CN1073614C - Preparation of hydrocarbon cracking catalyst for preventing vanadium poisoning - Google Patents
Preparation of hydrocarbon cracking catalyst for preventing vanadium poisoning Download PDFInfo
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- CN1073614C CN1073614C CN97122090A CN97122090A CN1073614C CN 1073614 C CN1073614 C CN 1073614C CN 97122090 A CN97122090 A CN 97122090A CN 97122090 A CN97122090 A CN 97122090A CN 1073614 C CN1073614 C CN 1073614C
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Abstract
The present invention relates to a preparation method of a rare earth containing hydrocarbon cracking catalyst for resisting vanadium poisoning, which is characterized in that the method comprises: a mixed rare earth solution is mixed with carrier slurry and molecular sieve slurry after being precipitated with a precipitating agent selected from ammonia water, ammonium hydrogen phosphate or ammonium phosphate, ammonium carbonate or a mixture of the ammonia water, the ammonium hydrogen phosphate or the ammonium phosphate and the ammonium carbonate, and then the mixture of the mixed rare earth solution, the carrier slurry and the molecular sieve slurry is dried in a spraying mode and formed. The method has the advantage of simple process. In addition, the obtained catalyst has favorable vanadium poisoning resisting performance.
Description
The present invention relates to a kind of preparation of catalyst and cracking of hydrocarbon, particularly relate to a kind of preparation of catalyst for heavy oil catalytic cracking of anti-vanadiumism.
The heaviness of crude oil and poor qualityization make heavy metal content increase in the heavy oil (＞350 ℃ of fractions), and wherein influencing bigger to catalytic cracking is nickel and vanadium.Nickel mainly influences the hydrogen transfer activity of catalyzer, and hydrogen and coke yield are increased, and product distributes and degenerates; Vanadium then mainly influences activity of such catalysts, destroys the structure of catalyzer.Before owing to Ni content height in the crude oil in China, V content generally is lower than 1ppm, content of vanadium is 1500-2000ppm on the catalytic cracking poiser, therefore it is many to the work of catalytic cracking catalyst to study nickel, and the research vanadium to the work of catalytic cracking catalyst influence seldom, do not have special anti-vanadium catalytic cracking catalyst Industrial products so far.Because the crude oil vanadiumcontent is higher, it is more to the work of catalytic cracking catalyst influence therefore to study vanadium abroad.Increase year by year owing to China's import middle-eastern crude quantity in recent years, and its heavy oil V content generally is higher than 20ppm after the oil-field development utilization of Tarim Basin, Xinjiang, even up to 60ppm, V content reaches 7000-11000ppm on the catalytic cracking poiser, the catalytic cracking catalyst structure is damaged, the agent consumption increases by 80%, quality product and product distribution variation.
The result of existing research catalytic cracking catalyst vanadiumism mechanism thinks that the vanadium in the heavy oil exists with porphyrin vanadium form, in the catalytic cracking reaction process, vanadium (+2 ,+3 ,+4 valencys) is deposited on catalyst surface at a low price, in catalyst regeneration process, vanadium is oxidized at a low price, changes V into
2O
5And vanadic acid, these two kinds of compounds further with molecular sieve in reactive aluminum, generate vanadic acid aluminium, molecular sieve structure is damaged, and vanadic acid aluminium can be decomposed into V
2O
5And AlO
3, this makes that vanadium is non-stoichiometric to the destruction of molecular sieve structure.
External each major oil companies are from the late nineteen seventies anti-vanadium catalytic cracking catalyst that just begins one's study, and wherein a kind of method is to do in order to the destruction of inhibition vanadium to molecular sieve with alkaline earth metal oxide and vanadium.The U.S. Pat P5 that for example belongs to Engelhard company uses MgO and the kaolin bead anti-vanadium assistant as catalytic cracking catalyst in 300,469; The U.S. Pat P4 that belongs to Ashland Oil company uses II A in the periodic table of elements in 485,184, III B, and IV B, the oxide compound of V B isofamily element is as the auxiliary agent of anti-vanadium catalytic cracking catalyst; USP4, in 843,052 and USP4,940,531 with tin, titanium mixed oxide as anti-vanadium component, these all have anti-preferably vanadium effect.
Another method is to introduce rare earth in catalyzer, utilize rare earth oxide can with V
2O
5The character that generates stable compound suppresses the destruction of vanadium to molecular sieve.USP4 for example, 900,428 and EP 0189267 in use soluble ree compound (as halogenide or nitrate) solution impregnation catalyst or matrix, drying and roasting then is incorporated into rare earth in the catalyzer; USP5, in 248,642 and USP5,394,299 with rare earth oxide as active ingredient, aluminium colloidal sol is as binding agent, kaolin or sour modified kaolin are that matrix is made catalyzer, show good anti-vanadium effect; USP4, the method that provides in 515,683 is to contact certain hour with soluble ree solution with catalyst mix, adds ammoniacal liquor again and makes rare-earth precipitation (PH=11) on catalyzer, filters then, washes with water and drying.With ammoniacal liquor rare earth chloride is deposited on the Y zeolite among the CN 88100418A, making with this Y zeolite is that the catalytic cracking catalyst of active component has certain anti-vanadium performance; USP5, the bastnasites with 5～10 heavy % in 173,174 directly join in the catalytic cracking catalyst, also have certain anti-vanadium effect.
Analyze existing patent and document, ammoniacal liquor of no use or other precipitation agent with rare-earth precipitation after as one of component of Preparation of Catalyst slurries, spraying drying prepares the report of catalyzer then.
The preparation method who the purpose of this invention is to provide a kind of catalyst and cracking of hydrocarbon of anti-vanadiumism directly adds rare earth in the slurries of spray catalyzer, with simplification preparation technology, and the gained catalyzer has better anti-vanadiumism performance.
The preparation method of the catalyst and cracking of hydrocarbon of anti-vanadiumism provided by the present invention comprises:
(1). prepare a kind of carrier pulp by the method for prior art, the amount of this carrier (by butt weight) is 50～80%, preferred 58～72% of a said catalyzer butt weight;
(2). add a kind of precipitation agent that is selected from ammoniacal liquor, ammonium hydrogen phosphate or ammonium phosphate, volatile salt or their mixture in the mixed type re chloride rare earth ion is precipitated fully, obtain a kind of sedimentary mixture that contains, the consumption of said rare earth is (with RE
2O
3The weight meter) is 1～5%, preferred 2～3.5% of said catalyzer butt weight;
(3). it is even that (2) gained mixture is joined in (1) said carrier pulp thorough mixing;
(4). it is even that a kind of molecular sieve pulp is joined in (3) gained mixture thorough mixing, and the consumption of this molecular sieve (by butt weight) is 15～45%, preferred 25～40% of a said catalyzer butt weight;
(5). with the spraying drying shaping according to a conventional method of (4) gained mixture.
Said carrier pulp has two kinds in full synthesis carrier and semi-synthetic carrier in the prior art in the step in the method provided by the invention (1), but for the preferably semi-synthetic carrier of catalyst for cracking heavy oil.
Said full synthesis carrier is meant the synthetic vectors that does not contain natural clay, is generally the silica-alumina gel system, and its preparation method can be referring to general Preparation of Catalyst handbook, as " support of the catalyst " (Zhu Hongfa compiles, Chemical Industry Press, version in 1980).
Said semi-synthetic carrier is meant and contains natural clay as matrix, is the carrier of caking agent with the inorganic oxide; Said natural clay is kaolin preferably; Said caking agent can be pseudo-boehmite, aluminium colloidal sol, silicon sol, or their mixture.
Said mixed type rare earth is rich lanthanum type mishmetal or rich cerium type mishmetal in the step in the method provided by the invention (2); La in the total amount of rare earth
2O
3Content be 15～85 heavy %, Ce
2O
3Content be 10～70 heavy %, all the other are elements such as a spot of yttrium, neodymium, praseodymium, samarium.The concentration of said re chloride has no particular limits.
Said molecular sieve is the conventional various molecular sieves that adopt in the hydrocarbon cracking catalyzer in the step in the method provided by the invention (4), be generally superstable gamma-type (USY), Y-type rare earth (REY) or rare earth hydrogen Y type (REHY) molecular sieve, wherein USY type molecular sieve preferably.
Also can be earlier in the method provided by the present invention with the molecular sieve pulp in the step (4) with mix with step (2) gained rare-earth precipitation mixture again after the carrier pulp in the step (1) is mixed, carry out spraying drying then.
Said butt weight is meant that sample removes the weight of gained resistates behind the volatilizable thing after drying again through roasting in 850 ℃/1 hour among the present invention.
Flood again behind the method for the anti-vanadiumism hydrocarbon cracking catalyzer of preparation provided by the present invention and the shaped catalyst rare earth and dry and roasting the prior art simplified in comparison processing step, reduced energy consumption, and, rare earth joins in the Preparation of Catalyst slurries because being form with rare-earth precipitation thing stable under acidic conditions, most of rare earth is existed with sedimentary oxide form in catalyzer, reduce rare earth ion because of the possibility that ion-exchange enters the molecular sieve intracrystalline, helped improving the anti-vanadiumism performance of catalyzer.With USP4,515,683, prior art such as CN88100428A compares, method gained catalyzer provided by the invention has better anti-vanadiumism performance.
The following examples will the present invention is described further.In each embodiment and Comparative Examples, the lattice constant a of catalyzer
0, crystallization reservation degree, rare earth oxide (RE
2O
3) micro-activity of content and catalyzer measures according to RIPP 145-90,146-90,131-90 and 92-90 standard method in " petrochemical complex analytical procedure (RIPP test method) " (nineteen ninety publishes for volume such as Yang Cuiding, Science Press) respectively.
Embodiment 1
Get 430 gram kaolin (dry basis), 907 gram aluminium colloidal sol (Al
2O
3Concentration is 20.94 heavy %, down with) and 1573 gram water mix making beating 60 minutes, obtain carrier pulp; Other gets RE
2O
3Content is the rich cerium type RECl of 228 grams per liters (g/l)
3(weight percentage of each composition is solution in its total amount of rare earth: Ce
2O
363%, La
2O
325%, Pr
6O
112.1%, Nd
2O
35.0%, Sm
2O
30.5%, other is 4.4% years old) 132ml, to wherein to splash into concentration be 28% strong aqua and constantly stir the companion, until the pH value to 8.0 of precipitation suspension, should precipitate suspension then and join in the above-mentioned carrier pulp stirring 20 minutes; (Chang Ling oil-refining chemical factory catalyst plant is produced to add the USY molecular sieve in the gained mixture, method preparation according to patent CN1088247A, silica alumina ratio is 10, down with) 350 grams (dry basis), stirring after 20 minutes on medium-sized spray drying unit according to a conventional method, spray becomes microspherical catalyst.With this microspherical catalyst with 20 times of 0.1NNH to catalyzer butt weight
4Cl solution in 60 ℃ of pulping and washing once again with the same method washed twice of deionized water, filters and in 110 ℃ of oven dry, obtains sample A.
Embodiment 2
Get kaolin 320 grams (dry basis), add 1600 gram deionized water making beating evenly, add 200 gram (dry basis) pseudo-boehmites again, continue to stir that to add 52ml concentration after 30 minutes be that 30% hydrochloric acid carries out acidifying, at this moment above-mentioned slurries PH is about 1.0～1.2, stop then stirring, be warming up to 65 ℃ and in 60～70 ℃ of temperature ranges aging 3 hours, this moment, slurries PH was about 3.2.Stop to restrain the aluminium colloidal sols to wherein adding 478 again after the heating, obtain carrier pulp after stirring.Other gets said rich cerium type RECl among the embodiment 1
3Solution 132ml to wherein to splash into concentration be 28% strong aqua and constantly stir the companion, until the pH value to 8.0 of precipitation suspension, should precipitate suspension then and join in the above-mentioned carrier pulp stirring 20 minutes; Add USY molecular sieve 350 grams (dry basis) in the gained mixture, stirring after 20 minutes on medium-sized spray drying unit according to a conventional method, spray becomes microspherical catalyst.With this microspherical catalyst with 20 times of 0.1N NH to catalyzer butt weight
4Cl solution in 60 ℃ of pulping and washing once again with the same method washed twice of deionized water, filters and in 110 ℃ of oven dry, obtains sample B.
Embodiment 3
Get 430 gram kaolin (dry basis), 907 gram aluminium colloidal sols and 1573 gram water mix making beating 60 minutes, obtain carrier pulp; Other gets RE
2O
3Content is the rich lanthanum type RECl of 228g/l
3(weight percentage of each composition is solution in its total amount of rare earth: Ce
2O
313%, La
2O
379%, Pr
6O
111.8%, Nd
2O
33.4%, Sm
2O
30.4%, other is 2.4% years old) 108ml, to wherein to splash into concentration be 28% strong aqua and constantly stir the companion, until the pH value to 8.0 of precipitation suspension, should precipitate suspension then and join in the above-mentioned carrier pulp stirring 20 minutes; Add USY molecular sieve 350 grams (dry basis) in the gained mixture, stirring after 20 minutes on medium-sized spray drying unit according to a conventional method, spray becomes microspherical catalyst.With this microspherical catalyst with 20 times of 0.1N NH to catalyzer butt weight
4Cl solution in 60 ℃ of pulping and washing once again with the same method washed twice of deionized water, filters and in 110 ℃ of oven dry, obtains sample C.
Embodiment 4
Get kaolin 320 grams (butt), add 1600 gram deionized water making beating evenly, add 250 gram (dry basis) pseudo-boehmites again, continue to stir that to add 65ml concentration after 30 minutes be that 30% hydrochloric acid stirs and carries out acidifying, stop then stirring, be warming up to 65 ℃ and in 60～70 ℃ of temperature ranges aging 3.5 hours, this moment, slurries PH was about 3.4, stopped heating.Other gets said rich lanthanum type RECl among the embodiment 3
3Solution 108ml to wherein to splash into concentration be 28% strong aqua and constantly stir the companion, until the pH value to 8.0 of precipitation suspension, should precipitate suspension then and join in the above-mentioned carrier pulp stirring 20 minutes; Add USY molecular sieve 350 grams (dry basis) in the gained mixture, stir after 20 minutes, (Chang Ling oil-refining chemical factory catalyst plant is produced, SiO to wherein adding 200 gram silicon sol again
2Content is 25 heavy %) and continue to stir 10 minutes, then with the gained slurries on medium-sized spray drying unit according to a conventional method spray become microspherical catalyst.With this microspherical catalyst with 20 times of 0.1N NH to catalyzer butt weight
4Cl solution in 60 ℃ of pulping and washing once again with the same method washed twice of deionized water, filters and in 110 ℃ of oven dry, obtains sample D.
Embodiment 5
Get 430 gram kaolin (dry basis), 907 gram aluminium colloidal sols and 1573 gram water mix making beating 60 minutes, obtain carrier pulp; Other gets said rich cerium type RECl among the embodiment 1
3Solution 132ml under agitation adds (the NH that concentration is 2M
4)
2HPO
4Solution 115ml precipitates rare earth fully, obtains precipitating suspended substance, and at this moment the pH value of suspension is 2.0, should precipitate suspension then and join in the above-mentioned carrier pulp and to stir 20 minutes; Add USY molecular sieve 350 gram (dry basis) in the gained mixture again, stirring after 20 minutes on medium-sized spray drying unit according to a conventional method, spray becomes microspherical catalyst.With this microspherical catalyst with 20 times of 0.1N NH to catalyzer butt weight
4Cl solution in 60 ℃ of pulping and washing once again with the same method washed twice of deionized water, filters and in 110 ℃ of oven dry, obtains sample E.
Embodiment 6
Get kaolin 320 grams (butt), add 1600 gram deionized water making beating evenly, add 200 gram (dry basis) pseudo-boehmites again, continue to stir that to add 52ml concentration after 30 minutes be that 30% hydrochloric acid stirs and carries out acidifying, stop then stirring, be warming up to 65 ℃ and in 60～70 ℃ of temperature ranges aging 3.5 hours, stop after the heating obtaining carrier pulp after stirring again to wherein adding 478 gram aluminium colloidal sols.Other gets said rich cerium type RECl among the embodiment 1
3Solution 132ml under agitation adds and contains 9.0 gram (NH
4)
2HPO
4With 5.0 gram NH
4The mixing solutions 150ml of OH precipitates rare earth fully and obtains precipitating suspension, at this moment the pH value of suspension is 5.0, this suspension joined in the above-mentioned carrier pulp stirred 20 minutes, add USY molecular sieve 350 gram (dry basis) in the gained mixture again, stirring after 20 minutes on medium-sized spray drying unit according to a conventional method, spray becomes microspherical catalyst.With this microspherical catalyst with 20 times of 0.1NNH to catalyzer butt weight
4Cl solution in 60 ℃ of pulping and washing once again with the same method washed twice of deionized water, filters and in 110 ℃ of oven dry, obtains sample F.
Embodiment 7
Get kaolin 320 grams (butt), add 1600 gram deionized water making beating evenly, add 200 gram (dry basis) pseudo-boehmites again, continue to stir that to add 52ml concentration after 30 minutes be that 30% hydrochloric acid stirs and carries out acidifying, stop then stirring, be warming up to 65 ℃ and in 60～70 ℃ of temperature ranges aging 3.5 hours, stop after the heating obtaining carrier pulp after stirring again to wherein adding 478 gram aluminium colloidal sols.Other gets said rich cerium type RECl among the embodiment 1
3Solution 132ml under agitation adds and contains 8.0 gram (NH
4)
2CO
3Solution 60ml rare earth is precipitated fully obtain precipitating suspension, at this moment the pH value of suspension is 3.0, this suspension joined in the above-mentioned carrier pulp stirred 20 minutes, add USY molecular sieve 350 gram (dry basis) in the gained mixture again, stirring after 20 minutes on medium-sized spray drying unit according to a conventional method, spray becomes microspherical catalyst.With this microspherical catalyst with 20 times of 0.1N NH to catalyzer butt weight
4Cl solution in 60 ℃ of pulping and washing once again with the same method washed twice of deionized water, filters and in 110 ℃ of oven dry, obtains sample G.
Embodiment 8
Get 550 gram kaolin (dry basis), 907 gram aluminium colloidal sols and 1500 gram water mix making beating 60 minutes, obtain carrier pulp; Other gets said rich cerium type RECl among the embodiment 1
3Solution 45ml to wherein to splash into concentration be 28% strong aqua and constantly stir the companion, until the pH value to 8.0 of precipitation suspension, should precipitate suspension then and join in the above-mentioned carrier pulp stirring 20 minutes; Add REHY type molecular sieve (Chang Ling oil-refining chemical factory catalyst plant is produced) 250 grams (dry basis) in the gained mixture, stirring after 20 minutes on medium-sized spray drying unit according to a conventional method, spray becomes microspherical catalyst.With this microspherical catalyst with 20 times of 0.1NNH to catalyzer butt weight
4Cl solution in 60 ℃ of pulping and washing once again with the same method washed twice of deionized water, filters and in 110 ℃ of oven dry, obtains sample H.
Embodiment 9
Get 251 gram kaolin (dry basis), 1430 gram aluminium colloidal sols and 1600 gram water mix making beating 60 minutes, obtain carrier pulp; Other gets said rich cerium type RECl among the embodiment 1
3Solution 220ml to wherein to splash into concentration be 28% strong aqua and constantly stir the companion, until the pH value to 8.0 of precipitation suspension, should precipitate suspension then and join in the above-mentioned carrier pulp stirring 20 minutes; Add said USY type molecular sieve 400 grams (dry basis) among the embodiment 1 in the gained mixture, stirring after 20 minutes on medium-sized spray drying unit according to a conventional method, spray becomes microspherical catalyst.With this microspherical catalyst with 20 times of 0.1N NH to catalyzer butt weight
4Cl solution in 60 ℃ of pulping and washing once again with the same method washed twice of deionized water, filters and in 110 ℃ of oven dry, obtains the sample I.
Comparative Examples 1
This Comparative Examples provides a kind of typical catalyst that does not add the rare earth oxide anti-vanadium assistant.
Repeat the step of embodiment 1, different is not add the rare-earth precipitation suspended substance when the preparation catalyst slurry.The gained sample is designated as DB-1.
Comparative Examples 2
This Comparative Examples provides a kind of rare earth oxide anti-vanadium assistant that do not add, but with the super-stable Y molecular sieves of the deposition of rare-earth type catalyzer as active component.
Repeat the step of Comparative Examples 1, different is that the super-stable Y molecular sieves (Chang Ling oil-refining chemical factory catalyst plant is produced, and according to the described method preparation of CN88100418A, trade names are SRNY) of using the deposition of rare-earth type replaces wherein used USY molecular sieve.The gained sample is designated as DB-2.
Comparative Examples 3
This Comparative Examples provides a kind of USP4, said anti-vanadium catalyst in 515,683.
Adopt USP4,515,683 method is deposited on rare earth on the Comparative Examples 1 gained catalyzer DB-1, and the gained sample is designated as DB-3.Concrete preparation method is: get said rich cerium type RECl among the embodiment 1
3Solution 132ml after the dilution of 378ml deionized water, joins it in 1kg (dry basis) DB-1 sample, stirred 20 minutes, and added ammoniacal liquor (3.7N) then and make the slurries pH value reach 11, restir is after 20 minutes, with deionized water wash three times, filter 177 ℃ of oven dry.
Embodiment 10
Present embodiment explanation the inventive method gained catalyzer and comparative catalyst's anti-vanadiumism performance.
The foregoing description and Comparative Examples gained catalyzer are used vanadium oxalate solution impregnation 12 hours according to required pickup, then in 120 ℃ of dryings 4 hours, and 550 ℃ of roastings 4 hours, then with each sample and not the sample of vanadium impregnated through 820 ℃/4 hours, 100% water vapour atmosphere aging after, measure their lattice constant a0, the crystallization reservation degree C.R and the micro-activity of aging front and back respectively, the results are shown in Table 1 for it.
Table 1
| The catalyzer numbering | RE 2O 3Content (%) | Soak V amount (ppm) | a 0(nanometer) | C.R(％) | Little index alive |
| DB-1 | 0.1 | 0 | 2.422 | 47 | 58 |
| 5000 | 2.421 | 36 | 55 | ||
| 8000 | 2.421 | 38 | 38 | ||
| 11000 | 2.421 | 33 | 25 | ||
| DB-2 | 3.2 | 0 | 2.424 | 62 | 60 |
| 5000 | 2.421 | 57 | 53 | ||
| 8000 | 2.423 | 26 | 47 | ||
| 11000 | 2.423 | 17 | 36 | ||
| DB-3 | 3.0 | 0 | 2.421 | 50 | 65 |
| 5000 | 2.421 | 37 | 64 | ||
| 8000 | 2.421 | 32 | 52 | ||
| 11000 | 2.421 | 25 | 47 | ||
| A | 3.2 | 0 | 2.422 | 55 | 67 |
| 5000 | 2.425 | 48 | 66 | ||
| 8000 | 2.421 | 45 | 64 | ||
| 11000 | 2.425 | 39 | 62 |
(table 1 is continued)
(continuous table 1)
| The catalyzer numbering | RE 2O 3Content (%) | Soak V amount (ppm) | a 0(nanometer) | C.R(％) | Little index alive |
| B | 3.2 | 0 | 2.426 | 32 | 57 |
| 5000 | 2.424 | 25 | 58 | ||
| 8000 | 2.426 | 27 | 57 | ||
| 11000 | 2.420 | 27 | 54 | ||
| C | 2.8 | 0 | 2.428 | 39 | 69 |
| 5000 | 2.428 | 37 | 65 | ||
| 8000 | 2.426 | 25 | 59 | ||
| 11000 | 2.425 | 16 | 46 | ||
| D | 2.9 | 0 | 2.427 | 26 | 60 |
| 5000 | 2.426 | 25 | 56 | ||
| 8000 | 2.425 | 25 | 56 | ||
| 11000 | 2.423 | 23 | 49 | ||
| E | 3.0 | 0 | 2.427 | 57 | 70 |
| 5000 | 2.426 | 41 | 61 | ||
| 8000 | 2.420 | 30 | 56 | ||
| 11000 | 2.426 | 34 | 56 | ||
| F | 3.0 | 0 | 2.425 | 42 | 67 |
| 5000 | 2.425 | 31 | 62 | ||
| 8000 | 2.426 | 35 | 62 | ||
| 11000 | 2.424 | 21 | 57 | ||
| G | 1.0 | 0 | 2.424 | 48 | 59 |
| 5000 | 2.420 | 42 | 58 | ||
| 8000 | 2.420 | 41 | 55 | ||
| 11000 | 2.422 | 35 | 52 | ||
| H | 4.5 | 0 | 2.463 | 62 | 71 |
| 5000 | 2.463 | 35 | 51 | ||
| 8000 | 2.461 | 30 | 45 | ||
| 11000 | 2.462 | 27 | 41 | ||
| I | 4.6 | 0 | 2.426 | 41 | 56 |
| 5000 | 2.425 | 38 | 54 | ||
| 8000 | 2.425 | 33 | 51 | ||
| 11000 | 2.420 | 30 | 50 |
Embodiment 11
Present embodiment explanation the inventive method gained catalyzer and comparative catalyst's anti-vanadiumism performance.
With catalyst sample DB-1 noted earlier, DB-2, DB-3 and sample A, B, it is 6800ppm that D and E made the pickup of vanadium on the catalyzer in 12 hours with the vanadium oxalate solution impregnation, then in 120 ℃ of dryings 4 hours, and 550 ℃ of roastings 4 hours, obtain flooding the sample VDB-1 of 6800ppm vanadium (V) respectively, VDB-2, VDB-3 and sample VA, VB, VD and VE, then with each sample and not the sample DB-1 of vanadium impregnated through 800 ℃/17 hours, after 100% water vapour atmosphere is aging, on the small fixed flowing bed device, estimate, appreciation condition is: stock oil is by Tarim Basin oil, tell and breathe out the long residuum that oil becomes with middle crude oil combined group, its character sees Table 2; The catalyzer loading amount is 150 grams, 500 ℃ of temperature of reaction, and 650～700 ℃ of regeneration temperatures are during weight space velocity 20
-1Evaluation result is listed in the table 3.
Table 2
| 20 ℃ of density (g/cm 3) | 0.9065 |
| Viscosity (mm 2/s)(100℃) | 15.35 |
| Carbon residue (heavy %) | 6.0 |
| Stable hydrocarbon (heavy %) | 51.3 |
| Aromatic hydrocarbons (heavy %) | 27.5 |
| Colloid (heavy %) | 20.7 |
| Bituminous matter (heavy %) | 0.5 |
| C (heavy %) | 86.43 |
| H (heavy %) | 12.28 |
| Heavy metal content (ppm) Fe Ni V Na K | 13.0 5.2 11.6 1.0 1.0 |
| Boiling range (℃) initial boiling point 5% 10% 30% 50% | 237 289 322 416 476 |
Table 3
| Catalyzer | DB-1 | VDB-1 | VDB-2 | VDB-3 | VA | VB | VD | VE |
| Material balance, heavy % dry gas liquefied gas gasoline, diesel heavy oil coke | 2.06 15.00 45.25 21.52 9.11 7.06 | 1.76 10.56 38.40 24.99 17.81 6.47 | 2.70 15.09 45.15 19.53 9.24 8.28 | 2.53 15.34 45.37 20.57 8.06 8.13 | 1.82 16.39 46.90 19.53 7.72 7.63 | 2.70 16.36 47.07 18.64 7.43 7.78 | 2.18 15.82 48.38 18.47 7.08 8.07 | 1.96 16.96 47.02 18.69 7.68 7.69 |
| Transformation efficiency, heavy % | 69.37 | 57.20 | 71.22 | 72.05 | 72.75 | 73.92 | 74.45 | 73.62 |
| Lightweight oil+liquefied gas (heavy %) | 81.77 | 73.95 | 79.77 | 81.28 | 82.82 | 82.07 | 82.67 | 82.67 |
| Coke/transformation efficiency | 0.102 | 0.113 | 0.116 | 0.111 | 0.105 | 0.105 | 0.108 | 0.104 |
From the result of table 1 and table 2 as can be seen, method gained catalyzer provided by the invention is compared anti-vanadiumism ability with typical catalyst (DB-1) and is improved greatly, compare with DB-3 with contrast medium DB-2, its specific activity contrast medium height after with vanadiumism, dry gas and coke yield are lower than contrast medium.
Claims (7)
1. the preparation method of the hydrocarbon cracking catalyzer of an anti-vanadiumism that contains rare earth is characterized in that this method comprises:
(1). prepare a kind of carrier pulp by the method for prior art, the amount of this carrier (by butt weight) is 50～80% of a said catalyzer butt weight;
(2). add a kind of precipitation agent that is selected from ammoniacal liquor, ammonium hydrogen phosphate or ammonium phosphate, volatile salt or their mixture in the mixed type re chloride rare earth ion is precipitated fully, obtain a kind of sedimentary mixture that contains, the consumption of said rare earth is (with RE
2O
3The weight meter) is 1～5% of said catalyzer butt weight;
(3). it is even that (2) gained mixture is joined in (1) said carrier pulp thorough mixing;
(4). it is even that a kind of molecular sieve pulp is joined in (3) gained mixture thorough mixing, and the consumption of this molecular sieve (by butt weight) is 15～45% of a said catalyzer butt weight;
(5). with the spraying drying shaping according to a conventional method of (4) gained mixture.
2. according to the process of claim 1 wherein that said carrier is the semi-synthetic carrier that contains natural clay and caking agent in the step (1).
3. according to the method for claim 2, wherein said natural clay is a kaolin; Said caking agent is pseudo-boehmite, aluminium colloidal sol, silicon sol or their mixture.
4. according to the process of claim 1 wherein that said rare earth is rich lanthanum type mishmetal or is rich cerium type mishmetal in the step (2).
5. according to the process of claim 1 wherein that said molecular sieve is superstable gamma-type, Y-type rare earth or rare earth hydrogen Y zeolite in the step (4).
6. according to the method for claim 5, wherein said molecular sieve is a super-stable Y molecular sieves.
7. according to the process of claim 1 wherein that the amount of said carrier is 58～72% in the step (1), the amount of said rare earth is 2～3.5% in the step (2), and the amount of said molecular sieve is 25～40% in the step (4).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97122090A CN1073614C (en) | 1997-12-23 | 1997-12-23 | Preparation of hydrocarbon cracking catalyst for preventing vanadium poisoning |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97122090A CN1073614C (en) | 1997-12-23 | 1997-12-23 | Preparation of hydrocarbon cracking catalyst for preventing vanadium poisoning |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1221016A CN1221016A (en) | 1999-06-30 |
| CN1073614C true CN1073614C (en) | 2001-10-24 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97122090A Expired - Lifetime CN1073614C (en) | 1997-12-23 | 1997-12-23 | Preparation of hydrocarbon cracking catalyst for preventing vanadium poisoning |
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| Country | Link |
|---|---|
| CN (1) | CN1073614C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106890675B (en) * | 2015-12-18 | 2020-02-14 | 中国石油天然气股份有限公司 | Preparation method of rare earth-containing catalytic cracking catalyst |
| CN106927482B (en) * | 2015-12-29 | 2019-09-03 | 中国石油天然气股份有限公司 | A kind of preparation method of super-stable Y molecular sieves |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1130199A (en) * | 1913-05-16 | 1915-03-02 | Washington W Rowley Jr | Multigraph printing-machine. |
| US4025458A (en) * | 1975-02-18 | 1977-05-24 | Phillips Petroleum Company | Passivating metals on cracking catalysts |
| US4515683A (en) * | 1983-09-15 | 1985-05-07 | Ashland Oil, Inc. | Passivation of vanadium accumulated on catalytic solid fluidizable particles |
| US4551231A (en) * | 1981-10-13 | 1985-11-05 | Ashland Oil, Inc. | Ammonia contacting to passivate metals deposited on a cracking catalyst during reduced crude processing |
| EP0077044B1 (en) * | 1981-10-13 | 1986-05-07 | Ashland Oil, Inc. | Method to passivate metals deposited on a cracking catalyst during reduced crude processing |
-
1997
- 1997-12-23 CN CN97122090A patent/CN1073614C/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1130199A (en) * | 1913-05-16 | 1915-03-02 | Washington W Rowley Jr | Multigraph printing-machine. |
| US4025458A (en) * | 1975-02-18 | 1977-05-24 | Phillips Petroleum Company | Passivating metals on cracking catalysts |
| US4551231A (en) * | 1981-10-13 | 1985-11-05 | Ashland Oil, Inc. | Ammonia contacting to passivate metals deposited on a cracking catalyst during reduced crude processing |
| EP0077044B1 (en) * | 1981-10-13 | 1986-05-07 | Ashland Oil, Inc. | Method to passivate metals deposited on a cracking catalyst during reduced crude processing |
| US4515683A (en) * | 1983-09-15 | 1985-05-07 | Ashland Oil, Inc. | Passivation of vanadium accumulated on catalytic solid fluidizable particles |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1221016A (en) | 1999-06-30 |
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