CN1162327C - A kind of rare earth Y-type zeolite - Google Patents
A kind of rare earth Y-type zeolite Download PDFInfo
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Abstract
一种稀土Y型沸石，以RE2O3计，稀土含量为4-15重%，晶胞常数为＞2.450nm至2.458nm，差热崩塌温度1000-1056℃，硅铝比8.3-8.8，氧化纳含量小于1.0重%。该沸石具有良好的重油裂化活性和选择性，氢转移活性好，能有效地提高轻质油收率，改善汽油质量，并具有良好的焦炭选择性，可以直接作为制备各类石油烃裂化催化剂的活性组元。A rare earth Y-type zeolite, calculated as RE 2 O 3 , the rare earth content is 4-15% by weight, the unit cell constant is >2.450nm to 2.458nm, the differential thermal collapse temperature is 1000-1056°C, and the silicon-aluminum ratio is 8.3-8.8. The sodium oxide content is less than 1.0% by weight. The zeolite has good heavy oil cracking activity and selectivity, good hydrogen transfer activity, can effectively increase the yield of light oil, improve gasoline quality, and has good coke selectivity, and can be directly used as a catalyst for preparing various petroleum hydrocarbon cracking catalysts active components.
Description
Technical field
The invention relates to a kind of rare earth Y type zeolite.
Background technology
Catalytically cracked gasoline is the main ingredient of motor spirit, and China's catalytically cracked gasoline accounts for 70% of motor spirit at present.In recent years, along with the further raising of protection environmental requirement, people were also more urgent to the demand of the catalytic cracking high quality clean gasoline of low alkene, low sulfur content.But, day by day become heavy catalytically cracked stock catalytic cracking catalyst is had higher requirement, namely require it not only to have higher activity, better selective and hydrogen transfer activity, and will have higher hydrothermal stability.
Y-type zeolite has experienced following several developmental stage as the main active component of catalytic cracking catalyst:
The NaY zeolite is not have activatedly to acid or catalytic reaction, and it is through NH
4 +Exchange Na
+After making HY type zeolite, just has very high activity.In the sixties, zeolite has been widely used in the oil refining processing, and the stability of zeolite usually is the major issue of considering in the catalyst preparation process, and particularly in catalytic cracking process, zeolite must have the ability of energy high-temperature resistant water heat.
Point out among USP3384572 and the USP3506440, use NH
4 +Na in the exchanging zeolite
+Make HY type zeolite, have very high activity, but its structural stability is relatively poor, in the dry air more than 500 ℃, will lose its degree of crystallinity, even be positioned in the air in room temperature, also can make its structural deterioration.On the basis of HY zeolite, further partly replace NH with rare earth ion
4 +The rare earth HY type zeolite of making (being called for short REHY) has very high activity, has also improved the shortcoming of HY zeolite poor heat stability.Along with the depth development of processing of heavy oil catalytic cracking, with rare earth ion and NH
4 +REHY and the REY of hybrid switching preparation, although its hydrogen transfer activity height, the cracking activity height is difficult for shrinking but still exist its structure cell, the stability problem of the higher hydrothermal temperature of ability in catalytic cracking unit, does not show as easy green coke and easy inactivation.
USP3293192 and C.V.MC Darid and P.K.Maher are at " zeolite stability and super steady zeolite " (Zeolite Chemistry and Catalysis, Acs Monograph 171, WashingtonD.C., 1976, reported under aqueous solution state in 285-231) and used NH
4 +Ion-exchange NaY zeolite, zeolite after the exchange is the process of roasting under 600-825 ℃ and steam again, this process can be repeated several times carries out, through so repeatedly exchange, after the multiple high temp calcination process, the zeolite structure cell shrinks, realize super stabilizing, namely obtain the ultrastable (being called for short USY) of hydro-thermal method preparation.This zeolite obtains a large amount of application in the nineties, and it is littler to be characterized in that structure cell shrinks, and good heat and hydrothermal stability are arranged, hydrogen transfer activity is low, coke selectivity is good, but also has the limited shortcoming of activity level, need take to improve its activity with the method for earth solution exchange.Because USY zeolitic frameworks silica alumina ratio is higher, the ion position is less, exists again simultaneously the part lattice and subside and stop up the phenomenon in duct in the super stabilizing process, and is little to the ion exchange capacity that makes zeolite, generally speaking in the USY zeolite of rare earth exchanged (brief note for REUSY), RE
2O
3Content be up to the heavy % of 3-4, the RE of considerable part is arranged
2O
3To be present in outside the zeolite crystalline substance with suction type.
In sum, although REY and REHY zeolite content of rare earth height, RE among the REY
2O
3Content be the heavy % of 10-20, RE among the REHY
2O
3Content be the heavy % of 6-14, have higher activity and hydrogen transfer activity, but structure cell can't further shrink lattice constant a
0=2.468-2.470nm, hydrothermal stability is relatively poor, and its differential heat collapse temperature is 900-980 ℃; And the USY zeolite is opposite, and structure cell shrinks a although have preferably
0=2.445-2.450nm, good hydrothermal stability, differential heat collapse temperature is more than 1000 ℃, but intracrystalline is difficult to exchanged rare earth, and content of rare earth is few.And above-mentioned two class zeolites are big owing to different reasons structure cell after wearing out shrinks, and the lattice constant of poised state only is 2.425-2.428nm, thereby the hydrogen transfer activity loss soon, is difficult to adapt to novel cracking catalytic to the requirement of selective hydrogen migration.
At present, when the preparation Cracking catalyst, have to adopt the overstable gamma zeolite of rare earth ion exchanged, i.e. super-stable Y zeolite containing rare-earth elements (the RE of REUSY
2O
3Content is generally about 3 heavy %) with the REHY zeolite (RE that contains Rare-Earth Content
2O
3Content is generally the heavy % of 6-14) and contain the REY zeolite (RE of high rare-earth content
2O
3Content is generally the heavy % of 10-20) each other collocation, press different proportion and mix use, although the activity level of catalyst is improved like this, but because REHY, the hydrothermal stability of REY own is poor, can make heat and the hydrothermal stability variation of catalyst, make catalyst in service at device, be easy to inactivation, it is low to show as the poising agent activity, and coke selectivity is poor.And if strengthen the REUSY consumption, make the 30-35% of catalyzer mesolite by routine, bring up to 40%, even higher by 45%, increased production cost undoubtedly greatly.
Summary of the invention
The purpose of this invention is to provide a kind ofly have simultaneously that intracrystalline content of rare earth height, lattice constant are less, heat and good hydrothermal stability, can be directly in order to the y-type zeolite of preparation cracking catalyst.
Y-type zeolite provided by the invention is with RE
2O
3Meter, intracrystalline content of rare earth are the heavy % of 4-15, and lattice constant is 2.450-2.458nm, differential heat collapse temperature 1000-1056 ℃.
Y-type high-Si zeolite provided by the present invention is with RE
2O
3Meter, the heavy % of the preferred 6-12 of intracrystalline content of rare earth, the preferred 2.452-2.456 of lattice constant, this zeolite has higher framework si-al ratio, and silica alumina ratio is 8.3-8.8, and sodium oxide content is preferably 0.5 heavy % less than 1.0 heavy %.
Type-Y high silicon zeolite provided by the present invention is prepared by following method: the y-type zeolite raw material that will contain rare earth carries out drying treatment, make its water-content be lower than 10 heavy %, according to silicon tetrachloride: Y zeolite=0.1-0.9: 1 weight ratio, feed the silicon tetrachloride gas that dry air carries, under temperature 150-600 ℃, reacted 10 minutes to 6 hours, after the reaction, purged 5 minutes to 2 hours with dry air, remove Na remaining in the zeolite with the decationized Y sieve water washing
+, Cl
-, Al
3+, RE
3+Etc. the solubility by product.
The said y-type zeolite raw material that contains rare earth can be industrial REY and the REHY zeolite that generally adopts, and also can be the product of NaY zeolite gained after rare earth exchanged.
In general, said REY zeolite, its content of rare earth is with RE
2O
3Count the heavy % of 6-14, Na
2O content is greater than 4 heavy %; Said REHY zeolite, its content of rare earth is with RE
2O
3Count the heavy % of 10-18, Na
2O content is greater than 2 heavy %.
Said NaY zeolite is as follows through the process of rare earth exchanged: adopt silica alumina ratio greater than 3.5 NaY zeolite and rare earth chloride solution according to NaY: RECl
3: H
2The weight ratio of O=1: 0.1-0.25: 5-15 in PH＞3.5, under temperature 80-90 ℃ the condition, was carried out rare earth exchanged 30-60 minute, through or not drying obtain.
Prepare the used REY of y-type zeolite provided by the invention, REHY raw material or the NaY zeolite after the rare earth chloride solution exchange, they all must pass through drying treatment before reaction, make the heavy % in its water-content＜10, are preferably＜5 heavy %.
Y-type zeolite provided by the invention, after 800 ℃/17h, 100% water vapour severe condition were handled, unit cell dimension still kept better, can reach 2.432-2.438nm, presented good heat and hydrothermal stability (example 9).
In addition, this zeolite has good heavy oil cracking activity, selectivity hydrogen transfer activity, high heat and hydrothermal stability, can improve yield of light oil effectively, improve quality of gasoline, and have good coke selectivity (example 10), can be directly as the active component for preparing all kinds of catalyst for cracking petroleum hydrocarbons.
Embodiment
Below will the present invention is further illustrated with example, but content of the present invention is not subjected to the restriction of these examples.
In the example, the silica alumina ratio of zeolite is calculated by following formula:
A wherein
0The lattice constant that records through X-ray diffraction method for zeolite.
Example 1
Be 85% NaY zeolite (Qilu Petrochemical Company Zhou village catalyst plant, silica alumina ratio are 4.0, and lattice constant is 2.473nm, and aluminium oxide is 24.8%, and sodium oxide molybdena is 16%) with solid content, under 80-90 ℃ of condition, press NaY: RECl
3: H
2O=1: 0.21: 10 ratio, carried out rare earth exchanged 60 minutes, make RE
2O
3Content be 16%, La wherein
2O
3Be 4.16%, Ce
2O
3Be 8.16%, the content of other rare earth oxide is 3.68%.Press NaY: SiCl
4=1: 0.5 ratio is carried SiCl with dry air
4In 450 ℃ of reactions 120 minutes, purge 20 minutes with dry air after, washing and filtering is to remove the Cl in the zeolite
-And Na
+, obtain sample, numbering RGY-1.
Example 2
With solid content is 75% NaY zeolite (Qilu Petrochemical company Zhou village catalyst plant, silica alumina ratio are 5.05, and lattice constant is 2.466nm, and aluminum oxide is 21.2%, and sodium oxide is 15.8%), under 80-95 ℃ of condition, presses NaY: RECl
3: H
2O=1: 0.25: 10 ratio, carried out rare earth exchanged 40 minutes, filter, wash.Press NaY: SiCl
4=1: 0.5 ratio is carried SiCl with dry air
4In 550 ℃ of reactions 60 minutes, after 120 minutes, washing and filtering obtained sample with the dry air purging, numbering RGY-2.
Example 3
Get REHY (Qilu Petrochemical Company Zhou village catalyst plant, RE
2O
3Content 13.4%, wherein La
2O
3Be 12.7 heavy %, Ce
2O
3Be 2.7 heavy %, the content of other rare earth oxide is 1.9 heavy %, and the lattice constant of zeolite is 2.469nm, and the differential thermal differential heat collapse temperature is 985 ℃, Na
2O content is 4.4 heavy %) put into reactor, be dried to water content less than 5%, press REY: SiCl
4=1: 0.5 ratio is carried SiCl with dry air
4In 350 ℃ of reactions 3 hours, after 60 minutes, washing and filtering obtained sample with the dry air purging, numbering RGY-3.
Example 4
Be 85% NaY zeolite (Qilu Petrochemical Company Zhou village catalyst plant, silica alumina ratio are 4.0, and lattice constant is 2.473nm, and aluminium oxide is 24.8%, and sodium oxide molybdena is 16%) with solid content, under 80-90 ℃ of condition, press NaY: RECl
3: H
2O=1: 0.21: 10 ratio, carried out rare earth exchanged 60 minutes, make RE
2O
3Content be 16%, La wherein
2O
3Be 4.16%, Ce
2O
3Be 8.16%, the content of other rare earth oxide is 3.68%.Press NaY: SiCl
4=1: 0.5 ratio is carried SiCl with dry air
4In 300 ℃ of reactions 5 hours, after 20 minutes, washing and filtering obtained sample with the dry air purging, numbering RGY-4.
Example 5
Be 65% NaY zeolite (Qilu Petrochemical Company Zhou village catalyst plant is produced, and silica alumina ratio 4.0, lattice constant are 2.473nm, and aluminium oxide is 24.8 heavy %, and it is 16 heavy % that oxidation is received) with solid content, press NaY: RECl
3: H
2O=1: 0.21: 15 ratio exchange RECl
3(chemical plant, packet header product, technical grade, wherein La
2O
3Be 26 heavy %, Ce
2O
3Be 51 heavy %, the content of other rare earth oxide is 23 heavy %), condition be in PH＞3.5,80-95 ℃ of lower exchange 30 minutes, then filtration washing oven dry will be dried sample as raw material, press itself and SiCl
4Be 1: 0.5 ratio, carry SiCl with dry air
4In 350 ℃ of reactions 120 minutes, after 20 minutes, washing and filtering obtained sample with the dry air purging, numbering RGY-5.
Example 6
Be 75% NaY zeolite (Qilu Petrochemical Company Zhou village catalyst plant is produced, and silica alumina ratio 4.5, lattice constant are 2.471nm, and aluminium oxide is 23.6 heavy %, and it is 15.8 heavy % that oxidation is received) with solid content, press NaY: RECl
3: H
2O=1: 0.1: 15 ratio exchange RECl
3(chemical plant, packet header product, technical grade, wherein La
2O
3Be 26 heavy %, Ce
2O
3Be 51 heavy %, the content of other rare earth oxide is 23 heavy %), in PH＞3.5,80-95 ℃ was carried out rare earth exchanged 40 minutes, filter then, wash, dry, with sample as raw material, by itself and SiCl
4Be 1: 0.5 ratio, carry SiCl with dry air
4In 350 ℃ of reactions 120 minutes, after 20 minutes, washing and filtering obtained sample with the dry air purging, numbering RGY-6.
Example 7
Be 80% NaY zeolite (Qilu Petrochemical Company Zhou village catalyst plant is produced, and silica alumina ratio 4.0, lattice constant are 2.473nm, and aluminium oxide is 23.8 heavy %, and it is 16 heavy % that oxidation is received) with solid content, press NaY: RECl
3: H
2O=1: 0.1: 10 ratio exchange RECl
3(chemical plant, packet header product, technical grade, wherein La
2O
3Be 26 heavy %, Ce
2O
3Be 51 heavy %, the content of other rare earth oxide is 23 heavy %), in PH＞3.5,80-95 ℃ was carried out rare earth exchanged 40 minutes, filter then, wash, dry, with sample as raw material, by itself and SiCl
4Be 1: 0.5 ratio, carry SiCl with dry air
4In 350 ℃ of reactions 120 minutes, after 20 minutes, washing and filtering obtained sample number into spectrum RGY-7 with the dry air purging.
Example 8
Be 75% NaY zeolite (Qilu Petrochemical Company Zhou village catalyst plant is produced, and silica alumina ratio 5.05, lattice constant are 2.466nm, and aluminium oxide is 21.2 heavy %, and it is 15.8 heavy % that oxidation is received) with solid content, press NaY: RECl
3: H
2O=1: 0.25: 15 ratio exchange RECl
3(chemical plant, packet header product, technical grade, wherein La
2O
3Be 26 heavy %, Ce
2O
3Be 51 heavy %, the content of other rare earth oxide is 23 heavy %), in PH＞3.5,80-95 ℃ was carried out rare earth exchanged 45 minutes, filter then, wash, dry, with sample as raw material, by itself and SiCl
4Be 1: 0.5 ratio, carry SiCl with dry air
4In 350 ℃ of reactions 120 minutes, after 60 minutes, washing and filtering obtained sample with the dry air purging, numbering RGY-8.
Comparative Examples
Contrast zeolite numbering DB-1 is the REHY zeolite, Qilu Petrochemical Company Zhou village catalyst plant product, RE
2O
3Content 13.4%, wherein La
2O
3Be 12.7 heavy %, Ce
2O
3Be 2.7 heavy %, the content of other rare earth oxide is 1.9 heavy %, and the lattice constant of zeolite is 2.469nm, and the differential thermal differential heat collapse temperature is 985 ℃, Na
2O content is 4.4 heavy %.
Contrast zeolite DB-2 is the REY zeolite, Qilu Petrochemical Company Zhou village catalyst plant product, RE
2O
3Content 19.2%, wherein La
2O
3Be 12.7 heavy %, Ce
2O
3Be 8.8 heavy %, the content of other rare earth oxide is 2.3 heavy %, and the lattice constant of zeolite is 2.465nm, and the differential thermal differential heat collapse temperature is 967 ℃, Na
2O content is 4.5 heavy %.
Contrast zeolite DB-3 is REUSY, is to be that 75% USY zeolite (Qilu Petrochemical company Zhou village catalyst plant is produced, lattice constant 2.453nm, aluminum oxide is 21 heavy %, sodium oxide is 3.8%) is pressed USY: RECl by solid content
3: H
2O=1: 0.21: 10 ratio, in PH＞3.5, carried out rare earth exchanged 60 minutes under the 80-90 ℃ of condition, filter then, wash, dry and obtain.
The physico-chemical parameter of the RGY-1 to RGY-8 of above example 1-8 preparation and three kinds of contrast zeolites is listed in the table 1.
Table 1
| Type | Lattice constant nm | SiO 2/Al 2O 3 | DTA ℃ | RE 2O 3Heavy % | Na 2The heavy % of O |
| DB-1 | 2.469 | 7.6 | 985 | 13.4 | 4.4 |
| DB-2 | 2.465 | 7.8 | 967 | 19.2 | 4.5 |
| DB-3 | 2.453 | 8.6 | 1000 | 3.6 | 1.0 |
| RGY-1 | 2.458 | 8.3 | 1005 | 14.5 | 0.24 |
| RGY-2 | 2.456 | 8.4 | 1008 | 13.4 | 0.30 |
| RGY-3 | 2.452 | 8.7 | 1015 | 9.6 | 0.26 |
| RGY-4 | 2.457 | 8.3 | 1015 | 12.9 | 0.24 |
| RGY-5 | 2.453 | 8.6 | 1001 | 11.6 | 0.16 |
| RGY-6 | 2.452 | 8.7 | 1056 | 9.0 | 0.17 |
| RGY-7 | 2.453 | 8.6 | 1031 | 5.6 | 0.23 |
| RGY-8 | 2.440 | 8.7 | 1038 | 4.5 | 0.30 |
Example 9
This example illustrates the hydrothermal stability of zeolite provided by the invention.
RGY-1, RGY-2 and RGY-4 zeolite that Comparative Examples agent DB-1, DB-2, DB-3 and example 1,2,4 are provided wear out through 800 ℃/4h, 100% water vapour and 800 ℃/17h, 100% water vapour severe condition respectively, and lattice constant, degree of crystallinity and their the relative crystallization reservation degree of aging back sample see Table 2.
Table 2
| Numbering | Treatment condition | Lattice constant nm | Relative crystallization reservation degree % |
| DB-1 | Fresh | 2.469 | - |
| 800℃/4h | 2.441 | 40 | |
| 800℃/17h | 2.430 | 12 | |
| DB-2 | Fresh | 2.465 | - |
| 800℃/4h | 2.435 | 59 | |
| 800℃/17h | 2.428 | 32 | |
| DB-3 | Fresh | 2.452 | - |
| 800℃/4h | 2.428 | 64 | |
| 800℃/17h | 2.424 | 21 | |
| RGY-1 | Fresh | 2.458 | - |
| 800℃/4h | 2.441 | 70 | |
| 800℃/17h | 2.438 | 54 | |
| RGY-2 | Fresh | 2.456 | - |
| 800℃/4h | 2.441 | 59 | |
| 800℃/17h | 2.436 | 41 | |
| RGY-4 | Fresh | 2.457 | - |
| 800℃/4h | 2.438 | 57 | |
| 800℃/17h | 2.439 | 63 |
As can be seen from Table 2, the hydrothermal stability that zeolite provided by the invention is high, its structure cell have after harsh conditions are processed and contrast the big lattice constant of zeolite, and its relative crystallization reservation degree all is better than the contrast zeolite.
Example 10
This example illustrates the little anti-performance evaluation of the heavy oil of Y zeolite provided by the invention.
Appreciation condition is: zeolite loading amount 4g, raw materials used oil are vacuum gas oil, and character is listed in the table 3, and reaction conditions is 520 ℃, and weight hourly space velocity is 16 hours
-1, agent-oil ratio is 3.0.
Each components contents adopts gas chromatography in the reaction.
Simultaneously after 800 ℃/17h, 100% water vapour severe condition are aging, through the heavy oil micro anti-evaluation, the results are shown in Table 4 with contrast medium DB-1, DB-3 and example RGY-2, RGY-4, RGY-6.
Table 3
| The feedstock oil parameter | Vacuum gas oil (VGO) |
| Proportion, g/cm 3Viscosity, mm 250 ℃ of 100 ℃ of carbon residues of/s, heavy % | 0.8652 14.58 4.37 0.04 |
| Boiling range, ℃ initial boiling point 5% 10 20 30% 40 50% 60 70% 80 90% 95% is done | 227 274 289 322 347 373 389 401 417 431 446 458 478 |
Table 4
As can be seen from Table 3, y-type zeolite RGY-2 provided by the invention compares with DB-1, under the close situation of transformation efficiency, and the yield of light oil height of zeolite provided by the invention, dry gas is few, particularly from hydrogen transference index ∑ C
4 0/ ∑ C
4 =See, be higher than nearly 1.4 units of contrast medium DB-1.
Y-type zeolite RGY-6 provided by the invention compares with DB-3, and under the close situation of transformation efficiency, heavy oil conversion performance is strong, hydrogen transfer activity index ∑ C
4 0/ ∑ C
=Be higher than nearly 0.7 unit of DB-3, show that zeolite product provided by the invention has strong heavy oil conversion performance, high activity, good selectivity and hydrogen transfer activity.
Claims (3)
1, a kind of rare earth Y type zeolite is characterized in that this zeolite is with RE
2O
3Meter, intracrystalline content of rare earth are the heavy % of 4-15, and lattice constant is＞2.450nm to 2.458nm that differential heat collapse temperature is 1000-1056 ℃.
2, according to the described y-type zeolite of claim 1, it is characterized in that this zeolite is with RE
2O
3Meter, intracrystalline content of rare earth are the heavy % of 6-12, and lattice constant 2.452-2.456nm, silica alumina ratio are 8.3-8.8, and sodium oxide content is less than 1.0 heavy %.
3, according to the described y-type zeolite of claim 1, the sodium oxide content that it is characterized in that described zeolite is less than 0.5 heavy %.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011156139A CN1162327C (en) | 2001-04-28 | 2001-04-28 | A kind of rare earth Y-type zeolite |
| DE60236792T DE60236792D1 (en) | 2001-04-28 | 2002-04-24 | RARE METAL Y-ZEOLITE AND METHOD OF MANUFACTURING THEREOF |
| JP2002585092A JP4282059B2 (en) | 2001-04-28 | 2002-04-24 | Method for preparing rare earth zeolite Y |
| CA2445597A CA2445597C (en) | 2001-04-28 | 2002-04-24 | A rare earth zeolite y and the preparation process thereof |
| PCT/CN2002/000288 WO2002087758A1 (en) | 2001-04-28 | 2002-04-24 | A rare earth zeolite y and the preparation process thereof |
| EP02726042A EP1390141B1 (en) | 2001-04-28 | 2002-04-24 | A rare earth zeolite y and the preparation process thereof |
| US10/132,911 US6787123B2 (en) | 2001-04-28 | 2002-04-26 | Rare earth zeolite Y and the preparation process thereof |
| US10/811,865 US6991774B2 (en) | 2001-04-28 | 2004-03-30 | Rare earth zeolite Y and the preparation process thereof |
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|---|---|---|---|
| CNB011156139A CN1162327C (en) | 2001-04-28 | 2001-04-28 | A kind of rare earth Y-type zeolite |
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Cited By (1)
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|---|---|---|---|---|
| US7776775B2 (en) | 2005-03-31 | 2010-08-17 | China Petroleum & Chemical Corporation | Cracking catalyst and a preparation process for the same |
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| CN101081369B (en) * | 2006-05-31 | 2010-05-12 | 中国石油化工股份有限公司 | A kind of rare earth-containing high silicon Y-type zeolite and its preparation method |
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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 |
| 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 |
| WO2018153301A1 (en) * | 2017-02-21 | 2018-08-30 | 中国石油化工股份有限公司 | Modified y-type molecular sieve, preparation method therefor, and catalyst containing same |
| US11053129B2 (en) * | 2017-02-21 | 2021-07-06 | China Petroleum & Chemical Corporation | Magnesium modified Y-type molecular sieve, preparation thereof and catalyst comprising the same |
| CN108455625B (en) * | 2017-02-21 | 2020-10-27 | 中国石油化工股份有限公司 | A kind of highly stable modified Y-type molecular sieve and preparation method thereof |
| MY204451A (en) | 2018-06-29 | 2024-08-29 | China Petroleum & Chem Corp | Modified y-type molecular sieve, catalytic cracking catalyst comprising the same, its preparation and application thereof |
| US11517886B2 (en) | 2018-06-29 | 2022-12-06 | China Petroleum & Chemical Corporation | Modified Y-type molecular sieve, catalytic cracking catalyst comprising the same, its preparation and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7776775B2 (en) | 2005-03-31 | 2010-08-17 | China Petroleum & Chemical Corporation | Cracking catalyst and a preparation process for the same |
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