CN102974386B - Catalytic cracking catalyst and preparation method thereof - Google Patents
Catalytic cracking catalyst and preparation method thereof Download PDFInfo
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- CN102974386B CN102974386B CN201210489240.3A CN201210489240A CN102974386B CN 102974386 B CN102974386 B CN 102974386B CN 201210489240 A CN201210489240 A CN 201210489240A CN 102974386 B CN102974386 B CN 102974386B
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- catalyst
- molecular sieve
- catalytic cracking
- aluminium glue
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- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 49
- 239000004411 aluminium Substances 0.000 claims abstract description 48
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 43
- 239000011574 phosphorus Substances 0.000 claims abstract description 42
- 239000003292 glue Substances 0.000 claims abstract description 41
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 40
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011230 binding agent Substances 0.000 claims abstract description 17
- 239000011787 zinc oxide Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 3
- 239000002808 molecular sieve Substances 0.000 claims description 52
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 52
- 238000010009 beating Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000005995 Aluminium silicate Substances 0.000 claims description 11
- 235000012211 aluminium silicate Nutrition 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 238000005507 spraying Methods 0.000 claims description 11
- 239000004927 clay Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 239000000084 colloidal system Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 7
- 239000007789 gas Substances 0.000 abstract description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 7
- 238000005299 abrasion Methods 0.000 abstract description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 229910052761 rare earth metal Inorganic materials 0.000 description 9
- 150000002910 rare earth metals Chemical class 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 239000000295 fuel oil Substances 0.000 description 7
- 238000005336 cracking Methods 0.000 description 5
- 235000011007 phosphoric acid Nutrition 0.000 description 5
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 3
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical group O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 phosphorous hydrocarbon Chemical class 0.000 description 2
- 150000003017 phosphorus Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002821 scintillation proximity assay Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- NHYCGSASNAIGLD-UHFFFAOYSA-N Chlorine monoxide Chemical compound Cl[O] NHYCGSASNAIGLD-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- DGWFDTKFTGTOAF-UHFFFAOYSA-N P.Cl.Cl.Cl Chemical compound P.Cl.Cl.Cl DGWFDTKFTGTOAF-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention belongs to catalyst technical field, be specifically related to a kind of catalytic cracking catalyst and preparation method thereof.Described catalytic cracking catalyst adopts phosphorus aluminium glue as binding agent, and adds zinc oxide as auxiliary agent in the process of catalyst preparing.Catalyst of the present invention contains zinc oxide and is prepared from for binding agent with phosphorus aluminium glue, has the performance of the arene content in propylene enhancing and raising gasoline.Compared with the colloidal sol containing chloride and aluminium catalyst high with adopting cost, do not have corrosion and the emission problem of hydrogen chloride gas, catalyst is substantially not chloride yet; Because phosphorus aluminium glue adhesive property is good, therefore catalyst abrasion intensity of the present invention is high.Preparation method of the present invention is simple, be easy to realize.
Description
Technical field
The invention belongs to catalyst technical field, be specifically related to a kind of catalytic cracking catalyst and preparation method thereof.
Background technology
Current industrial catalytic cracking catalyst used is all generally be made up of molecular sieve (active component), matrix clay and binding agent, and the binding agent used mostly is boehmite and Alumina gel.But use aluminium base binding agent, particularly use Alumina gel can bring serious problem, chlorion higher contained by it can produce a large amount of hydrogen chloride gas when spraying dry, thus etching apparatus cause atmosphere pollution.Catalyst is when device uses, and chlorion meeting etching apparatus residual in catalyst also affects the activity of catalyst.
In recent years, phosphorus aluminium glue starts as binding agent the preparation introducing catalytic cracking catalyst, to improve the tear strength of catalyst, selective, and hydrothermal stability, also solves problem of environmental pollution.
CN1076714A discloses a kind of phosphorous hydrocarbon cracking catalyzer taking phosphorated aluminiferous collosol as binding agent and prepare.Phosphorated aluminiferous collosol used is according to method preparation disclosed in CN170384A and CN170385A.Orthophosphoric acid or aluminium dihydrogen phosphate add in colloidal sol containing chloride and aluminium by CN170384A preparation method, obtain phosphorous and Alumina gel that is chlorine through high temperature decondensation.Metallic aluminium, hydrochloric acid (or aluminium salt), phosphoric acid (or aluminium dihydrogen phosphate) react and obtain phosphorated aluminiferous collosol through high temperature decondensation by CN170385A preparation method under certain condition.A lot of weak points that the method exists, one is need high temperature decondensation in preparation process, preparation more complicated.Two is stability for ensureing phosphorus aluminium glue and mobility, and the content of phosphorus is lower, and general Al/P weight ratio is greater than 4.Three is the chlorine of phosphorus aluminium glue still containing higher amount prepared.
It is phosphorous hydrocarbon cracking catalyzer prepared by binding agent that CN1180059C discloses a kind of phosphorated aluminiferous collosol.Its preparation method first makes not chloride phosphorus aluminium glue with aluminium oxide or aluminium hydroxide and phosphatase reaction, then used in combination with colloidal sol containing chloride and aluminium.Although the method simplifies the process of phosphorated aluminiferous collosol, but still the just chloride Alumina gel of Some substitute, still can not get rid of corrosion and the environmental issue of chlorine.
USP5194412 discloses a kind of production of cracking catalyst being binding agent with phosphorus aluminium glue, and phosphorus aluminium glue aluminium salt used and phosphatase reaction obtain, Al/P atomic ratio=0.65 ~ 1.1.The catalyst of preparation has voluminous light olefin and reduces the effect of Aromatic Hydrocarbon in Gasoline.
USP6355591 discloses a kind of production of cracking catalyst being binding agent with phosphorus aluminium glue, and phosphorus aluminium glue metallic aluminium powder used and phosphatase reaction obtain, Al/P atomic ratio=3.The catalyst of preparation can voluminous liquefied gas.
Summary of the invention
The object of the present invention is to provide a kind of catalytic cracking catalyst and preparation method thereof, this catalyst is containing zinc oxide and with the molecular sieve type Cracking catalyst that phosphorus aluminium glue is binding agent, has the performance of producing more propylene and increase Aromatic Hydrocarbon in Gasoline content.
Catalytic cracking catalyst of the present invention, comprise active component, carrier and binding agent, wherein active component is molecular sieve, and carrier is clay, this catalyst adopts phosphorus aluminium glue as binding agent, and adds zinc oxide as auxiliary agent in the process of catalyst preparing.
Described zinc oxide accounts for 0.5 ~ 2.0% of total catalyst weight.
Described molecular sieve is one or more in Y zeolite, ZSM-5 molecular sieve, SAPO-11 molecular sieve, and molecular sieve accounts for 15 ~ 45% of total catalyst weight.
Described clay is kaolin, bentonite or montmorillonite, and clay accounts for 25 ~ 70% of total catalyst weight.
Described phosphorus aluminium glue accounts for 10 ~ 50% of total catalyst weight, and the weight of phosphorus aluminium glue is with Al
2o
3and P
2o
5meter, wherein, P
2o
5account for 5 ~ 35% of phosphorus aluminium glue gross weight, in phosphorus aluminium glue, Al/P atomic ratio is 0.30 ~ 1.0:1.
Described phosphorus aluminium glue preparation process is: aluminium oxide that can be acid-soluble or aluminium hydroxide deionized water dispersion making beating, solid content 20 ~ the 40wt.% of slurries, then 95 ~ 120 DEG C are warming up to, be the ratio of 0.30 ~ 1.0:1 in Al/P atomic ratio, add phosphoric acid and keep reaction 0.5 ~ 2 hour, until become transparent colloid.
The preparation method of described catalytic cracking catalyst, comprises the following steps:
(1) by the making beating of clay use water evenly, slurry solid content is 15 ~ 50wt.%, obtained clay slurry;
(2) by the making beating of molecular sieve use water evenly, slurry solid content 25 ~ 60wt.%, obtained molecular sieve pulp;
(3) aluminium oxide that can be acid-soluble or aluminium hydroxide deionized water dispersion making beating, solid content 20 ~ the 40wt.% of slurries, then 95 ~ 110 DEG C are warming up to, be the ratio of 0.30 ~ 1.0:1 in Al/P atomic ratio, add phosphoric acid, and keep reaction 0.5 ~ 2 hour, and until become transparent colloid, obtained phosphorus aluminium glue;
(4) above-mentioned clay slurry, molecular sieve pulp, phosphorus aluminium glue and soluble zinc compound are mixed, make the catalyst slurry that solid content is 20 ~ 45wt.%;
Catalytic cracking catalyst is made in obtained catalyst slurry spraying dry, roasting.
Described soluble zinc compound is zinc nitrate, zinc chloride or zinc sulfate etc.
Catalyst prepared by the present invention has following beneficial effect:
Catalyst of the present invention contains zinc oxide and is prepared from for binding agent with phosphorus aluminium glue, has the performance of the arene content in propylene enhancing and raising gasoline.Compared with the colloidal sol containing chloride and aluminium catalyst high with adopting cost, do not have corrosion and the emission problem of hydrogen chloride gas, catalyst is substantially not chloride yet; Because phosphorus aluminium glue adhesive property is good, therefore catalyst abrasion intensity of the present invention is high.Preparation method of the present invention is simple, be easy to realize.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.
In the embodiment of the present invention, Kaolinite Preparation of Catalyst is raw materials used as follows:
Boehmite: Zhong Lv Shandong branch company produces
Kaolin: China Kaolin Co., Ltd produces
Alumina gel: China Petrochemical Industry's catalyst Shandong branch company (former Qilu Petrochemical Zhou village catalyst plant)
Aluminium hydrate powder: Zhong Lv Shandong branch company produces
Containing rare earth overtemperature Y molecular sieve: China Petrochemical Industry's catalyst Shandong branch company
ZSM-5 molecular sieve: China Petrochemical Industry's catalyst Shandong branch company
Phosphoric acid: Xin Yuan chemical plant, Qingzhou in Shandong province
Analysis and evaluation method is as follows:
Sodium oxide molybdena measures: flare photometer
Phosphorus detection: colorimetric method
Chlorine monoxid assay: compleximetry
Zinc-content determination: compleximetry
Catalyst abrasion strength detection: be placed on by the catalyst of 10 grams of roastings in a straight tube, blows mill 5 hours with the air of the constant gas speed of humidification, and except first hour, the average abrasion percentage of latter four hours is called catalyst abrasion intensity.
Heavy oil micro anti-evaluation condition: reaction raw materials is the triumph wax oil of 227 ~ 110 DEG C, and reaction temperature is 490 DEG C, and weight space velocity is 16h
-1, 70 seconds reaction time, catalyst loading amount 5 grams.
Embodiment 1
The phosphorus aluminium glue preparation of Al/P=0.45:1:
By 1200 grams of aluminium hydroxides (containing Al
2o
365%) with 6500 grams of deionized water dispersion making beating, be then warming up to 100 ± 5 DEG C, stir and slowly add 3918.5 grams of SPAs, and keep reaction 1 hour, until become transparent colloid at 100 ± 5 DEG C.This phosphorus aluminium glue is containing 7.6%Al by analysis
2o
3, containing the %P of 23.5 weight
2o
5, Al/P=0.45.
Embodiment 2
The phosphorus aluminium glue preparation of Al/P=0.75:1:
By 1200 grams of boehmites (containing Al
2o
365%) with 4200 grams of deionized water dispersion making beating, be then warming up to 100 ± 5 DEG C, stir and slowly add 2351 grams of SPAs, and keep reaction 2 hours, until become transparent colloid at 100 ± 5 DEG C.This phosphorus aluminium glue is containing 11.4 % by weight Al by analysis
2o
3, containing 21.2 % by weight P
2o
5, Al/P=0.75.
Embodiment 3
1500 grams (butts) are added 4000 grams of water making beating evenly containing rare earth overtemperature Y molecular sieve and 400 grams of (butt) ZSM-5 molecular sieves, makes molecular sieve pulp for subsequent use.
1700 grams of kaolin and 4000 water are pulled an oar evenly, adds 1400 grams (with Al
2o
3meter) Alumina gel, add Manufactured molecular sieve pulp again, spraying dry after homogeneous after making beating evenly, 650 DEG C of roastings 3 hours, i.e. obtained catalyst A.Its composition and tear strength are in table 1, and heavy oil micro anti-evaluation the results are shown in Table 2.
Embodiment 4
1500 grams (butts) are added 4000 grams of water making beating evenly containing rare earth overtemperature Y molecular sieve and 4000 grams of (butt) ZSM-5 molecular sieves, makes molecular sieve pulp for subsequent use.
1700 grams of (butt) kaolin and 4000 water are pulled an oar evenly, adds 1400 grams (with Al
2o
3and P
2o
5meter) the phosphorus aluminium glue prepared of embodiment 1, add Manufactured molecular sieve pulp again, spraying dry after homogeneous after making beating evenly, 650 DEG C of roastings 3 hours, i.e. obtained catalyst B.Its composition and tear strength are in table 1, and heavy oil micro anti-evaluation the results are shown in Table 2.
Embodiment 5
1500 grams (butts) are added 4000 grams of water making beating evenly containing rare earth overtemperature Y molecular sieve and 400 grams of (butt) ZSM-5 molecular sieves, makes molecular sieve pulp for subsequent use.
1675 grams of (butt) kaolin and 4000 water are pulled an oar evenly, adds 1400 grams (with Al
2o
3and P
2o
5meter) the phosphorus aluminium glue prepared of embodiment 1, add the molecular sieve pulp made after making beating evenly, finally add the zinc nitrate of 25 grams (in ZnO), spraying dry after homogeneous, 650 DEG C of roastings 3 hours, i.e. obtained catalyst C.Its composition and tear strength the results are shown in Table 2 in table 1 heavy oil micro anti-evaluation.
Embodiment 6
1500 grams (butts) are added 4000 grams of water making beating evenly containing rare earth overtemperature Y molecular sieve and 400 grams of (butt) ZSM-5 molecular sieves, makes molecular sieve pulp for subsequent use.
1625 grams of (butt) kaolin and 4000 water are pulled an oar evenly, adds 1400 grams (with Al
2o
3and P
2o
5meter) the phosphorus aluminium glue prepared of embodiment 1, add the molecular sieve pulp made again after making beating evenly, finally add the zinc nitrate of 75 grams (in ZnO), spraying dry after homogeneous, 650 DEG C of roastings 3 hours, i.e. obtained catalyst D.Its composition and tear strength are in table 1, and heavy oil micro anti-evaluation the results are shown in Table 2.
Embodiment 7
1050 grams (butts) are added 2600 grams of water making beating evenly containing rare earth overtemperature Y molecular sieve and 200 grams of (butt) ZSM-5 molecular sieves, makes molecular sieve pulp for subsequent use.
3000 grams of (butt) kaolin and 7500 water are pulled an oar evenly, adds 750 grams (with Al
2o
3meter) Alumina gel, add the molecular sieve pulp made again, spraying dry after homogeneous after making beating evenly, 650 DEG C of roastings 3 hours, i.e. obtained catalyst E.Its composition and tear strength are in table 1.
Embodiment 8
1050 grams (butts) are added 4000 grams of water making beating evenly containing rare earth overtemperature Y molecular sieve and 200 grams of (butt) ZSM-5 molecular sieves, makes molecular sieve pulp for subsequent use.
3000 grams of (butt) kaolin and 7500 water are pulled an oar evenly, adds 750 grams (with Al
2o
3and P
2o
5meter) the phosphorus aluminium glue prepared of embodiment 2, add the molecular sieve pulp made again, spraying dry after homogeneous after making beating evenly, 650 DEG C of roastings 3 hours, i.e. obtained catalyst F.Its composition and tear strength are in table 1.
Embodiment 9
1500 grams (butts) are added 4000 grams of water making beating evenly containing rare earth overtemperature Y molecular sieve and 400 grams of (butt) ZSM-5 molecular sieves, makes molecular sieve pulp for subsequent use.
2950 grams of kaolin and 7500 water are pulled an oar evenly, adds 750 grams (with Al
2o
3and P
2o
5meter) the phosphorus aluminium glue prepared of embodiment 2, add the molecular sieve pulp made again after making beating evenly, finally add the zinc nitrate of 50 grams (in ZnO), spraying dry after homogeneous, 650 DEG C of roastings 3 hours, i.e. obtained catalyst G.Its composition and tear strength are in table 1.
Embodiment 10
1500 grams (butts) are added 4000 grams of water making beating evenly containing rare earth overtemperature Y molecular sieve and 400 grams of (butt) ZSM-5 molecular sieves, makes molecular sieve pulp for subsequent use.
2900 grams of kaolin and 7500 water are pulled an oar evenly, adds 750 grams (with Al
2o
3and P
2o
5meter) the phosphorus aluminium glue prepared of embodiment 2, add the molecular sieve pulp made again after making beating evenly, finally add the zinc nitrate of 100 grams (in ZnO), spraying dry after homogeneous, 650 DEG C of roastings 3 hours, i.e. obtained catalyst H.Its composition and tear strength are in table 1.
As can be seen from Table 1, under equal conditions, catalyst B that phosphorus aluminium glue is binding agent, C, D and F, G, H is used to have better tear strength than the catalyst A and E using Alumina gel.
Table 2 heavy oil micro anti-evaluation result can be found out, catalyst B, C, D and A compare, and the density of propylene in its yield of liquefied gas and liquefied gas is all improved, and propene yield increases.Catalyst C, D and A, B compare, and Aromatic Hydrocarbon in Gasoline content improves.
Table 1 and table 2 data result show, catalyst abrasion intensity prepared by the present invention is good, have the feature of producing more propylene and raising Aromatic Hydrocarbon in Gasoline content.
Table 1 catalyst composition and intensity
The micro-opposition of table 2 heavy oil is than evaluation result (m%)
Claims (5)
1. a preparation method for catalytic cracking catalyst, is characterized in that comprising the following steps:
(1) by the making beating of clay use water evenly, slurry solid content is 15 ~ 50wt.%, obtained clay slurry;
(2) by the making beating of molecular sieve use water evenly, slurry solid content 25 ~ 60wt.%, obtained molecular sieve pulp;
(3) aluminium oxide that can be acid-soluble or aluminium hydroxide deionized water dispersion making beating, solid content 20 ~ 40 wt.% of slurries, then 95 ~ 110 DEG C are warming up to, be the ratio of 0.30 ~ 1.0:1 in Al/P atomic ratio, add phosphoric acid, and keep reaction 0.5 ~ 2 hour, and until become transparent colloid, obtained phosphorus aluminium glue;
(4) above-mentioned clay slurry, molecular sieve pulp, phosphorus aluminium glue and zinc oxide are mixed, make the catalyst slurry that solid content is 20 ~ 45 wt.%;
Catalytic cracking catalyst is made in obtained catalyst slurry spraying dry, roasting;
Described molecular sieve accounts for 15 ~ 45% of total catalyst weight;
Described clay accounts for 25 ~ 70% of total catalyst weight;
Described phosphorus aluminium glue accounts for 10 ~ 50% of total catalyst weight, and the weight of phosphorus aluminium glue is with Al
2o
3and P
2o
5meter;
Described zinc oxide accounts for 0.5 ~ 2.0 % of total catalyst weight;
Described catalytic cracking catalyst, comprises active component, carrier and binding agent, and wherein active component is molecular sieve, and carrier is clay, and this catalyst adopts phosphorus aluminium glue as binding agent, and adds zinc oxide as auxiliary agent in the process of catalyst preparing.
2. the preparation method of catalytic cracking catalyst according to claim 1, is characterized in that described molecular sieve is one or more in Y zeolite, ZSM-5 molecular sieve, SAPO-11 molecular sieve.
3. the preparation method of catalytic cracking catalyst according to claim 1, is characterized in that described clay is kaolin, bentonite or montmorillonite.
4. the preparation method of catalytic cracking catalyst according to claim 1, is characterized in that in described phosphorus aluminium glue, P
2o
5account for 5 ~ 35% of phosphorus aluminium glue gross weight.
5. the preparation method of catalytic cracking catalyst according to claim 4, is characterized in that, in described phosphorus aluminium glue, Al/P atomic ratio is 0.30 ~ 1.0:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210489240.3A CN102974386B (en) | 2012-11-27 | 2012-11-27 | Catalytic cracking catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210489240.3A CN102974386B (en) | 2012-11-27 | 2012-11-27 | Catalytic cracking catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102974386A CN102974386A (en) | 2013-03-20 |
| CN102974386B true CN102974386B (en) | 2015-08-19 |
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| CN107303479B (en) * | 2016-04-19 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of phosphorus Aluminum sol and its preparation method and application and catalytic cracking catalyst and preparation method thereof |
| CN107376887B (en) * | 2016-05-16 | 2020-05-19 | 中国石油化工股份有限公司 | Silica sol, silicon-aluminum sol, preparation method and application thereof, catalytic cracking catalyst and preparation method |
| CN108097303B (en) * | 2017-11-22 | 2021-06-11 | 青岛惠城环保科技股份有限公司 | Preparation method of catalyst for preparing low-carbon olefin by catalytic cracking of diesel oil |
| CN112279262A (en) * | 2020-11-16 | 2021-01-29 | 四川奥力奋催化材料有限公司 | Silicoaluminophosphate molecular sieve, catalyst for preparing olefin from methanol, preparation method and application thereof |
| CN113262813A (en) * | 2021-05-18 | 2021-08-17 | 湖北赛因斯科技开发有限公司 | Method for improving strength of catalytic cracking propylene additive and application |
| CN115025806A (en) * | 2022-05-19 | 2022-09-09 | 青岛惠城环保科技集团股份有限公司 | Preparation method of iron pollution resistant catalytic cracking catalyst |
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| US6355591B1 (en) * | 2000-01-03 | 2002-03-12 | Indian Oil Corporation Limited | Process for the preparation of fluid catalytic cracking catalyst additive composition |
| CN1872957A (en) * | 2005-05-31 | 2006-12-06 | 中国石油化工股份有限公司 | Method for catalytic cracking petroleum hydrocarbons |
| CN101062477A (en) * | 2006-04-28 | 2007-10-31 | 中国石油化工股份有限公司 | Cracking product sulfur-lowing catalyst |
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| US6355591B1 (en) * | 2000-01-03 | 2002-03-12 | Indian Oil Corporation Limited | Process for the preparation of fluid catalytic cracking catalyst additive composition |
| CN1872957A (en) * | 2005-05-31 | 2006-12-06 | 中国石油化工股份有限公司 | Method for catalytic cracking petroleum hydrocarbons |
| CN101062477A (en) * | 2006-04-28 | 2007-10-31 | 中国石油化工股份有限公司 | Cracking product sulfur-lowing catalyst |
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