CN1291789C - Hydrocarbon cracking catalyst containing modcfied faujasite - Google Patents
Hydrocarbon cracking catalyst containing modcfied faujasite Download PDFInfo
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- CN1291789C CN1291789C CN 200410088564 CN200410088564A CN1291789C CN 1291789 C CN1291789 C CN 1291789C CN 200410088564 CN200410088564 CN 200410088564 CN 200410088564 A CN200410088564 A CN 200410088564A CN 1291789 C CN1291789 C CN 1291789C
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Abstract
The present invention relates to a hydrocarbon cracking catalyst containing modified faujasite obtained through filtration, washing and water vapor calcining treatment after a primary exchange reaction among faujasite, a phosphorus compound and an ammonium compound and then a rare earth solution is led into exchange slurry to further react. The catalyst contains 5 to 45 wt% of modified faujasite, 0 to 30 wt% of one or a plurality of other kinds of modified zeolite, 15 to 85 wt% of clay and 15 to 85 wt% of a high temperature resisting inorganic oxide. The zeolite components, the clay and a precursor of the high temperature resisting inorganic oxide are uniformly mixed according to certain proportion, formed in a spraying mode and washed. The obtained catalyst has the advantages of high activity stability, high gasoline yield, low coke yield, high heavy oil cracking capability and high heavy metal pollution resisting capability.
Description
The application is to be on February 7th, 2002 applying date, and application number is 02103910.0, and denomination of invention is divided an application for " a kind of modcfied faujasite and contain the hydrocarbon cracking catalyzer of this modcfied faujasite " patent application.
Technical field
The invention relates to a kind of hydrocarbon cracking catalyzer that contains modcfied faujasite, more particularly, the present invention relates to a kind of Cracking catalyst of phosphorous and rare-earth element modified zeolite, mainly as the catalytic cracking reaction process of hydro carbons.
Background technology
Along with catalytically cracked stock heaviness day by day, require to improve Cracking catalyst activity and product selectivity.Y-type zeolite activity after rare earth exchanged is greatly improved, but because the increase of hydrogen transfer activity causes the selectivity variation of cracked product.For addressing the above problem, two kinds of measures have been taked, the one, the content of rare earth of reduction molecular sieve active component, as USP4218307 and CN87104086, the 2nd, the introducing mode of change rare earth is as CN86107531A, CN86107598A, in Y zeolite, introduce rare earth oxide and rare earth hydrate in the precipitating rare earth mode, improved the coke selectivity and the preventing from heavy metal pollution performance of molecular sieve cracking catalyst to a certain extent, but shortcoming is a complicated process of preparation.Because the pH value of molecular sieve switching architecture is not suitable for the requirement of rare-earth precipitation, so molecular sieve exchange process and rare-earth precipitation process can only be carried out step by step.
In recent years, people take phosphorus is introduced Cracking catalyst to improve activity of such catalysts, selectivity, hydrothermal stability, preventing from heavy metal pollution performance and wear strength.These methods can be divided three classes substantially, i.e. zeolite phosphorus modification, and the modification of matrix phosphorus, (referring to USP4584091, USP4567152, CN1070384A), the modification of catalyst post processing phosphorus is (referring to USP4504382, CN1062157).Its mesolite phosphorus modification is an important developing direction.At present, the modification of zeolite phosphorus roughly has exchange, impregnation drying and crystallization three approach:
Zeolite has by the method for exchange phosphorus modification: JP62212219 repeatedly exchanges NaY zeolite and phosphorous ammonium salt solution, and the P-USY zeolite of Heat stability is good has been made in repeatedly roasting.
Zeolite has by the method for dipping phosphorus modification: EP397183 exchanges to Na in the zeolite with the NaY zeolite in advance with ammonium sulfate
2O is 1～5 weight %, then be selected from H
3PO
4, (NH
4)
2HPO
4, NH
4H
2PO
4And NaH
2PO
4Phosphorus-containing compound in pH=4～7, temperature is under 20～350 ℃, combination drying, its P
2O
5Content is 0.1～4 weight %, and at 500～700 ℃, phosphorous overstable gamma zeolite is made in roasting under 10～100% steam, has improved the cracking activity and the gasoline selective of catalyst.Document (J.Cat., 145,27-36,1994) adopts H
3PO
4Dipping USY Buddhist stone, document (J.Cat., 132,229～243,1991) is then with phosphorus-containing compound dipping ZSM-5 zeolite, all to a certain extent modulation the acidity of zeolite molecular sieve, improved the selectivity of corresponding catalyst product.
Zeolite is introduced aluminum phosphate in the zeolite crystallization system by crystallization phosphorus modifying method: CN1058382A, has directly synthesized phosphorous five-membered ring silica-rich zeolite, and made Cracking catalyst activity stability is good, the octane number height.
Since zeolite by the phosphorus modification and rare earth modified after, product respectively has its distinguishing feature, people have prepared zeolite molecular sieve and the catalyst thereof that contains rare earth and phosphorus simultaneously again.CN1147420A adopts REY, one of REHY or REX are zeolite seed crystal, crystal seed is evenly dispersed in the colloidal state system of being made up of waterglass, aluminium salt, inorganic acid and water, synthesized the molecular sieve that contains rare earth with MFI structure by crystallization, at high temperature handle with phosphorus-aluminium activator then, obtained phosphorous and molecular sieve rare earth, when being used for hydro carbons pyrolytic conversion reaction, shown excellent hydrothermal stability and good low-carbon alkene selectivity of product.CN1062750A then handles the hyperastable Y-type RE zeolite catalyst with the aqueous solution of phosphorus-containing compound, has improved Cracking catalyst activity stability, cracking selectivity and wear strength greatly.
In sum, Cracking catalyst by rare earth modified, phosphorus modification and rare earth and phosphorus composite modified after, can obviously improve catalyst activity stability and cracking selectivity.But the shortcoming of prior art is the modified technique complexity, all is that substep carries out such as the super stabilizing of zeolite and phosphorus modifying process, and the production cycle is long; The composite modified process of phosphorus and rare earth generally is to carry out rare earth modifiedly earlier, carries out the phosphorus modification again and handles, the utilization rate of phosphorus lower (generally being lower than 60%).In order to adapt to Cracking catalyst processing heavy raw oil, the requirement of producing light-end products and low-carbon alkene is developed the excellent more new modified Cracking catalyst of performance and is seemed very urgent.
Summary of the invention
The purpose of this invention is to provide a kind of hydrocarbon cracking catalyzer that contains rare earth and the composite modified faujasite of phosphorus.This modcfied faujasite preparation technology is simple, has good activity stability; The hydrocarbon cracking catalyzer that contains this modcfied faujasite also has higher yield of gasoline and low coke yield.
The present invention realizes by following manner:
Modcfied faujasite is to carry out exchange reaction by faujasite and phosphorus compound and ammonium compounds, water and zeolite weight ratio 2～25, pH=2.0～6.5, temperature is 10～150 ℃, be 0.1～4 hour swap time, in the exchange slurries, introduce earth solution then, 1～60 minute reaction time, after filtration, washing, through phosphorus and rare earth modified zeolite at 250～800 ℃, roasting 0.1～3.5 hour under 1～100% steam and obtaining, these zeolite lattice constant 2.440～2.465 nanometers, sodium oxide molybdena 2.0～6.5 weight %, phosphorus 0.01～3.0 weight %, rare earth oxide 0.1～15 weight %.
Phosphorus compound of the present invention can be general orthophosphoric acid, phosphorous acid, ammonium phosphate, ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, aluminum phosphate, pyrophosphoric acid, can be wherein one or more, the kind of phosphorus compound does not influence enforcement of the present invention; Ammonium compounds can be general ammonium chloride, ammonium nitrate, ammonium carbonate, carbonic hydroammonium, ammonium oxalate, ammonium sulfate, ammonium hydrogen sulfate, can be wherein one or more; Described earth solution can be the mixed rare earth solution of any composition, preferably rare earth chloride or rare earth nitrate solution.
Faujasite give-and-take conditions of the present invention are: water and zeolite weight ratio 2～2 5, preferred 4～10; The weight ratio 0.001～0.10 of phosphorus and zeolite in the phosphorus compound, preferred 0.002～0.06; The weight ratio 0.05～1.0 of ammonium compounds and zeolite, preferred 0.1～0.8; PH=2.0～6.5, temperature are 10～150 ℃, and be 0.1～4 hour swap time; The rare earth oxide of in the exchange slurries, introducing and the weight ratio 0.001～0.2 of zeolite, 1～60 minute reaction time, filter, wash, filter cake is at 250～800 ℃, and preferred 300～700 ℃, roasting is 0.1～3.5 hour under 1～100% steam.
According to phosphorous and composite modified faujasite lattice constant 2.440～2.465 nanometers of rare earth of the present invention's preparation, sodium oxide molybdena 2.0～6.5 weight %, phosphorus 0.01～3.0 weight %, rare earth oxide 0.1～1 5 weight %; Wherein a phosphorus part is to enter molecular sieve by exchange in the modcfied faujasite, another part then forms composite oxides by phosphorus and rare earth reaction and is evenly distributed on the surface of molecular sieve, the existing chemical action of this modification, physical action is arranged again, and acid and surface nature can play promotor action well to the structure of molecular sieve.In addition, preparation of the present invention is phosphorous also has following characteristics with the method rare-earth ultra-steady modified zeolite:
(1) introduce phosphorus and rare earth element simultaneously on zeolite molecular sieve, technology is very simplified, and production cost has reduction by a relatively large margin.
(2) because phosphorus and rare earth can react by stoichiometry, the utilization rate of phosphorus and rare earth can have been saved raw material effectively up to 95%.
The invention provides a kind of hydrocarbon cracking catalyzer that contains above-mentioned modcfied faujasite, this catalyst is made up of the modcfied faujasite of 5～45 weight %, one or more other modified zeolites of 0～30 weight %, the clay of 15～48 weight %, the high-temperature inorganic oxide that adds in addition except that clay of 15～18 weight %.
The Preparation of catalysts method can be with above-mentioned zeolite component, clay and the predecessor that except that clay, adds high-temperature inorganic oxide in addition in required ratio, conventional catalyst preparation methods such as homogeneous spray shaping, post processing obtain the catalyst finished product thus.
Phosphorus and rare earth modified faujasite that zeolite component during catalyst of the present invention is formed can adopt the present invention to prepare separately, or be composited with other modified zeolite; Modcfied faujasite comprises phosphorus and rare earth modified Y zeolite, phosphorus and rare earth modified X zeolite; Other modified zeolite is selected from X type zeolite, y-type zeolite, zeolite L, ZSM-5 zeolite, modenite, β zeolite, the omega zeolite one or more modified zeolite that obtains through conventional physics or chemical modification, preferably modified zeolite of Y-type, modified ZSM-5 zeolites; Clay is kaolin, galapectite, imvite, sepiolite etc., can be wherein one or more.The high-temperature inorganic oxide that adds in addition except that clay is Al
2O
3, SiO
2, SiO
2-Al
2O
3, AlPO
4, MgO, can be wherein one or more; Its predecessor comprises silica-alumina gel, Ludox, aluminium colloidal sol, sial complex sol, boehmite, can be wherein one or more.
Preparation of catalysts can adopt conventional method and condition, is chosen as the spray-drying condition: 300～800 ℃ of inlet temperatures, 50～350 ℃ of exhaust temperatures.The roasting of catalyst can be chosen in 200～700 ℃ of following roastings, and preferred 300～650 ℃, 0.05～4 hour time, preferred 0.1～3.5 hour; The catalyst detergent condition can be: water is 1～35 with the catalyst weight ratio, and is best 5～30,15～100 ℃ of wash temperatures, 0.1～2 hour time, preferred 0.15～1.5 hour.
Cracking catalyst provided by the invention has good hydrothermal stability, reaction conversion ratio height, the advantage that product selectivity is good.Simultaneously,, shortened whole Preparation of catalysts flow process greatly, can reduce cost more than 1/3rd because it is easy to prepare the preparation technology who contains rare earth and phosphorus modcfied faujasite.
The specific embodiment
The following examples will be described further Cracking catalyst provided by the invention and preparation method thereof, but these embodiment can not limit the present invention.
(1) used analysis test method among the present invention.
1. lattice constant: x-ray diffraction method.
2. degree of crystallinity retention rate: x-ray diffraction method.
3. quartz content: x-ray diffraction method.
4. kaolinite content: x-ray diffraction method.
5. sodium oxide content: flame spectrometry.
6. phosphorus content: colorimetric method
7. rare earth oxide content: colorimetric method.
(2) raw materials used specification in the embodiment of the invention
1, liquid ammonium phosphate 23.0 grams per liters are (with PO4
3-Meter); Solid phosphoric acid hydrogen two ammoniums; Solid ammonium sulfate; Solid ammonium chloride; NaY zeolite lattice constant 2.465 nanometers, degree of crystallinity 89 weight %:NaX zeolite lattice constants 2.474 nanometers, degree of crystallinity 92 weight %; The aluminium oxide 24.1% of aluminium colloidal sol, the mol ratio 1.21 of aluminium and chlorine; The silica 25.0% of Ludox; Re chloride contains rare earth oxide 200 grams per liters, and nitric acid rare earth contains rare earth oxide 215 grams per liters, all takes from the qualified industrial goods of PetroChina Company Limited.'s Catalyst Factory of Lanzhou Petrochemical Company.
2, ZSM-5: igloss 3.0 weight %, silica alumina ratio 500, Fudan University in Shanghai production; The β zeolite: igloss 3.5 weight %, Fushun produces, and is industrial certified products.
3, kaolin: aluminium oxide 42.5 weight %, quartzy 3.5 weight %, kaolinite 86 weight %; Galapectite: aluminium oxide 43.2 weight %, quartzy 2.9 weight %, kaolinite 88 weight % are China Kaolin Co., Ltd and produce.
4, it is pure that hydrochloric acid, sulfuric acid are analysis
Embodiment 1:
Get 3 kilograms of NaY (butt), add 22.2 liters deionized water, making beating adds 1.44 kilo sulfuric acid ammoniums and 8.1 liters of ammonium phosphate in addition.Hydrochloric acid adjusting slurry pH with 3 mol is 3.8, heat up, reacted 50 minutes down at 82 ℃, under agitation slowly add 0.90 liter of earth solution then, continue reaction 30 minutes, filter, wash, filter cake is at 620～640 ℃, roasting is 1.5 hours under 80% water vapor conditions, obtains modcfied faujasite of the present invention-1.
With 2.50 kilograms of kaolin (butt), use said method to make modcfied faujasite-1 1.74 kilogram and 0.20 kilogram of ZSM-5 zeolite, 3.26 kg aluminium colloidal sols and 7.5 kilograms of deionized waters mix pulls an oar, and stirs 1.5 hours, after crossing colloid mill, spray drying forming.With thus obtained microsphere 400 ℃ of roastings 0.5 hour.Get 2 kilograms of roasting microballoons, add 10 kilograms of deionized waters and 0.54 kilo sulfuric acid ammonium and stir, transfer pH=3.6,60 ℃ of washings 15 minutes.Filter the back and add 5 liters of ammonium phosphate and 22 kilograms of deionized waters, stir, 60 ℃ of washings 15 minutes, filtration drying promptly got the phosphorous and composite modified faujasite Cracking catalyst-1 of rare earth of the present invention's preparation.
Embodiment 2:
Get 3 kilograms of NaY (butt), add 21.0 liters deionized water, making beating adds 1.20 kilograms of ammonium chlorides and 4.0 liters of ammonium phosphate in addition.Hydrochloric acid adjusting slurry pH with 2 mol is 3.0, heat up, reacted 30 minutes down at 89 ℃, under agitation slowly add 0.45 liter of earth solution then, continue reaction 30 minutes, filter, wash, filter cake is at 600～620 ℃, roasting is 2.5 hours under 100% water vapor conditions, obtains modcfied faujasite of the present invention-2.
Adopt condition similarly to Example 1 to prepare catalyst, just make modcfied faujasite-1 into modcfied faujasite-2, add 0.20 kilogram of β zeolite in addition again, kaolin is changed into galapectite, addition is constant, makes the phosphorous and rare earth composite modified zeolite catalyst-2 of the present invention.
Embodiment 3:
Get 3 kilograms of NaX (butt), add 31.50 liters deionized water, making beating adds 1.30 kilograms of ammonium chlorides and 64 gram diammonium hydrogen phosphates in addition.Hydrochloric acid adjusting slurry pH with 2 mol is 4.0, heat up, reacted 30 minutes down at 92 ℃, under agitation slowly add 0.31 liter of rare earth nitrate solution then, continue reaction 10 minutes, filter, wash, filter cake is at 600～620 ℃, roasting is 1.0 hours under 100% water vapor conditions, obtains modcfied faujasite of the present invention-3.
With 2.45 kilograms of kaolin (butt), use said method to make modcfied faujasite-1 1.5 kilogram and 0.40 kilogram of modcfied faujasite-3,3.89 kilogram Ludox and 7.0 kilograms of deionized waters and mix and pull an oar, stirred 1.2 hours, after crossing colloid mill, spray drying forming.With thus obtained microsphere 410 ℃ of roastings 0.6 hour.Get 2 kilograms of roasting microballoons, add 10 kilograms of deionized waters and 0.54 kilo sulfuric acid ammonium and stir, transfer pH=3.6,60 ℃ of washings 15 minutes.Filter the back and add 4.5 liters of ammonium phosphate and 21 kilograms of deionized waters, stir, 60 ℃ of washings 15 minutes, filtration drying promptly got the modcfied faujasite Cracking catalyst-3 of the present invention's preparation.
Comparative Examples 1:
Get 3 kilograms of NaY (butt), add 21.0 liters of deionized waters, making beating adds the earth solution of 1.20 kilograms of ammonium chlorides, 4.0 liters of ammonium phosphate and 0.45 liter in addition, mixes, hydrochloric acid adjusting slurry pH with 2 mol is 3.5, heat up, reacted 40 minutes down, filter, wash at 89 ℃, filter cake is at 600～620 ℃, and roasting is 2.5 hours under 100% water vapor conditions; Adding 15 liters of deionized waters and 4.0 liters of ammonium phosphate after the roasting in the molecular sieve, mix, is 3.5 with the hydrochloric acid adjusting slurry pH of 2 mol, heats up, and reacts 40 minutes down at 89 ℃, and filtration, washing, drying obtain contrasting modcfied faujasite-a.
Adopt condition similarly to Example 1 to prepare catalyst, just make modcfied faujasite-1 into above-mentioned modcfied faujasite a, addition is constant, makes comparative catalyst-A.
The modcfied faujasite and the catalyst of embodiment 1～3, Comparative Examples 1 gained are carried out following evaluation, contrast.
1. modcfied faujasite physical and chemical performance contrast.
Table 1 is the physical and chemical performance contrast of modified zeolite,
The physical and chemical performance contrast of table 1 modified zeolite
| Project | Embodiment | Comparative Examples | ||
| Modcfied faujasite-1 | Modcfied faujasite-2 | Modcfied faujasite-3 | Modcfied faujasite-a | |
| Sodium oxide molybdena, weight % | 4.60 | 4.10 | 4.85 | 4.50 |
| Rare earth oxide, weight % | 5.70 | 2.95 | 2.02 | 2.25 |
| Phosphorus, weight % | 1.90 | 0.93 | 0.48 | 0.50 |
| Lattice constant, nanometer | 2.460 | 2.459 | 2.466 | 2.462 |
| Phosphorus utilization, % are 1. | 95 | 93 | 96 | 50 |
| The rare earth utilization rate, % 2. | 95 | 98 | 98 | 75 |
| Zeolite stability, % 3. | 45 | 46 | 43 | 44 |
1. the theory throwing amount that refers to phosphorus content ÷ phosphorus in the molecular sieve.
2. the theory throwing amount that refers to molecular sieve middle rare earth content ÷ rare earth.
3. degree of crystallinity * 100% that refers to degree of crystallinity (800 ℃ * 4 hours, 100% steam) the ÷ fresh molecular sieve of aging molecular sieve.
As can be seen from Table 1, embodiment 1-3 uses among the modcfied faujasite 1-3 of preparation technology's acquisition of the present invention, phosphorus and rare earth can produce precipitation reaction by stoichiometry, the utilization rate of phosphorus and rare earth can reach more than 90%, and the rare earth utilization rate of the modcfied faujasite a that the technology that adopts Comparative Examples obtains is 75%, phosphorus utilization has only about 50%, and its preparation process complexity in the Comparative Examples.So the good stability of phosphorus provided by the invention and the composite modified faujasite of rare earth, preparation technology is simple, the utilization rate height of phosphorus and rare earth.
2. the anti-vanadium reactivity by little anti-measuring Cracking catalyst 1-3 of the present invention and comparative catalyst A.
Experiment condition: 800 ℃, 100% water vapor conditions is aging down after 4 hours, reacts 70 seconds down at 460 ℃.Catalyst loading amount 5.0g, oil ratio 3.2, feedstock oil are straight distillation light diesel oil, oil inlet quantity 1.56g.
Getting 5.74 gram ammonium metavanadates is dissolved in 3% the aqueous hydrogen peroxide solution and is made into 500 milliliters of solution that contain vanadium 0.5%.With reference to Mitchell method (Ind.Eng.Chem.Prod.Dev.19,209,1980) catalyst is carried out pollution of vanadium.Catalyst is at first 540 ℃ of roastings 1.5 hours, at room temperature soaks catalyst 16 hours with an amount of above-mentioned vanadium solution, 120 ℃ dry 24 hours down, then 540 ℃ of roastings 4 hours, measure the micro-activity of polluting catalyst again.
The catalyst 1～3 of embodiment 1～3, Comparative Examples gained and catalyst A are carried out little anti-experiment, the results are shown in Table 2.
The little anti-experiment and the contamination data of table 2 catalyst
*
| Project | Embodiment | Comparative example | |||
| Catalyst-1 | Catalyst-2 | Catalyst-3 | Catalyst-A | ||
| Micro-activity, % | Before the pollution | 74 | 75 | 73 | 71 |
| After the pollution | 55 | 56 | 53 | 50 | |
| Activity preservation rate, % | 74 | 75 | 73 | 70 | |
*Level of pollution: vanadium=5000ppm
As seen from Table 2, compare, adopt the Cracking catalyst 1～3 of the present invention's preparation to have higher micro-activity, and under the condition of polluting the 5000ppm vanadium, activity preservation rate exceeds 4～5 units with contrast medium.
3. the cracking reaction selectivity by fixed fluidized bed measuring Cracking catalyst 1～3 of the present invention and comparative catalyst-A
Experiment condition: at 800 ℃, the down aging 10 hours afterreactions of 100% steam, 500 ℃ of reaction temperatures, 650 ℃ of regeneration temperatures, weight space velocity 16h
-1, catalyst loading amount 150 grams, oil ratio 3.75, feedstock oil are long distillate oil+30% Xinjiang decompression residuum of 70%.The fixed bed evaluation result sees Table 3.
As seen from Table 3, compare with comparative catalyst-A, the catalyst 1～3 of the present invention's preparation has high yield of gasoline and low heavy oil productive rate, and coke selectivity is good simultaneously.
The fixed fluidized bed evaluating data of table 3
| Project | Embodiment | Comparative example | ||
| Catalyst-1 | Catalyst-2 | Catalyst-3 | Catalyst-A | |
| Dry gas, weight % | 1.5 | 1.5 | 1.4 | 1.6 |
| Liquefied gas, weight % | 23.6 | 22.0 | 22.5 | 22.7 |
| Gasoline, weight % | 47.0 | 48.5 | 47.6 | 45.9 |
| Diesel oil, weight % | 15.2 | 15.2 | 15.0 | 15.6 |
| Heavy oil, weight % | 7.1 | 8.0 | 7.5 | 8.6 |
| Coke, weight % | 3.8 | 3.2 | 3.6 | 3.9 |
| Conversion ratio, weight % | 75.9 | 75.2 | 75.1 | 74.1 |
| Coke/conversion ratio | 0.050 | 0.043 | 0.048 | 0.053 |
Claims (7)
1. hydrocarbon cracking catalyzer that contains modcfied faujasite is characterized in that: catalyst is made up of the modcfied faujasite of 5～45 weight %, one or more other modified zeolites of 0～30 weight %, the clay of 15～48 weight % and the high-temperature inorganic oxide that 15～18 weight % add except that clay in addition; Wherein modcfied faujasite is meant by faujasite and phosphorus compound and ammonium compounds and carries out exchange reaction, water and zeolite weight ratio 2～25, pH=2.0～6.5, temperature is 10～150 ℃, be 0.1～4 hour swap time, in the exchange slurries, introduce earth solution then, 1～60 minute reaction time, after filtration, washing, through phosphorus and rare earth modified zeolite at 250～800 ℃, roasting 0.1～3.5 hour under 1～100% steam and obtaining, these zeolite lattice constant 2.440～2.465 nanometers, sodium oxide molybdena 2.0～6.5 weight %, phosphorus 0.01～3.0 weight %, rare earth oxide 0.1～15 weight %.
2. hydrocarbon cracking catalyzer according to claim 1 is characterized in that described phosphorus compound is selected from one or more in orthophosphoric acid, phosphorous acid, ammonium phosphate, ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, aluminum phosphate, the pyrophosphoric acid.
3. hydrocarbon cracking catalyzer according to claim 1 is characterized in that described ammonium compounds is selected from one or more in ammonium chloride, ammonium nitrate, ammonium carbonate, carbonic hydroammonium, ammonium oxalate, ammonium sulfate, the ammonium hydrogen sulfate.
4. hydrocarbon cracking catalyzer according to claim 1 is characterized in that described other modified zeolite is selected from X type zeolite, y-type zeolite, L zeolite, ZSM-5 zeolite, modenite, β zeolite, the omega zeolite modified zeolite that one or more obtain through conventional physics or chemical modification.
5. hydrocarbon cracking catalyzer according to claim 1, the predecessor that it is characterized in that described high-temperature inorganic oxide is selected from one or more in silica-alumina gel, Ludox, aluminium colloidal sol, sial complex sol, the boehmite.
6. hydrocarbon cracking catalyzer according to claim 1 is characterized in that described clay is selected from one or more in kaolin, galapectite, imvite, the sepiolite.
7. hydrocarbon cracking catalyzer according to claim 1, when it is characterized in that described modcfied faujasite prepares, the earth solution of introducing in the exchange slurries is re chloride or rare earth nitrate solution.
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| CN101433857B (en) * | 2007-11-15 | 2011-05-11 | 石大卓越科技股份有限公司 | Method for preparing rare-earth ultra-steady Y molecular sieve |
| CN102019195B (en) * | 2009-09-09 | 2013-02-13 | 中国石油天然气股份有限公司 | Modified Y molecular sieve-containing catalytic cracking catalyst |
| CN103073024B (en) | 2011-10-26 | 2014-12-31 | 中国石油化工股份有限公司 | Modified 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 |
| WO2014000423A1 (en) | 2012-06-27 | 2014-01-03 | 中国石油化工股份有限公司 | Catalytic cracking catalyst containing modified y type molecular sieve and preparation method therefor |
| JP6301336B2 (en) | 2012-09-14 | 2018-03-28 | 中国石油化工股▲ふん▼有限公司 | Catalytic cracking catalyst having rare earth-containing Y-type zeolite and method for producing the same |
| CN103771445B (en) * | 2012-10-19 | 2016-03-23 | 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 |
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