CN100497175C - Method for raising content of rare earth of ultra stable Y type zeolite - Google Patents
Method for raising content of rare earth of ultra stable Y type zeolite Download PDFInfo
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Abstract
This invention discloses a method for raising rare earth content in super-stable Y-type zeolite. The method comprises: mixing super-stable Y-type zeolite and 0.01-2 N acid solution at a liquid/solid ratio of 4-20 at 20-100 deg.C, treating for 10-300 min, washing, filtering, adding rare earth salt solution for rare earth ion exchange, washing, filtering, and drying to obtain rare earth reinforced super-stable Y-type zeolite. The obtained rare earth reinforced super-stable Y-type zeolite has through pores without any blockage, and has obviously raised rare earth content. Cracking catalyst containing the rare earth reinforced super-stable Y-type zeolite as the active component has high heavy oil conversion ability.
Description
Technical field
The present invention relates to a kind of method of modifying of y-type zeolite.It exactly is a kind of RE ion exchange method that can effectively improve content of rare earth on the ultrastable Y.
Background technology
Along with catalytically cracked stock become the strict day by day of heavy and environmental regulation day by day, people require catalytic cracking process 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 ultrastable Y 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, making the catalyzer that contains the rare earth zeolite can 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 type-Y high silicon zeolite with RE
2O
3The content of rare earth of meter can reach 2～3 heavy %, 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 effective 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 be 2.420～2.464nm after handling, reduce 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 then is again with mineral acid or network and agent processing.
Chinese patent CN1042558A and CN1019094B have introduced a kind of chemical dealuminization and hydrothermal treatment consists process and have combined and be used alternatingly the method that the NaY zeolite prepares ultrastable Y of handling.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.Prepared super steady zeolite has framework aluminum and is evenly distributed characteristics such as secondary pore prosperity.Described zeolite has very high thermostability and hydrothermal stability.But this patent does not relate to further rare earth ion exchanged, and only is a kind of method for preparing ultrastable Y.
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.
Summary of the invention
On the bases of above-mentioned analysis and a large amount of experiments, the inventor finds, takes cleaning zeolite cavity earlier, and exchanged rare earth ionic method again can effectively improve the content of rare earth on the super steady zeolite of Hydrothermal Preparation.Rare earth ion in the exchange can enter in the intracrystalline cage of zeolite, rather than is deposited on the surface of zeolite.
Therefore, the method that the purpose of this invention is to provide a kind of effective raising ultrastable Y middle-weight rare earths content, this method is taked non-framework aluminum fragment in the duct of first cleaning overstable gamma zeolite, on the basis in mediation duct, carry out rare earth ion exchanged again, can improve the content of rare earth of ultrastable Y effectively.
Method provided by the invention is: with ultrastable Y and concentration is ratio under 20～100 ℃ temperature range the thorough mixing of the acid solution of 0.01～2N with liquid-solid ratio 4～20, handle 10～300 minutes after scouring, filtration, add rare earths salt again and carry out rare earth ion exchanged, exchange after scouring, filtration, drying obtain extremely steady y-type zeolite of rare earth.
In the method provided by the invention, described ultrastable Y and acid solution blended condition optimization are that the equivalent concentration of acid solution is 0.05～0.5N, are 20～60 minutes 25～95 ℃ following treatment times of temperature.
In the method provided by the invention, described raw material ultrastable Y can be the ultrastable Y through any method preparation, the wherein preferred Industrial products two that prepare through the method for hydrothermal dealumination are handed over the DASY-0.0 of two roastings, DASY-2.0, or the ultrastable Y of a friendship one roasting, more preferably one hand over the ultrastable Y of a roasting.
In the method provided by the invention, 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.The mixture of one or more in preferred hydrochloric acid, oxalic acid, the formic acid.
In the method provided by the invention, described rare-earth salts is rare earth chloride or rare earth nitrate compound.
In the method provided by the invention, the rare earth ion exchanged of described zeolite adopts conventional RE ion exchange method.
Method provided by the invention, be characterized at first adopting acid the duct of the ultrastable Y of Hydrothermal Preparation to be cleared up as the duct cleaning agent, remove the non-framework aluminum fragment in the zeolite cavity of being blocked in that produces in the water-heat process, make the unimpeded ultrastable Y in duct, adopt conventional rare earth ion exchanged on this basis.
Method advantage provided by the invention is: the extremely steady y-type zeolite of rare earth duct of adopting method of the present invention to make is unimpeded, and content of rare earth significantly improves and adopt ordinary method to carry out the zeolite facies ratio of rare earth exchanged, and content of rare earth is (with RE
2O
3Meter) brings up to 8～10% weights by 2～4 heavy %, improved 4～8 percentage points; The zeolite of this method modification is except that the content of rare earth height, and sample X diffraction analysis result shows that rare earth ion enters into the intracrystalline cage of zeolite, so the existence of rare earth not only can be played the cracking activity that the effect of stablizing zeolite framework can also improve zeolite.With this zeolite is that the catalytic cracking catalyst that active ingredient prepares has stronger heavy oil conversion performance.
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 Y sample with the inventive method modification front and back.
Embodiment
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, DASY6.0 and one hand over a roasting sample to provide by catalyzer Shandong branch office of China Petrochemical Industry, and its physical data is shown in Table 1.
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 complex analytical procedure " (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.Crystalline 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 100 gram DASY2.0 (butt), join in 1 liter of 0.2N oxalic acid aqueous solution to stir it is mixed, be warming up to 90～100 ℃ and keep 1 hour after-filtration, washing, taking-up filter cake, place 1 liter of decationized Y sieve water, add the RECl of 32ml
3Solution (319g/L) stirs, and is warming up to 90～95 ℃ and kept 1 hour, filters 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, and its physical data sees Table 2.
Embodiment 2
Get 100 gram DASY2.0 (butt), join in 1 liter of 0.1N oxalic acid aqueous solution to stir it is mixed, be warming up to 90～100 ℃ and keep after 1 hour, filter, washing, take out filter cake, place 1 liter of decationized Y sieve water and add the RE (NO of 32ml
3)
3Solution (319g/L) stirs, and is warming up to 90～95 ℃ and keeps 1 hour, filters 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, and its physical data sees Table 2.
Embodiment 3
Get 100 gram DASY2.0 (butt), join in 1 liter of 0.2N aqueous citric acid solution to stir it is mixed, be warming up to 90～100 ℃ and keep after 1 hour, filter, washing, take out filter cake, place 1 liter of decationized Y sieve water and add the RECl of 32ml
3Solution (319g/L) stirs, and is warming up to 90～95 ℃ and keeps 1 hour, filters 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, and its physical data sees Table 2.
Comparative Examples 1
Get 100 gram DASY2.0 samples (butt) and join in 1 liter of decationized Y sieve water, and in solution, add the RECl of 32ml
3Solution (319g/L) stirs, and is warming up to 90 ℃ and kept 1 hour, filters then, washing, filter cake be in 120 ℃ of dryings, promptly gets and contrast the extremely steady y-type zeolite of rare earth sample, is designated as B1, and its physical data sees Table 2.
Embodiment 4
Get 100 gram DASY0.0 samples (butt), join in 1 liter of 0.2N aqueous nitric acid to stir it is mixed, be warming up to 90～100 ℃ and keep after 1 hour, filter, washing, take out filter cake, place 1 liter of decationized Y sieve water and add the RECl of 32ml
3Solution (319g/L) stirs, and is warming up to 90 ℃ and keeps 1 hour, filters 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, and its physical data sees Table 3.
Embodiment 5
Get one of 100 gram Hydrothermal Preparation and hand over a roasting sample DY-0 (butt), joining to stir in 1 liter of 0.15N aqueous formic acid mixes it, be warming up to 90～100 ℃ and keep after 1 hour, filter, washing, take out filter cake, place 1 liter of decationized Y sieve water and add the RE (NO of 40ml
3)
3Solution (255g/L) stirs, and is warming up to 90～95 ℃ and keeps 1 hour, filters then, washing, filter cake be in 120 ℃ of dryings, promptly get the extremely steady y-type zeolite of rare earth sample, is designated as A5, and its physical data sees Table 3, and the X-ray diffraction spectrogram of material modification front and back is seen accompanying drawing 1.
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.The USY zeolite that does not contain rare earth shows very strong diffraction peak in the meeting of (311) crystal face, 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.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.
Embodiment 6
Get 100 gram Y zeolite one and hand over a roasting sample DY-0 (butt), joining to stir in 1 liter of 0.15N aqueous hydrochloric acid mixes it, be warming up to 90～100 ℃ and keep after 1 hour, filter, washing, take out filter cake, place 1 liter of decationized Y sieve water and add the RE (NO of 40ml
3)
3Solution (255g/L) stirs, and is warming up to 90 ℃ and keeps 1 hour, filters 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, and its physical data sees Table 3.
Embodiment 7～8
Embodiment 7～8 adopts method provided by the invention, is example with small-sized catalytic cracking reaction device (ACE), and the catalytic performance of extremely steady y-type zeolite of rare earth provided by the invention is described.
Extremely steady y-type zeolite of rare earth with method preparation provided by the invention is an active ingredient, with the pseudo-boehmite is caking agent, with kaolin is carrier, and the preparation method of catalytic cracking catalyst routinely is prepared into catalyzer, and the content of catalyzer mesolite is 30 heavy %.
Embodiment 7 is that active ingredient is prepared into catalyst sample with hyperastable Y-type RE zeolite Al, carries out activity rating with the ACE device.
Embodiment 8 is that active ingredient is prepared into catalyst sample with hyperastable Y-type RE zeolite A6, carries out activity rating with the ACE device.
Feedstock property sees Table 4, and operational condition and evaluation result see Table 5.
Comparative Examples 2～3
Comparative Examples 2,3 is an example with small-sized catalytic cracking reaction device (ACE), and the catalytic performance with the reference extremely steady y-type zeolite of rare earth of ordinary method preparation is described.
Be active ingredient with Hydrothermal Preparation ultrastable Y respectively through the non-modified of ammonium exchange, with the pseudo-boehmite is caking agent, with kaolin is carrier, and the preparation method of catalytic cracking catalyst routinely is prepared into catalyzer, and the content of catalyzer mesolite is 30 heavy %.
Comparative Examples 2 is that active ingredient is prepared into catalyst sample with hyperastable Y-type RE zeolite DASY2.0, carries out activity rating with the ACE device.
Comparative Examples 3 is that active ingredient is prepared into catalyst sample with hyperastable Y-type RE zeolite DASY6.0, carries out activity rating with the ACE device.
Feedstock property sees Table 4, and operational condition and evaluation result see Table 5.
The materialization data of table 1. overstable gamma zeolite raw material
The materialization data (1) of zeolite sample after table 2. modification
By table 1, table 2 as seen, the content of rare earth on the y-type zeolite DASY-2.0 of two friendships, two roastings is (with RE
2O
3Meter) is 1.9 heavy %; Directly carry out the zeolite that obtains after the conventional rare earth exchanged, content of rare earth only has 4.1 heavy %; The content of rare earth of the zeolite that passes through different acid treatment and then carry out obtaining after the rare earth ion exchanged is increased to 4.5 heavy %, 7.8 heavy %, 10.7 heavy % respectively, has increased by 0.4～6.6 heavy %.
After the inventive method modification, the content of rare earth in the zeolite significantly improves, and wherein the content of rare earth of DASY-2.0 is the highest is increased to 10.7%, has improved 8.8%; And, Na
2The content of O also drops to below 0.5%; The structural breakdown temperature is brought up to more than 1038 ℃ from 1006 ℃, and crystalline structure is more stable.
The materialization characterization data (2) of zeolite sample after table 3. modification
By table 3 as seen, hand over two roasting ultrastable Y DASY-0.0, to hand over a roasting ultrastable Y DY-0 to carry out the modification processing to the industry two that does not contain rare earth respectively with method of the present invention, the content of rare earth of the hyperastable Y-type RE zeolite that obtains is respectively 10.0 heavy %, 8.1 heavy %, 7.3 heavy %.
Table 4 stock oil character
| Density (20 ℃), gram per centimeter 3 | 0.9044 |
| Viscosity, millimeter 2/ second | 1.5217(20℃) |
| 100℃ | 9.96 |
| Zero pour, ℃ | 40 |
| Carbon residue, weight % | 3.0 |
| Elementary composition, 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％ | - |
The ACE activity rating data of table 5 catalyzer
*Catalyzer is all through 800 ℃ in the table 5, and 100% water vapor wore out in 17 hours.
By the catalyst activity evaluating data of embodiment in the table 57 and Comparative Examples 2 as seen, behind the Zeolite modifying, the index little alive of catalyzer has improved 15 units, shows that modification significantly improves the hydrothermal stability of catalyzer; Little anti-evaluation result shows, behind the Zeolite modifying, is reduced under 5.92 the situation by 8.04 at agent-oil ratio, the transformation efficiency of catalyzer has improved 6 percentage points, unconverted heavy oil reduces 5.71 percentage points, show Zeolite modifying after, the heavy oil conversion performance of catalyzer significantly improves.
By the catalyst activity evaluating data of embodiment in the table 58 and Comparative Examples 3 as seen, under the close situation of activity of such catalysts component extremely steady y-type zeolite of rare earth middle-weight rare earths content, the catalyst aging activity index that contains the inventive method modified zeolite has improved 11 percentage points, be reduced under 5.92 the situation by 8.04 at agent-oil ratio, the transformation efficiency of catalyzer has improved 0.39 percentage point, and unconverted heavy oil has reduced 1.08 percentage points.
Claims (6)
1. method that improves content of rare earth of ultra stable Y type zeolite, it is characterized in that this method comprises: ultrastable Y is mixed with acid earlier carry out acid treatment, wash then, filter, add rare earths salt again and carry out rare earth ion exchanged, exchange after scouring, filtration, drying obtain extremely steady y-type zeolite of rare earth; Described acid treatment condition is: and concentration is ratio under 20～100 ℃ temperature range the thorough mixing of the acid solution of 0.01～2N with liquid-solid ratio 4～20, handled 10～300 minutes, 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.
2. in accordance with the method for claim 1, it is characterized in that described acid is one or more the mixture that is selected from hydrochloric acid, oxalic acid, the formic acid.
3. in accordance with the method for claim 1, it is characterized in that described acid treatment condition is: and concentration is ratio under 25～95 ℃ temperature range the thorough mixing of the acid solution of 0.05N～0.5N with liquid-solid ratio 4～20, handles 20～60 minutes.
4. in accordance with the method for claim 1, it is characterized in that described ultrastable Y is the Industrial products that the method through hydrothermal dealumination prepares, comprising: two hand over the DASY-0.0 of two roastings, DASY-2.0, or the ultrastable Y of a friendship one roasting.
5. in accordance with the method for claim 4, it is characterized in that described ultrastable Y is the ultrastable Y of a friendship one roasting.
6. in accordance with the method for claim 1, it is characterized in that described rare-earth salts is rare earth chloride or rare earth nitrate salt.
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| US9630171B2 (en) | 2012-06-27 | 2017-04-25 | China Petroleum & Chemical Corporation | Catalyst containing a modified Y-type zeolite and a preparation process thereof |
| US9656255B2 (en) | 2012-09-14 | 2017-05-23 | China Petroleum & Chemical Corporation | Catalytic cracking catalyst having a rare earth-containing Y zeolite and a preparation process thereof |
| US9789475B2 (en) | 2011-12-15 | 2017-10-17 | Petrochina Company Limited | Ultra-stable rare earth Y-type molecular sieve and preparation method therefor |
| US9840422B2 (en) | 2011-12-15 | 2017-12-12 | Petrochina Company Limited | Magnesium modified ultra-stable rare earth Y-type molecular sieve and preparation method therefor |
| US9844772B2 (en) | 2011-12-15 | 2017-12-19 | Petrochina Company Limited | Heavy oil catalytic cracking catalyst and preparation method therefor |
| US9889439B2 (en) | 2011-12-15 | 2018-02-13 | Petrochina Company Limited | High light received heavy oil catalytic cracking catalyst and preparation method therefor |
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| CN104069889A (en) * | 2013-03-28 | 2014-10-01 | 中国科学院大连化学物理研究所 | Preparation method of rare earth MCM-49 molecular sieve catalyst |
| US11084024B2 (en) | 2015-08-05 | 2021-08-10 | Petrochina Company Limited | Method for modifying molecular sieve and a catalytic cracking catalyst containing the molecular sieve |
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| US9789475B2 (en) | 2011-12-15 | 2017-10-17 | Petrochina Company Limited | Ultra-stable rare earth Y-type molecular sieve and preparation method therefor |
| US9840422B2 (en) | 2011-12-15 | 2017-12-12 | Petrochina Company Limited | Magnesium modified ultra-stable rare earth Y-type molecular sieve and preparation method therefor |
| US9844772B2 (en) | 2011-12-15 | 2017-12-19 | Petrochina Company Limited | Heavy oil catalytic cracking catalyst and preparation method therefor |
| US9889439B2 (en) | 2011-12-15 | 2018-02-13 | Petrochina Company Limited | High light received heavy oil catalytic cracking catalyst and preparation method therefor |
| US9630171B2 (en) | 2012-06-27 | 2017-04-25 | China Petroleum & Chemical Corporation | Catalyst containing a modified Y-type zeolite and a preparation process thereof |
| US9656255B2 (en) | 2012-09-14 | 2017-05-23 | China Petroleum & Chemical Corporation | Catalytic cracking catalyst having a rare earth-containing Y zeolite and a preparation process thereof |
| US11111152B2 (en) | 2015-08-05 | 2021-09-07 | Petrochina Company Limited | Preparation method for modified molecular sieve and modified molecular sieve-containing catalytic cracking catalyst |
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