixes it, be warming up to 90～100 ℃ and keep after 1 hour, filter, washing, take out filter cake, place 15 liters of decationized Y sieve water and add the RE (NO of 600ml
3)
3(solution concentration is with RE for solution
2O
3Count 255g/L), stir, be warming up to 90～95 ℃ 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.
Get 5154 and restrain the decationized Y sieve water, open and stir, adding 2526 gram solid contents are that the kaolin of 76 weight % was pulled an oar 60 minutes.Getting 1311 gram alumina contents is in the boehmite adding 2973 gram decationized Y sieve water of 61 weight %, under stirring, add the chemical pure hydrochloric acid of 142ml (concentration 31 weight %), acidifying adds the good kaolin slurry of making beating after 60 minutes, add levigate A5 molecular sieve 1280 grams (butt) then, after stirring, carry out spray-drying and carrying out washing treatment (with example 1), oven dry is designated as C5.
Embodiment 6
Get 2000 gram Y zeolites one and hand over a roasting sample DY-0 (butt), joining to stir in 20 liters of 0.15N aqueous hydrochloric acid solutions mixes it, be warming up to 90～100 ℃ 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(solution concentration 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 A6, its physical data sees Table 2.
The aluminium colloidal sol of getting 571 gram alumina contents and be 21 weight % adds in the 2170 gram decationized Y sieve water, opens and stirs, and adds 1526 gram solid contents and be the kaolin making beating 60 minutes of 76 weight %.Getting 1967 gram alumina contents is in the boehmite adding 6444 gram decationized Y sieve water of 61 weight %, under stirring, add the chemical pure hydrochloric acid of 142ml (concentration 31 weight %), acidifying adds the good kaolin slurry of making beating after 60 minutes, add levigate A6 molecular sieve 1520 grams (butt) then, after stirring, carry out spray-drying and carrying out washing treatment (with example 1), oven dry is designated as C6.
Embodiment 7
C1～C6 and CC1 catalyst are estimated with fixed fluidized bed evaluating apparatus, estimate and to see Table 3 with feedstock property, 500 ℃ of reaction temperatures, the agent weight of oil is than 5.92, and catalyst all hour wears out through 800 ℃/100% water vapour/8, and evaluation result sees Table 4.Heavy oil conversion performance by visible catalyst in the table 4 improves, and gasoline yield obviously increases.
Table 1
Table 2
Table 3
| Density (20 ℃), gram per centimeter 3 | 0.9044 |
| Viscosity, millimeter 2/ second | 1.5217(20℃) |
| 100℃ | 9.96 |
| Freezing point, ℃ | 40 |
| Carbon residue, weight % | 3.0 |
| Element is formed, weight % | |
| C | 85.98 |
| H | 12.86 |
| S | 0.55 |
| N | 0.18 |
| Boiling range, ℃ | |
| Initial boiling point | 243 |
| 5％ | 294 |
| 10％ | 316 |
| 30％ | 395 |
| 50％ | 429 |
| 70％ | 473 |
| 90％ |
Table 4
Claims (9)
1, a kind of Cracking catalyst contains high extremely steady y-type zeolite of rare earth in butt 10 weight %～50 weight %, in the alumina binder of aluminium oxide 10 weight～40 weight % with in the clay of butt 10 weight～70 weight %; The content of rare earth of described high extremely steady y-type zeolite of rare earth is 7～15 weight %, and obtained by the step that comprises following method: with ultrastable and equivalent concentration is ratio under 20 ℃～100 ℃ temperature range the fully mixing of the acid solution of 0.01N～2N with liquid-solid ratio 4～20, stir washing after 10 minutes～300 minutes, filter, add rare earths salt again and carry out rare earth ion exchanged, exchange back washing, filtration, drying.
According to the described catalyst of claim 1, it is characterized in that 2, described acid is one or more the mixture that is selected from sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, citric acid, oxalic acid, acetic acid, the formic acid.
According to the described catalyst of claim 2, it is characterized in that 3, described acid is one or more the mixture that is selected from hydrochloric acid, oxalic acid, the formic acid.
According to the described catalyst of claim 1, it is characterized in that 4, the equivalent concentration of described acid solution is 0.05N～0.5N, described temperature is 25 ℃～95 ℃, and mixing time is 20 minutes～60 minutes.
According to the described catalyst of claim 1, it is characterized in that 5, described ultrastable is the ultrastable through the method preparation of hydrothermal dealumination.
According to the described catalyst of claim 5, it is characterized in that 6, described ultrastable is handed over the ultrastable or of two roastings for two of hydrothermal dealumination method preparation and handed over the ultrastable of a roasting.
7,, it is characterized in that described rare-earth salts is rare earth chloride or nitric acid rare earth compound according to the described catalyst of claim 1.
8, according to the described catalyst of claim 1, it is characterized in that, described catalyst also contain be selected from have the MFI structural zeolite, one or more other molecular sieve in the Beta zeolite, y-type zeolite, non-zeolite molecular sieve, the content of other molecular sieve is no more than 20 weight %.
9, catalyst according to claim 1 is characterized in that, described high extremely steady y-type zeolite of rare earth content of rare earth is 7 weight～12 weight %, and lattice constant is 2.445nm～2.465nm.
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| RU2628071C2 (en) * | 2012-09-14 | 2017-08-14 | Чайна Петролеум Энд Кемикал Корпорейшн | Catalytic cracking catalyst containing ree-containing zeolite, and how to obtain it |
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| CN101386788B (en) * | 2007-09-12 | 2012-09-05 | 中国石油化工股份有限公司 | Catalyst for heavy oil catalytic cracking and preparation method thereof |
| CN101745418B (en) * | 2008-11-28 | 2012-10-10 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation and application 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 |
| 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 |
| CN103508467B (en) | 2012-06-27 | 2015-09-23 | 中国石油化工股份有限公司 | A kind of rare-earth Y molecular sieve and preparation method thereof |
| AU2013284234B2 (en) | 2012-06-27 | 2018-03-01 | China Petroleum & Chemical Corporation | Catalytic cracking catalyst containing modified Y type molecular sieve and preparation method therefor |
| CN103771447B (en) * | 2012-10-19 | 2015-09-23 | 中国石油化工股份有限公司 | The method of modifying of Y zeolite and the preparation method of catalytic cracking catalyst |
| CN104096586A (en) * | 2013-04-03 | 2014-10-15 | 中国石油天然气股份有限公司 | USY molecular sieve modification method |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2628071C2 (en) * | 2012-09-14 | 2017-08-14 | Чайна Петролеум Энд Кемикал Корпорейшн | Catalytic cracking catalyst containing ree-containing zeolite, and how to obtain it |
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