CN1341697A - Vanadium-resistant hydrocarbon cracking catalyst and preparation method thereof - Google Patents
Vanadium-resistant hydrocarbon cracking catalyst and preparation method thereof Download PDFInfo
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Abstract
The phosphorus and rare earth containing vanadium-resisting hydrocarbon cracking catalyst is formed from 10-60 wt% of Y-type molecular sieve or Y-type molecular sieve and MFI structure molecular sieve and/or beta-molecular sieve, 10-75 wt% of clay, 10-70 wt% of two kinds of aluminium oxide, 0.1-7.0 wt% (by P2O5) of phosphorus and 0.1-22 wt% (by RE2O3) of rare earth, in which the sedimentary rare earth is 0.1-10 wt%. Said catalyst is made up by using Y-type molecular sieve treated by phosphorus-contained solution to mix or not to mix with MFI structure molecular sieve and/or beta-molecular sieve, then mixing them with clay, double aluminium binder and rare earth hydroxide precipitated suspension; roasting at 500 deg.C or spray-drying and treating by using phosphorus-contained solution. Said catalyst can reduce olefine content in the gasoline fraction to 19-24 wt%, and possesses good vanadium-resisting property.
Description
The invention relates to hydrocarbon cracking catalyzer of a kind of anti-vanadium and preparation method thereof, specifically, is about a kind of anti-vanadium hydrocarbon cracking catalyzer of molecular sieve type that contains rare earth and phosphorus and preparation method thereof.
From the mid-1970s, countries in the world have gradually adopted fluid catalytic cracking (FCC) catalyzer that contains ultra-steady Y molecular sieve (USY) to improve the octane value of catalytically cracked gasoline, this is because the USY molecular sieve has the low characteristics of acid site density, reduced the hydrogen transfer reactions in the FCC process, increase the olefin(e) centent in the gasoline fraction, thereby improved the octane value of gasoline.But alkene is as a kind of more active hydro carbons, and meeting photochemical reaction took place and generates ozone after not only volatilization entered atmosphere, make environment be subjected to severe contamination, and its existence can affect the stability of gasoline and the use of engine.Therefore, various countries increase day by day to the attention of olefin(e) centent in the gasoline, the olefin(e) centent in the gasoline are made restriction in the gasoline standard of many countries.
The capacity to reprocess of China's refinery is based on catalytic cracking, device (catalytic reforming+isomerization+alkylation+etherificate) ability of production high-quality stop bracket gasoline component is low, catalytically cracked gasoline in gasoline pool ratio up to about 80%, olefin(e) centent about 40～60 (volume) % in the gasoline is apparently higher than the new gasoline standard of China.Therefore, the olefin(e) centent that reduces in the FCC gasoline fraction is to make Chinese commodity gasoline reach an important and real approach of new standard.
In the last few years, people had adopted phosphorus had been introduced method in the Cracking catalyst with the abrasion resistance of improving catalyst, activity, selective and hydrothermal stability etc.These methods can be divided three classes substantially:
The first kind: earlier the precursor with molecular sieve, clay and/or high-temperature inorganic oxide mixes, and carries out aftertreatment with the aqueous solution of P contained compound behind the spray shaping and makes catalyzer.As CN1062750A and CN102157A.Or handle the Y zeolite catalyzer of making by the carclazyte converted in-situ with dihydrogen phosphate ions, dihydrogen phosphite root or its ammonium salt, to improve its catalytic activity.Such as USP4454241, USP4465780 and USP4504382.
Second class: handle matrix or, add active ingredient then and make catalyzer with P contained compound all or part of as matrix with P contained compound.In USP4584091, reported and anticipated aluminum oxide, then this phosphorus-containing alumina has been mixed and made into catalyzer mutually with carclazyte, USY and silicon-aluminum sol with P contained compound.Reported in USP4873211 with the specific surface is 50-300 rice
2The aluminum phosphate of/gram is as matrix, and adding specific surface again is 200-1000 rice
2The cracking catalyst that the Y zeolite of/gram is made.The borophosphoric acid that then contains the heavy % of 0.1-5 in the cracking catalyst matrix in USP5151394.
The 3rd class: process earlier molecular sieve or directly add silicoaluminophosphamolecular molecular sieves as the part of active component or active component with phosphorus-containing compound, and then adding matrix is made catalyst.Make Cracking catalyst as in EP300500, having reported the inorganic oxide matrix of the heavy % of at least a silicoaluminophosphamolecular molecular sieves and 0-99 be combined, for the production of high-knock rating gasoline.Disclosed method is that the NaY molecular sieve after the ammonium exchange is handled the Y zeolite that obtains the heavy % of phosphorous 0.1-4 with the P contained compound aqueous solution of phosphoric acid or its ammonium salt among the EP397183, obtain P-USY through hydrothermal treatment consists again, with high-temperature inorganic oxide and clay pulping, spraying drying makes catalyzer then.This agent has preferably gasoline selective.In USP5110776, reported various molecular sieves (comprising X, Y, USY, REX, REY, RE-USY, ZSM-5, ZSM-22 etc.) are handled with phosphate solution after, drying not, mixes with the matrix precursor pull an oar after, spraying drying is made catalyzer.This agent has good abrasion resistance and higher gasoline octane rating.In WO9421378 be with the phosphoric acid solution of the heavy % of 0.5-4 after under 20-100 ℃ USY equimolecular sieve being carried out modification, be aided with kaolin matrix and make catalyzer, can reduce dry gas and coke.Molecular sieve after will exchanging among the USP5378670, particularly USY molecular sieve are processed with phosphorus-containing compound successively, and hydrothermal treatment consists is processed with phosphorus-containing compound again, obtains phosphorus modified molecular sieves.This molecular sieve can improve cracking activity, the gasoline selective of catalyst and reduce the growing amount of dry gas, coke.
In sum, to the phosphorus modification technology of catalyzer, its purpose is nothing more than being hydrothermal stability and wear resistance for the selectivity that improves product gasoline and octane value, catalyzer in the prior art, and improves coke selectivity.
In recent years, along with the increase year by year and Tarim Basin, the Xinjiang Oilfield developing of China's middle-eastern crude import volume are utilized, content of vanadium generally is higher than 20ppm even up to 60ppm in heavy oil, content of vanadium reaches 7000-11000ppm on the catalytic cracking poiser, high content of vanadium not only makes the structure of catalytic cracking catalyst be damaged, dose consumes more than 80%, and causes quality product and product distribution variation.
The vanadiumism mechanism of catalytic cracking catalyst is: the vanadium in the heavy oil mainly exists to pounce on quinoline vanadium form, in the catalytic cracking reaction process ,+2 ,+3 ,+Low Valent Vanadiums such as 4 valencys are deposited on catalyst surface; In catalyst regeneration process, Low Valent Vanadium is oxidized, changes V into
2O
5And vanadic acid; V
2O
5With vanadic acid further with molecular sieve in reactive aluminum, generate vanadic acid aluminium, molecular sieve structure is damaged.
External each major oil companies are from the late nineteen seventies anti-vanadium catalytic cracking catalyst that just begins one's study.A kind of method is with alkaline earth oxide and vanadium effect, suppresses vanadium to the destruction of molecular sieve.As using MgO and kaolin bead as the anti-vanadium assistant of catalytic cracking catalyst among the USP5300469 (Engelhard company).Use IIA among the USP4485184 (Ashland Oil company), IIIB, IVB, the oxide compound of VB isofamily element is as anti-vanadium catalytic cracking catalyst auxiliary agent.USP4843052, the mixed oxide of using tin, titanium among the USP4940531 has anti-preferably vanadium effect as anti-vanadium component.
Another method is to introduce rare earth in catalyst or matrix, utilizes rare earth oxide to generate the character of stable compound to suppress vanadium to the destruction of molecular sieve with V2O5.In USP4900428 and EP0189267, use soluble ree compound solution impregnated catalyst or matrix such as halogenide, nitrate, rare earth is incorporated in the catalyzer.The catalyst that discloses among USP5248642 and the USP5394299 be take rare earth oxide as active component, aluminium colloidal sol as binding agent, kaolin and sour modified kaolin as matrix, this catalyst shows good anti-vanadium effect.Be with ammoniacal liquor rare earth chloride to be deposited on the Y zeolite among USP4515683 and the ZL88100418, making with this Y zeolite is that the catalytic cracking catalyst of active component has certain anti-vanadium performance.Use the 5-10% bastnasite among the USP5173174, directly join in the catalytic cracking catalyst, this catalyst also has certain anti-vanadium effect.
Up to now, had no molecular sieve and catalyst have all been reduced olefin(e) centent purpose in the FCC gasoline fraction with the phosphorus modification to reach, simultaneously again with the report of deposition of rare-earth as the catalyst of anti-vanadium constituent element.
Purpose of the present invention is exactly to provide a kind of both can reduce olefin(e) centent in the FCC gasoline fraction on the basis of above-mentioned prior art, has molecular sieve type catalytic cracking catalyst of good resistance vanadium effect and preparation method thereof again.
Catalyst provided by the invention is by two kinds of aluminium oxide of the clay of the Y zeolite of the heavy % of 10-60 or Y zeolite and MFI structure molecular screen and/or beta-molecular sieve, the heavy % of 10-75, the heavy % of 10-70, with P
2O
5The phosphorus of the heavy % of the 0.1-7.0 of meter and with RE
2O
3The rare earth of the heavy % of the 0.1-22 of meter forms, and wherein deposition of rare-earth is the heavy % of 0.1-10.
Wherein said Y zeolite is selected from one or more the mixture among HY, REY, REHY, USY, REUSY, the REDASY, and the content of rare earth of said Y zeolite is with RE
2O
3Weight is counted 0-20.0%.
Said MFI structure molecular screen is selected from ZSM-5 or belongs to one or more molecular sieve in the MFI structure with it together, as disclosed among CN1052290A, CN1058382A, CN1147420A, the CN1194181A.
When using multiple molecular sieve in the catalyzer, the weight ratio with MFI structure molecular screen and Y zeolite should be 0.01-0.5, preferred 0.015-0.25; The weight ratio of beta-molecular sieve and Y zeolite should be 0.025-0.8.
In the catalyzer provided by the present invention, sedimentary rare earth constituent element, it is different from containedly in the Y zeolite passes through the rare earth existence form that the ionic liquid phase exchanging form occupies the molecular sieve cation-bit, its precursor is a rare earth hydrate, be the surface that is deposited on catalyzer with rare earth hydrate precipitation suspension, drying, roasting obtain.This rare earth constituent element forms stable rare-earth vanadate and loses flowability be deposited on vanadic acid chemical combination that the vanadium on the catalyst generates in the regenerative agent environment, has avoided the destruction to the catalyst activity component, thereby has played the effect of anti-vanadium, and it is with RE
2O
3Meter accounts for the heavy % of 0.1-10.0 of catalyst, the heavy % of preferred 0.1-5,
Said clay is a catalytic cracking catalyst matrix clay commonly used, as kaolin, halloysite, polynite, wilkinite etc.
Said two kinds of aluminum oxide are respectively from the mixture of the aluminum oxide of pseudo-boehmite and aluminium colloidal sol.Wherein account for the 6-40% of catalyst weight, preferably 10-25% from the aluminum oxide of pseudo-boehmite; Account for the 4-30% of catalyst weight from the aluminum oxide of aluminium colloidal sol, preferably 10-20%.
Catalyzer provided by the invention makes according to following method: Y zeolite is carried out one or many with P contained compound solution handle, make the phosphorus content on the molecular sieve reach desired value, dry, after 350-750 ℃ of roasting 0.1-8 hour, or will be through the Y zeolite of above-mentioned processing with after molecular sieve with MFI structure and/or beta-molecular sieve mix, with double aluminium binder, clay, rare earth hydrate suspension mixes, homogeneous is after 500 ℃ of roasting 0.5-6 hour or spraying dryings, washing then, filter, use the aftertreatment of P contained compound solution again, promptly obtain cracking catalyst provided by the invention after the drying.
In method provided by the invention, said method with phosphorus-containing compound solution-treated molecular sieve is: with molecular sieve with its butt weight ratio be 0.5-3.0, elemental phosphorous content be in the phosphorus-containing compound solution of 0.05-5.0% in 4-80 ℃ of lower dipping or after stirring 0.1-8 hour, 100-120 ℃ dry 1-10 hour.So carry out one or many, phosphorus content is with P in the dried molecular sieve
2O
5Count the heavy % of 0.05-10.
Said double aluminium binder is the mixture of pseudo-boehmite and aluminium colloidal sol, and wherein all or part of pseudo-boehmite needs acidified and burin-in process.Concrete processing method is: after clay and boehmite are mixed making beating, with the sour aluminium weight ratio hcl acidifying that is 0.15-0.50, in 40-90 ℃ of aging 0.5-5 hour.
Said with the phosphorus-containing compound last handling process be with gained roasting or spray-drying product with its butt weight ratio be 0.5-4.0, elemental phosphorous content be stirred 1-8 hour in the phosphorus-containing compound solution of 0.1-2.0% or filter carry out with the exchange of phosphorus-containing compound solution and absorption after, 100-120 ℃ dry 1-10 hour.
Said P contained compound be phosphorus water-soluble cpds, comprise ortho-phosphoric acid, phosphorous acid, phosphoric anhydride, ammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate, ammonium phosphite, aluminum phosphate etc., be best with phosphoric acid and ammonium salt thereof wherein, this ammonium salt also can be formulated with phosphoric acid and ammoniacal liquor.The concentration of P contained compound solution is with the elemental phosphorous heavy % of 0.05-5.0 that counts.
Said rare earth hydrate suspension mixes formation with re chloride with a kind of inorganic alkali lye.Use NaOH or potassium hydroxide as inorganic base, unavoidably can be with Na
+Or K
+Ion is introduced, and catalyst is had adverse influence, and therefore, preferred ammoniacal liquor is as the inorganic base of preparation rare earth hydrate suspension, and concrete preparation process is: will be with RE
2O
3Meter concentration is the re chloride of 100-300 grams per liter, and ammoniacal liquor to the precipitated liquid pH value that suspends that under agitation adds the heavy % of 10-30 is 8-10.
Compare with the catalyzer of the phosphorous and rare earth of other prior art, the advantage that when catalyzer provided by the invention is used for catalytic cracking process, have that activity stability height, strong, the anti-pollution of vanadium of heavy oil conversion performance are effective, olefin(e) centent is low, coke is few in the product gasoline.
Following example will be described further Catalysts and its preparation method provided by the invention.
In example, the vanadium in the sample catalyst and content of rare earth are measured with XRF, and phosphorus content is that chemical colorimetry is measured.
The method of catalyzer pollution of vanadium is in the laboratory: in proportion with the cyclohexane solution impregnated catalyst of naphthenic acid vanadium 1 hour, and 120 ℃ of oven dry 4 hours, 550 ℃ of roastings 4 hours, hydrothermal aging then.
The catalyzer that is used for the little anti-and fixed fluidized bed evaluation of light oil is in advance through aging 4 hours or 17 hours of 800 ℃, 100% water vapour.
The little anti-appreciation condition of light oil is: 235-335 ℃ huge port solar oil is a raw material, and agent-oil ratio is 3.2, and weight space velocity is 16h
-1, temperature is 460 ℃.
Fixed fluidized bed appreciation condition is: temperature of reaction is 520 ℃, weight space velocity 20h
-1, the catalyzer loading amount is 90 grams, and agent-oil ratio is 5, and reaction raw materials is the defeated VGO+20% vacuum residuum of 80% pipe.
Olefin(e) centent is by gas Chromatographic Determination in the gasoline.
Example 1
Will be in elemental phosphorous, 450 milliliters of ammonium dibasic phosphate solutions of phosphorous 100 grams per liters add 2 kilograms of REHY molecular sieve (Qilu Petrochemical Company catalyst plant product, RE that (butt) is wetting
2O
3Content is 7.5 heavy %, Na
2O content 4.1 heavy %, silica alumina ratio 5.6), mixing stirred 3 hours, in 120 ℃ lower dry 2 hours, then roasting 2 hours in air under 500 ℃.
Other gets RE
2O
3Be the RECl of 228 grams per liters
3Solution (Inner Mongol Baotou rare earth factory product, wherein CeO
250%, La
2O
321%, Pr
2O
314%, Nd
2O
313%) 692 milliliters is that 28% concentrated ammonia liquor slowly splashes into and constantly stir the companion with concentration, until the pH value to 8.8 of precipitation suspension.
In the making beating tank, add 1.67 kilograms of kaolin (solid contents 85.0%, China Kaolin Co., Ltd's industrial products), add the making beating of 4 kg water, add then 3.02 kilograms of boehmites (solid content 34.8 heavy %, Shandong Aluminum Plant's product), stir after 2 hours, the hydrochloric acid that adds again 777 grams, 37 heavy %, stir after 1 hour, 75 ℃ of lower wearing out 2 hours, add then 2.5 kilograms of aluminium colloidal sols and (contain Al
2O
321 heavy %, Qilu Petrochemical Company catalyst plant product), pulled an oar 1 hour.
The rare earth suspension of precipitation is added in the above-mentioned making beating tank and stirs.
(Qilu Petrochemical company catalyst plant is produced for the phosphorous REHY molecular sieve that roasting is good and 105 gram (butt) MFI structure molecular screens, silica alumina ratio 60), 3.9 kg water were mixed making beating after 2 hours, join in the making beating jar in second step making beating homogeneous 5 hours, spraying drying then.
The catalyst that spray-drying is obtained washs at filter under 60 ℃, and be that the ammonium dibasic phosphate solutions of 1.0 heavy % are processed in order to elemental phosphorous meter solution containing phosphate concentration, filtration, 120 ℃ of lower dryings namely obtain phosphorous and rare earth containing zeolite catalyst A provided by the invention.
Consisting of of catalyst A: kaolin 26.2 heavy %, from the aluminium oxide of boehmite be 19.4 heavy %, aluminium oxide 9.7 heavy %, Y zeolite 34.2 heavy % from aluminium colloidal sol, MFI structure molecular screen 1.9 heavy %, P
2O
53.0 heavy %, RE
2O
35.6 heavy %, wherein deposition of rare-earth is with RE
2O
3Count 2.9 heavy %.
Comparative Examples 1
Prepare catalyzer by example 1 described method, but the REHY molecular sieve is handled without phosphorus.This contrast medium is designated as DA1.
Catalyst DA1 consists of: kaolin 26.8 heavy %, from the aluminium oxide of boehmite be 19.8 heavy %, aluminium oxide 9.9 heavy %, Y zeolite 35.2 heavy % from aluminium colloidal sol, MFI structure molecular screen 2 heavy %, P
2O
50.9 heavy %, RE
2O
35.4 heavy %, wherein deposition of rare-earth is with RE
2O
3Count 2.8 heavy %.
Comparative Examples 2
Prepare contrast medium by example 1 described method, but without solution containing phosphate catalyzer is handled in the washing process after spraying drying, obtain contrast medium DA2.
Catalyst DA2 consists of: kaolin 26.5 heavy %, from the aluminium oxide of boehmite be 19.6 heavy %, aluminium oxide 9.8 heavy %, Y zeolite 37.2 heavy % from aluminium colloidal sol, MFI structure molecular screen 2.0 heavy %, P
2O
52.0 heavy %, RE
2O
35.9 heavy %, the wherein RE of deposition
2O
3Be 2.9 heavy %.
Comparative Examples 3
Prepare contrast medium by example 1 described method, but in becoming the glue process, do not add the rare earth hydrate as anti-vanadium constituent element.This contrast medium is designated as DA3.
Catalyst DA3 consists of: kaolin 29.1 heavy %, from the aluminium oxide of boehmite be 19.4 heavy %, aluminium oxide 9.7 heavy %, Y zeolite 34.2 heavy % from aluminium colloidal sol, MFI structure molecular screen 1.9 heavy %, P
2O
52.9 heavy %, RE
2O
32.8 heavy %.
The catalyst sample of above-mentioned preparation is carried out pollution of vanadium: in proportion with the cyclohexane solution impregnated catalyst of naphthenic acid vanadium 1 hour, 120 ℃ of oven dry 4 hours, 550 ℃ of roastings 4 hours, hydrothermal aging then.Relevant Analysis and evaluation result are listed in table 1.
Table 1
| Catalyst | A | DA1 | DA2 | DA3 |
| Content of vanadium ppm | 5000 | 5000 | 5000 | 5000 |
| Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % | 78 60 | 79 62 | 75 56 | 71 49 |
| Fixed fluidized bed, heavy % casing head gasoling light diesel fuel coke | 15.2 51.3 21.1 5.8 | 16.4 50.1 20.5 6.8 | 14.2 49.2 22.7 5.7 | 13.3 48.4 23.3 5.2 |
| Olefin(e) centent in the gasoline, heavy % | 19.9 | 24.3 | 23.9 | 26.3 |
Can find out that from table 1 data catalyst A has than contrast medium DA1 and DA2 and has the ability of better reduction gasoline olefin.Compare with DA3, because the adding of anti-vanadium constituent element makes it possess good anti-vanadium ability.
Embodiment 2
(the Qilu Petrochemical Company catalyst plant is produced, RE to 2.1 kilograms of (butt) REY molecular sieves
2O
3Content is 19.5 heavy %, Na
2O content 1.6 heavy %, silica alumina ratio 5.4) in 3.2 kilograms of concentration be the ammonium dihydrogen phosphates of 4.1 heavy % (in the ammonium dihydrogen phosphate (ADP) amount), stir and evenly mix 2 hours, in 110 ℃ lower dry 3 hours, then roasting 3 hours in air under 550 ℃.
Other gets RE
2O
3Be the RECl of 279 grams per liters
3Solution (Inner Mongol Baotou rare earth factory product, wherein La
2O
3Content 70%, CeO
220%, Pr
2O
35%, Nd
2O
33%) 602 milliliters is that 28% concentrated ammonia liquor slowly splashes into and constantly stir the companion with concentration, until the pH value to 9.2 of precipitation suspension.
In the making beating tank, add 2.96 kilograms of kaolin (solid content 85.0%), add the making beating of 5 kg water, add then 5.32 kilograms of boehmites (solid content 34.8 heavy %), stir after 2 hours, the hydrochloric acid that adds again 1.32 kilogram of 37 heavy %, stir after 1 hour, 85 ℃ of lower wearing out 3 hours, add then 6.4 kilograms of aluminium colloidal sols and (contain Al
2O
321 heavy %), pulled an oar 2 hours.
The rare earth suspension of precipitation is added in the above-mentioned making beating tank and stirs.
The phosphorous REY molecular sieve that roasting is good and 420 gram (butt) beta-molecular sieves (Chang Ling catalyst plant produce, silica alumina ratio 30), 3.9 kg water were mixed making beating after 2 hours, joined in the making beating jar in second step, the homogeneous 4 hours of pulling an oar again, spraying drying then.
The catalyst that spray-drying is obtained washs at filter under 60 ℃, and is that the ammonium dibasic phosphate solution of 0.5 heavy % is processed in order to elemental phosphorous meter solution containing phosphate concentration, filter, 120 ℃ lower dry, namely obtain phosphorus containing molecular sieve catalyst B provided by the invention.
Consisting of of catalyst B: kaolin 29.3 heavy %, from the aluminium oxide of boehmite be 21.5 heavy %, aluminium oxide 15.6 heavy %, Y zeolite 19.6 heavy % from aluminium colloidal sol, beta-molecular sieve 4.9 heavy %, P
2O
52.3 heavy %, RE
2O
3Be 6.8 heavy %, wherein deposition of rare-earth is with RE
2O
3Count 2.0 heavy %.
Comparative Examples 4
It is described that step is pressed example 2, but do not deposit rare earth hydrate, but by patent USP4900428, after the 3rd step catalyst was processed with the phosphorus ammonium salt solution, other got RE
2O
3Be the rich cerium type RECl of 228 grams per liters
3Solution (CeO
265%, La
2O
322%, Pr
2O
34%, Nd
2O
37%) 737ml, impregnated catalyst after the suitable quantity of water dilution was dried 2 hours for 110 ℃, put into 500 ℃ of muffle furnaces again and did roasting 2 hours, obtained contrast medium DB1.
Catalyst DB consists of: kaolin 29.3 heavy %, from the aluminium oxide of boehmite be 21.5 heavy %, aluminium oxide 15.6 heavy %, Y zeolite 19.6 heavy % from aluminium colloidal sol, beta-molecular sieve 4.9 heavy %, P
2O
52.3 heavy %, RE
2O
36.8 heavy %, wherein the rare earth of catalyst proofing is with RE
2O
3Count 2.0 heavy %.
The catalyst sample of above-mentioned preparation is carried out pollution of vanadium: in proportion with the cyclohexane solution impregnated catalyst of naphthenic acid vanadium 1 hour, 120 ℃ of oven dry 2 hours, 550 ℃ of roastings 4 hours, hydrothermal aging then.Relevant Analysis and evaluation result are listed in table 2.
Table 2
| Catalyst | B | DB |
| Content of vanadium ppm | 5000 | 5000 |
| Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % | 81 63 | 77 53 |
| Fixed fluidized bed, heavy % casing head gasoling light diesel fuel coke | 16.2 49.3 21.1 6.2 | 15.1 48.1 22.5 6.7 |
| Olefin(e) centent in the gasoline, heavy % | 20.3 | 25.6 |
From table 2 data as seen, adopt the catalyst B of the inventive method preparation, have better anti-vanadium performance than contrast medium, the corresponding ability that it reduces gasoline olefin is also stronger, and olefin(e) centent is lower in the gasoline.
Example 3
Will be in elemental phosphorous, 300 milliliters of phosphoric acid of phosphorous 150 grams per liters and ammoniacal liquor mixing solutions add 2 kilograms of (butt) USY molecular sieves (the Chang Ling catalyst plant are produced, Na
2O content 0.8 heavy %, silica alumina ratio 7,8), mixing stirred 2 hours, in 140 ℃ dry 1 hour down, then roasting 2 hours in air under 450 ℃.
Other gets RE
2O
3Rich cerium type RECl for 228g/l
3Solution (Inner Mongol Baotou rare earth factory product, wherein CeO
275%, La
2O
315%, Pr
2O
35%, Nd
2O
33%) 548 milliliters is that 28% concentrated ammonia liquor slowly splashes into and constantly stir the companion with concentration, until the pH value to 9.5 of precipitation suspension.
In the making beating tank, add 1.38 kilograms of kaolin (solid content 85.0%), add the making beating of 4 kg water, add then 2.59 kilograms of boehmites (solid content 34.8 heavy %), stir after 4 hours, the hydrochloric acid that adds again 647 grams, 37 heavy %, stir after 2 hours, 60 ℃ of lower wearing out 5 hours, add then 2.86 kilograms of aluminium colloidal sols and (contain Al
2O
321 heavy %), pulled an oar 2 hours.
The rare earth suspension of precipitation is added in the above-mentioned making beating tank and stirs.
Phosphorous USY molecular sieve that roasting is good and 200 gram (butt) MFI structure molecular screens (Chang Ling catalyst plant product, silica alumina ratio 30), 4.0 kg water were mixed making beating after 2 hours, joined in the making beating jar in second step, the homogeneous 3 hours of pulling an oar again, spraying drying then.
The catalyst that spray-drying is obtained washs at filter under 60 ℃, and is that the ammonium dibasic phosphate solutions of 1.5 heavy % are processed in order to elemental phosphorous meter solution containing phosphate concentration, filter, 120 ℃ lower dry, namely obtain phosphorus containing molecular sieve catalyst C provided by the invention.
Catalyst C consists of: kaolin 22.9 heavy %, from the aluminium oxide of boehmite be 17.5 heavy %, aluminium oxide 11.7 heavy %, USY molecular sieve 38.9 heavy % from aluminium colloidal sol, MFI structure molecular screen 3.9 heavy %, P
2O
52.6 heavy %, deposition of rare-earth are with RE
2O
3Count 2.5 heavy %.
Comparative Examples 5
Step is pressed described in the example 3, but does not deposit rare earth hydrate, but prepares 2 kilograms in molecular sieve of deposition of rare-earth type USY (butt) by patent CN88100418A method, wherein on the molecular sieve deposition of rare-earth amount with RE
2O
3Count 6.0 heavy %, obtain contrast medium DC.
Catalyst DC consists of: kaolin 24.3 heavy %, from the aluminium oxide of boehmite be 17.5 heavy %, aluminium oxide 11.7 heavy %, USY type molecular sieve 37.6 heavy % from aluminium colloidal sol, MFI structure molecular screen 3.9 heavy %, P
2O
52.7 heavy %, RE
2O
32.3 heavy %.
The catalyst sample of above-mentioned preparation is carried out pollution of vanadium: in proportion with the cyclohexane solution impregnated catalyst of naphthenic acid vanadium 1 hour, 120 ℃ of oven dry 2 hours, 550 ℃ of roastings 4 hours, hydrothermal aging then.Relevant Analysis and evaluation result are listed in table 3.
Table 3
| Catalyst | C | DC |
| Content of vanadium ppm | 5000 | 5000 |
| Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % | 72 55 | 63 40 |
| Fixed fluidized bed, heavy % casing head gasoling light diesel fuel coke | 15.1 51.2 22.6 4.7 | 13.2 48.2 24.5 4.9 |
| Olefin(e) centent in the gasoline, heavy % | 24.3 | 31.6 |
From table 3 data as seen, adopt the catalyst C of the inventive method preparation, have better anti-vanadium performance than contrast medium, the corresponding ability that it reduces gasoline olefin is also stronger, and olefin(e) centent is lower in the gasoline.
Example 4
Will be in elemental phosphorous, 218 milliliters of ammonium phosphate solutions of phosphorous 100 grams per liters join wetting 2 kilograms of (butt) REUSY molecular sieves (Chang Ling catalyst plant product, RE
2O
3Content 6.2 heavy %, Na
2O content 0.8 heavy %, silica alumina ratio 6.8), mixing stirred 2 hours, in 140 ℃ lower dry 1 hour, then roasting 8 hours in air under 350 ℃.
Other gets RE
2O
3Rich lanthanum type RECl for 240g/l
3Solution (Inner Mongol Baotou rare earth factory product, wherein La
2O
375%, CeO
218%, Pr
2O
32%, Nd
2O
33%) 438 milliliters is that 28% concentrated ammonia liquor slowly splashes into and constantly stir the companion with concentration, until the pH value to 9.2 of precipitation suspension.
In the making beating tank, add 1.73 kilograms of kaolin (solid content 85.0%), add the making beating of 4 kg water, add then 1.51 kilograms of boehmites (solid content 34.8 heavy %), stir after 4 hours, the hydrochloric acid that adds again 378 grams, 37 heavy %, stir after 1 hour, 85 ℃ of lower wearing out 2 hours, add then 5.01 kilograms of aluminium colloidal sols and (contain Al
2O
321 heavy %), pulled an oar 2 hours.
The rare earth suspension of precipitation is added in the above-mentioned making beating tank and stirs.
Phosphorous REUSY molecular sieve that roasting is good and 105 gram (butt) MFI structure molecular screens (silica alumina ratio 200), 4.0 kg water were mixed making beating after 2 hours, joined in the second making beating jar that goes on foot, the homogeneous 4 hours of pulling an oar again, spraying drying then.
The catalyst that spray-drying is obtained washs at filter under 70 ℃, and be that the ammonium dibasic phosphate solutions of 1.0 heavy % are processed in order to elemental phosphorous meter solution containing phosphate concentration, filter, 120 ℃ lower dry, namely obtain the molecular sieve catalyst D of phosphorous and rare earth provided by the invention.
Catalyst D consists of: kaolin 27.6 heavy %, be 9.8 heavy %, the aluminium oxide 19.6 heavy % from aluminium colloidal sol, phosphorous REUSY type molecular sieve 35.1 heavy %, MFI structure molecular screen 2.0 heavy %, P from the aluminium oxide of boehmite
2O
51.6 heavy %, RE
2O
3Be 4.3 heavy %, wherein deposition of rare-earth is with RE
2O
3Count 2.0 heavy %.
Example 5
Prepare catalyzer by example 4 described methods, but the mixed molecular sieve of 1 kilogram of (butt) REUSY and 1 kilogram of (butt) REHY is carried out the phosphorus processing, the gained catalyzer is designated as E.
Catalyst E consists of: kaolin 27.6 heavy %, from the aluminium oxide of boehmite be 9.8 heavy %, aluminium oxide 19.6 heavy %, REUSY type molecular sieve 17.5 heavy % from aluminium colloidal sol, REHY type molecular sieve 17.3 heavy %, MFI structure molecular screen 2.0 heavy %, P
2O
51.6 heavy %, RE
2O
3Be 4.6 heavy %, wherein deposition of rare-earth is with RE
2O
3Count 2.0 heavy %.
Comparative Examples 6
Press example 4 described method Kaolinite Preparation of Catalysts, but the roasting when molecular sieve phosphorus is processed is in 100% steam, and solution containing phosphate useless is processed to filter cake in the 3rd step, this contrast medium is denoted as DD1.
Catalyst DD1 consists of: kaolin 27.6 heavy %, be 10.0 heavy %, the aluminium oxide 20.0 heavy % from aluminium colloidal sol, phosphorous REUSY type molecular sieve 35.1 heavy %, MFI structure molecular screen 2.0 heavy %, P from the aluminium oxide of boehmite
2O
51.0 heavy %, RE
2O
34.3 heavy %, wherein deposition of rare-earth is with RE
2O
3Count 2.0 heavy %.
Comparative Examples 7
Prepare contrast medium by example 4 described methods, but in becoming the glue process, do not add the rare earth hydrate as anti-vanadium constituent element.This contrast medium is designated as DD2.
Catalyst DD2 consists of: kaolin 29.5 heavy %, from the aluminium oxide of boehmite be 9.8 heavy %, aluminium oxide 19.6 heavy %, REUSY type molecular sieve 35.1 heavy % from aluminium colloidal sol, MFI structure molecular screen 2.0 heavy %, P
2O
51.6 heavy %, RE
2O
32.3 heavy %.
The catalyst sample of above-mentioned preparation is carried out pollution of vanadium: in proportion with the cyclohexane solution impregnated catalyst of naphthenic acid vanadium 1 hour, 120 ℃ of oven dry 2 hours, 550 ℃ of roastings 4 hours, hydrothermal aging then.Relevant Analysis and evaluation result are listed in table 4.
From table 4 data as seen, adopt catalyst D and the E of the inventive method preparation, have better anti-vanadium performance than contrast medium, the corresponding ability that it reduces gasoline olefin is also stronger, and olefin(e) centent is lower in the gasoline.
Table 4
| Catalyst | D | E | DD1 | DD2 |
| Content of vanadium ppm | 5000 | 5000 | 5000 | 5000 |
| Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % | 77 58 | 78 60 | 75 54 | 70 43 |
| Fixed fluidized bed, heavy % casing head gasoling light diesel fuel coke | 15.9 50.7 21.7 5.5 | 15.5 51.0 21.9 5.7 | 15.3 49.8 22.3 5.6 | 14.0 48.1 23.9 5.2 |
| Olefin(e) centent in the gasoline, heavy % | 20.5 | 20.4 | 25.3 | 29.1 |
Example 6
Will be in elemental phosphorous, 87.3 milliliters of ammonium dibasic phosphate solutions of phosphorous 100 grams per liters add 2 kilograms of REHY molecular sieve (Chang Ling catalyst plant product, RE that (butt) is wetting
2O
3Content is 8.4 heavy %, Na
2O content 3.7 heavy %, silica alumina ratio 5.6), mixing stirred 5 hours, in 120 ℃ lower dry 1.5 hours, then roasting 3 hours in air under 575 ℃.
Other gets RE
2O
3Rich cerium type RECl for 228g/l
3Solution (originates from Inner Mongol Baotou rare earth factory, wherein CeO
2Content 50%, La
2O
321%, Pr
2O
314%, Nd
2O
313%) 250 milliliters is that 28% concentrated ammonia liquor slowly splashes into and constantly stir the companion with concentration, until the pH value to 9.1 of precipitation suspension.
In the making beating tank, add 0.67 kilogram of kaolin (solid content 85.0 heavy %), add the making beating of 4 kg water, add then 4.59 kilograms of boehmites (solid content 34.8 heavy %), stir after 2 hours, the hydrochloric acid that adds again 919 grams, 37 heavy %, stir after 3 hours, 70 ℃ of lower wearing out 5 hours, add then 5.43 kilograms of aluminium colloidal sols and (contain Al
2O
321 heavy %), pulled an oar 3 hours.
The rare earth suspension of precipitation is added in the above-mentioned making beating tank and stirs.
(the Chang Ling catalyst plant is produced for the phosphorous REHY molecular sieve that roasting is good and 114 gram (butt) MFI structure molecular screens, silica alumina ratio 120), 286 gram (butt) beta-molecular sieves (produce by the Chang Ling catalyst plant, silica alumina ratio 25), 4 kg water were mixed making beating after 3 hours, join in the making beating jar in second step, pull an oar again homogeneous 5 hours, spraying drying then.
The catalyst that spray-drying is obtained washs at filter under 60 ℃, and is that the ammonium dibasic phosphate solutions of 1.0 heavy % are processed in order to elemental phosphorous meter solution containing phosphate concentration, filter, 120 ℃ lower dry, namely obtain phosphorus containing molecular sieve catalyst F provided by the invention.
Catalyst F consists of: kaolin 10.0 heavy %, from the aluminium oxide of boehmite be 27.6 heavy %, aluminium oxide 19.8 heavy %, REHY type molecular sieve 31.7 heavy % from aluminium colloidal sol, MFI structure molecular screen 2.0 heavy %, beta-molecular sieve 4.9 heavy %, P
2O
51.1 heavy %, RE
2O
32.9 heavy %, wherein deposition of rare-earth is with RE
2O
3Count 1.0 heavy %.
Comparative Examples 8
Prepare contrast medium by example 6 described methods, but in becoming the glue process, do not add the rare earth hydrate as anti-vanadium constituent element.This contrast medium is designated as DF.
The rate of charge of catalyst DF is: kaolin 10.0 heavy %, from the aluminium oxide of boehmite be 27.6 heavy %, aluminium oxide 19.8 heavy %, REHY type molecular sieve 31.7 heavy % from aluminium colloidal sol, MFI structure molecular screen 2.0 heavy %, beta-molecular sieve 4.9 heavy %, P
2O
51.1 heavy %, RE
2O
32.9 heavy %.
Example 7
Will be in elemental phosphorous, 933 milliliters of ammonium hydrogen phosphate solution of phosphorous 150 grams per liters add 2 kilograms of REHY molecular sieve (Chang Ling catalyst plant product, RE that (butt) is wetting
2O
3Content is 8.4 heavy %, Na
2O content 3.7 heavy %, silica alumina ratio 5.6), mixing stirred 5 hours, in 120 ℃ lower dry 3.5 hours, then roasting 6 hours in air under 475 ℃.
Other gets RE
2O
3Rich cerium type RECl for 228g/l
3Solution (originates from Inner Mongol Baotou rare earth factory, wherein CeO
250%, La
2O
321%, Pr
2O
314%, Nd
2O
313%) 1465 milliliters is that 28% concentrated ammonia liquor slowly splashes into and constantly stir the companion with concentration, until the pH value to 9.0 of precipitation suspension.
In the making beating tank, add 3.2 kilograms of kaolin (solid content 85.0 heavy %), add the making beating of 5 kg water, add then 1.15 kilograms of boehmites (solid content 34.8 heavy %), stir after 1 hour, the hydrochloric acid that adds again 287 grams, 37 heavy %, stir after 3 hours, 70 ℃ of lower wearing out 3 hours, add then 1.9 kilograms of aluminium colloidal sols and (contain Al
2O
321 heavy %), pulled an oar 3 hours.
The rare earth suspension of precipitation is added in the above-mentioned making beating tank and stirs.
(the Chang Ling catalyst plant is produced for the phosphorous REHY molecular sieve that roasting is good and 267 gram (butt) MFI structure molecular screens, silica alumina ratio 200), 534 gram (butt) beta-molecular sieves (produce by the Chang Ling catalyst plant, silica alumina ratio 60), 4 kg water were mixed making beating after 3 hours, join in the making beating jar in second step, pull an oar again homogeneous 5 hours, spraying drying then.
The catalyst that spray-drying is obtained washs at filter under 60 ℃, and is that the ammonium dibasic phosphate solutions of 1.0 heavy % are processed in order to elemental phosphorous meter solution containing phosphate concentration, filter, 120 ℃ lower dry, namely obtain phosphorus containing molecular sieve catalyst G provided by the invention.
The rate of charge of catalyst G is: kaolin 38.4 heavy %, from the aluminium oxide of boehmite be 5.6 heavy %, aluminium oxide 5.6 heavy %, REHY type molecular sieve 25.7 heavy % from aluminium colloidal sol, MFI structure molecular screen 3.7 heavy %, beta-molecular sieve 7.4 heavy %, P
2O
56.5 heavy %, RE
2O
37.1 heavy %, wherein deposition of rare-earth is with RE
2O
3Count 4.7 heavy %.
Comparative Examples 9
Prepare contrast medium by example 7 described methods, but in becoming the glue process, do not add the rare earth hydrate as anti-vanadium constituent element.This contrast medium is designated as DG.
The rate of charge of catalyst DG is: kaolin 43.1 heavy %, from the aluminium oxide of boehmite be 5.6 heavy %, aluminium oxide 5.6 heavy %, REHY type molecular sieve 25.7 heavy % from aluminium colloidal sol, MFI structure molecular screen 3.7 heavy %, beta-molecular sieve 7.5 heavy %, P
2O
56.4 heavy %, RE
2O
32.4 heavy %.
The catalyst sample of above-mentioned preparation is carried out pollution of vanadium: in proportion with the cyclohexane solution impregnated catalyst of naphthenic acid vanadium 1 hour, 120 ℃ of oven dry 2 hours, 550 ℃ of roastings 4 hours, hydrothermal aging then.Relevant Analysis and evaluation result are listed in table 5.
Table 5
| Catalyst | F | DF | G | DG |
| Content of vanadium ppm | 5000 | 5000 | 5000 | 5000 |
| Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % | 79 54 | 73 47 | 84 68 | 71 40 |
| Fixed fluidized bed, heavy % casing head gasoling light diesel fuel coke | 18.0 53.7 23.3 5.0 | 15.2 51.0 29.0 4.8 | 19.1 54.2 20.6 6.1 | 16.0 51.1 28.8 4.1 |
| Olefin(e) centent in the gasoline, heavy % | 22.4 | 28.4 | 18.8 | 31.0 |
From table 5 data as seen, catalyst F provided by the invention and G have better anti-vanadium performance than contrast medium, and the corresponding ability that it reduces gasoline olefin is also stronger, and olefin(e) centent is lower in the gasoline.
Example 8
Will be in elemental phosphorous, 480 milliliters of ammonium phosphate solutions of phosphorous 100 grams per liters add 2 kilograms of (butt) REHY molecular sieves (Qilu Petrochemical Company catalyst plant product, RE
2O
3Content is 10 heavy %, Na
2O content 3.2 heavy %, silica alumina ratio 5.5), mixing stirred 3 hours, in 120 ℃ lower dry 2 hours, then roasting 2 hours in air under 500 ℃.
Other gets RE
2O
3Be the RECl of 228 grams per liters
3Solution (Inner Mongol Baotou rare earth factory product, wherein CeO
250%, La
2O
321%, Pr
2O
314%, Nd
2O
313%) 923 milliliters is that 28% concentrated ammonia liquor slowly splashes into and constantly stir the companion with concentration, until the pH value to 9.2 of precipitation suspension.
In the making beating tank, add 1.8 kilograms of kaolin (solid contents 85.0%, China Kaolin Co., Ltd's industrial products), add the making beating of 4 kg water, add then 3.02 kilograms of boehmites (solid content 34.8 heavy %, Shandong Aluminum Plant's product), stir after 2 hours, the hydrochloric acid that adds again 777 grams, 37 heavy %, stir after 1 hour, 75 ℃ of lower wearing out 2 hours, add then 2.5 kilograms of aluminium colloidal sols and (contain Al
2O
321 heavy %, Qilu Petrochemical Company catalyst plant product), pulled an oar 1 hour.
The rare earth suspension of precipitation is added in the above-mentioned making beating tank and stirs.
The phosphorous REHY molecular sieve that roasting is good mixed making beating after 2 hours with 4.0 kg water, join in the making beating tank of second step making beating homogeneous 3 hours, then spray-drying.
The catalyst that spray-drying is obtained washs at filter under 60 ℃, and be that the ammonium dibasic phosphate solutions of 1.0 heavy % are processed in order to elemental phosphorous meter solution containing phosphate concentration, filtration, 120 ℃ of lower dryings namely obtain phosphorous and rare earth containing zeolite catalyst H provided by the invention.
Catalyst H consists of: kaolin 27.8 heavy %, from the aluminium oxide of boehmite be 19.2 heavy %, aluminium oxide 9.6 heavy %, Y zeolite 32.8 heavy %, P from aluminium colloidal sol
2O
53.1 heavy %, RE
2O
37.5 heavy %, wherein deposition of rare-earth is with RE
2O
3Count 3.9 heavy %.
Comparative Examples 10
Press example 8 described method Kaolinite Preparation of Catalysts, but in becoming the glue process, do not add the rare earth hydrate as anti-vanadium constituent element.The DH that this contrast medium is designated as.
The rate of charge of catalyst DH is: kaolin 28.9 heavy %, from the aluminium oxide of boehmite be 20.0 heavy %, aluminium oxide 10 heavy %, REHY type molecular sieve 34.1 heavy %, P from aluminium colloidal sol
2O
53.2 heavy %, RE
2O
33.8 heavy %.
The catalyst sample of above-mentioned preparation is carried out pollution of vanadium: in proportion with the cyclohexane solution impregnated catalyst of naphthenic acid vanadium 1 hour, 120 ℃ of oven dry 2 hours, 550 ℃ of roastings 4 hours, hydrothermal aging then.Relevant Analysis and evaluation result are listed in table 6.
Table 6
| Catalyst | H | DH |
| Content of vanadium ppm | 5000 | 5000 |
| Micro-activity, 800 ℃/17hr of 800 ℃/4hr of heavy % | 77 58 | 71 42 |
| Fixed fluidized bed, heavy % casing head gasoling light diesel fuel coke | 13.1 52.7 22.6 4.9 | 12.2 48.2 29.5 4.0 |
| Olefin(e) centent in the gasoline, heavy % | 22.3 | 31.2 |
From table 6 data as seen, catalyst H provided by the invention has better anti-vanadium performance than contrast medium, and the corresponding ability that it reduces gasoline olefin is also stronger, and olefin(e) centent is lower in the gasoline.
Claims (17)
1, a kind of hydrocarbon cracking catalyzer of anti-vanadium is characterized in that:
(1) by two kinds of aluminium oxide of the clay of the Y zeolite of the heavy % of 10-60 or Y zeolite and MFI structure molecular screen and/or beta-molecular sieve, the heavy % of 10-75, the heavy % of 10-70, with P
2O
5The phosphorus of the heavy % of the 0.1-7.0 of meter and with RE
2O
3The rare earth of the heavy % of the 0.1-22 of meter forms, and wherein deposition of rare-earth is the heavy % of 0.1-10;
(2) its preparation method is as follows: Y zeolite is carried out one or many with P contained compound solution handle, make the phosphorus content on the molecular sieve reach desired value, dry, after 350-750 ℃ of roasting 0.1-8 hour with double aluminium binder, clay, rare earth hydrate precipitation suspension mixes, or will be through the Y zeolite of above-mentioned processing with after molecular sieve with MFI structure and/or beta-molecular sieve mix and double aluminium binder, clay, rare earth hydrate precipitation suspension mixes, homogeneous is after 500 ℃ of roasting 0.5-6 hour or spraying dryings, washing then, filter, use the aftertreatment of P contained compound solution again, drying.
2,, it is characterized in that wherein said Y zeolite is selected from one or more the mixture among HY, REY, REHY, USY, REUSY, the REDASY according to the described catalyzer of claim 1.
3, according to the described catalyst of claim 2, it is characterized in that the content of rare earth of said Y zeolite wherein is with RE
2O
3Weight is counted 0-20.0%.
4,, it is characterized in that said MFI structure molecular screen is selected from ZSM-5 or its and belongs to one or more molecular sieve in the MFI structure together according to the described catalyzer of claim 1.
5,, it is characterized in that having the molecular sieve of MFI structure and the weight ratio of Y zeolite is 0.01-0.5 when using multiple molecular sieve in the catalyzer according to the described catalyzer of claim 1; The weight ratio of beta-molecular sieve and Y zeolite is 0.025-0.8.
6,, it is characterized in that having the molecular sieve of MFI structure and the weight ratio of Y zeolite is 0.015-0.25 according to the described catalyzer of claim 5.
7,, it is characterized in that said clay is the cracking catalyst matrix common clay that comprises kaolin, halloysite, polynite, wilkinite etc. according to the described catalyzer of claim 1.
8, according to the described catalyzer of claim 1, it is characterized in that said two kinds of aluminum oxide are respectively from the mixture of the aluminum oxide of pseudo-boehmite and aluminium colloidal sol, they account for the 6-40% and the 4-30% of catalyst weight separately.
9,, it is characterized in that the aluminum oxide from pseudo-boehmite and aluminium colloidal sol accounts for the 10-25% and the 10-20% of catalyst weight separately according to the described catalyzer of claim 8.
10,, it is characterized in that said double aluminium binder is the mixture of pseudo-boehmite and aluminium colloidal sol according to the described catalyzer of claim 1.
11, according to the described catalyzer of claim 10, following acidifying and the burin-in process of all or part of process that it is characterized in that said pseudo-boehmite: after clay and pseudo-boehmite mixing making beating, with the sour aluminium weight ratio hcl acidifying that is 0.15-0.50, in 40-90 ℃ of aging 0.5-5 hour.
12, according to the described catalyst of claim 1, it is characterized in that said deposition of rare-earth constituent element precipitates suspension from rare earth hydrate, with RE
2O
3Meter accounts for the 0.1-5% of catalyst weight.
13, according to claim 1 or 12 described catalyst, it is characterized in that the preparation process of said rare earth hydrate precipitation suspension is: will be with RE
2O
3Meter concentration is the re chloride of 100-300 grams per liter, and the ammonia spirit that under agitation adds the heavy % of 10-30 is 8-10 to precipitating the pH of suspension value.
14, according to the described catalyst of claim 1, it is characterized in that with the method for phosphorus-containing compound solution-treated molecular sieve being: with molecular sieve with its butt weight ratio be that 0.5-3.0, elemental phosphorous content are in 4-80 ℃ of lower dipping or after stirring 0.1-8 hour in the phosphorus-containing compound solution of 0.05-5.0%, 100-120 ℃ dry 1-10 hour, repeat one or many to the dried molecular sieve phosphorus content with P
2O
5Count the heavy % of 0.05-10.
15, according to the described catalyzer of claim 1, it is characterized in that said process with the P contained compound aftertreatment be with gained roasting or spraying drying product with its butt weight ratio be 0.5-4.0, elemental phosphorous content be stirred 1-8 hour in the P contained compound solution of 0.1-2.0% or carrying out on the filter with the exchange of P contained compound solution and absorption after, 100-120 ℃ dry 1-10 hour.
16,, it is characterized in that said P contained compound is selected among ortho-phosphoric acid, phosphorous acid, phosphoric anhydride, ammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate, ammonium phosphite, the aluminum phosphate one or more mixture according to claim 1, one of 14 and 15 described catalyzer.
17, according to claim 1, one of 14 and 15 described catalyzer, it is characterized in that the concentration of said P contained compound solution is counted 0.05-5.0% with elemental phosphorous weight.
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|---|---|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313570C (en) * | 2004-01-19 | 2007-05-02 | 中国石油化工股份有限公司 | Hydrocarbon oil cracking method |
| CN1323134C (en) * | 2004-01-19 | 2007-06-27 | 中国石油化工股份有限公司 | Method for cracking hydrocarbon oil |
| CN1323133C (en) * | 2004-01-19 | 2007-06-27 | 中国石油化工股份有限公司 | Hydrocarbon cracking catalyst and its preparing method |
| US7485595B2 (en) | 2003-05-30 | 2009-02-03 | China Petroleum & Chemical Corporation | Molecular sieve-containing catalyst for cracking hydrocarbons and a method for preparing the same |
| CN100478421C (en) * | 2004-08-31 | 2009-04-15 | 中国石油化工股份有限公司 | Catalytic cracking adjuvant and its preparing method |
| CN101234764B (en) * | 2007-01-31 | 2011-01-19 | 中国石油化工股份有限公司石油化工科学研究院 | Method of preparing MFI structure molecular sieve containing phosphorus and transition metal |
| US9175230B2 (en) | 2004-07-29 | 2015-11-03 | China Petroleum & Chemical Corporation | Cracking catalyst and a process for preparing the same |
| CN113492014A (en) * | 2020-03-20 | 2021-10-12 | 中国石油化工股份有限公司 | Heavy metal pollution resistant catalytic cracking catalyst, and preparation method and application thereof |
-
2000
- 2000-09-07 CN CNB001244515A patent/CN1142252C/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7485595B2 (en) | 2003-05-30 | 2009-02-03 | China Petroleum & Chemical Corporation | Molecular sieve-containing catalyst for cracking hydrocarbons and a method for preparing the same |
| CN1313570C (en) * | 2004-01-19 | 2007-05-02 | 中国石油化工股份有限公司 | Hydrocarbon oil cracking method |
| CN1323134C (en) * | 2004-01-19 | 2007-06-27 | 中国石油化工股份有限公司 | Method for cracking hydrocarbon oil |
| CN1323133C (en) * | 2004-01-19 | 2007-06-27 | 中国石油化工股份有限公司 | Hydrocarbon cracking catalyst and its preparing method |
| US9175230B2 (en) | 2004-07-29 | 2015-11-03 | China Petroleum & Chemical Corporation | Cracking catalyst and a process for preparing the same |
| CN100478421C (en) * | 2004-08-31 | 2009-04-15 | 中国石油化工股份有限公司 | Catalytic cracking adjuvant and its preparing method |
| CN101234764B (en) * | 2007-01-31 | 2011-01-19 | 中国石油化工股份有限公司石油化工科学研究院 | Method of preparing MFI structure molecular sieve containing phosphorus and transition metal |
| CN113492014A (en) * | 2020-03-20 | 2021-10-12 | 中国石油化工股份有限公司 | Heavy metal pollution resistant catalytic cracking catalyst, and preparation method and application thereof |
| CN113492014B (en) * | 2020-03-20 | 2023-11-10 | 中国石油化工股份有限公司 | Heavy metal pollution resistant catalytic cracking catalyst and preparation method and application thereof |
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