CN102974386A - Catalytic cracking catalyst and preparation method thereof - Google Patents
Catalytic cracking catalyst and preparation method thereof Download PDFInfo
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- CN102974386A CN102974386A CN2012104892403A CN201210489240A CN102974386A CN 102974386 A CN102974386 A CN 102974386A CN 2012104892403 A CN2012104892403 A CN 2012104892403A CN 201210489240 A CN201210489240 A CN 201210489240A CN 102974386 A CN102974386 A CN 102974386A
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- catalyst
- catalytic cracking
- molecular sieve
- cracking catalyst
- preparation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 22
- 239000003292 glue Substances 0.000 claims abstract description 42
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011787 zinc oxide Substances 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 55
- 239000004411 aluminium Substances 0.000 claims description 54
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 54
- 239000002808 molecular sieve Substances 0.000 claims description 52
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 52
- 229910052698 phosphorus Inorganic materials 0.000 claims description 41
- 239000011574 phosphorus Substances 0.000 claims description 40
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 38
- 238000010009 beating Methods 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 12
- 239000005995 Aluminium silicate Substances 0.000 claims description 11
- 235000012211 aluminium silicate Nutrition 0.000 claims description 11
- 238000001694 spray drying Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 239000004927 clay Substances 0.000 claims description 9
- YAPQBXQYLJRXSA-UHFFFAOYSA-N theobromine Chemical compound CN1C(=O)NC(=O)C2=C1N=CN2C YAPQBXQYLJRXSA-UHFFFAOYSA-N 0.000 claims description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229960004559 theobromine Drugs 0.000 claims description 4
- 150000003752 zinc compounds Chemical class 0.000 claims description 3
- 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
- 229910052570 clay Inorganic materials 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
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 7
- 238000005299 abrasion Methods 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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000460 chlorine Substances 0.000 abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 abstract 3
- 239000000853 adhesive Substances 0.000 abstract 2
- ILXDAXZQNSOSAE-UHFFFAOYSA-N [AlH3].[Cl] Chemical compound [AlH3].[Cl] ILXDAXZQNSOSAE-UHFFFAOYSA-N 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 10
- 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
- 239000000203 mixture Substances 0.000 description 8
- 239000000295 fuel oil Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 235000011007 phosphoric acid Nutrition 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 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
- 239000004215 Carbon black (E152) Substances 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
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 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
- 239000003643 water by type Substances 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
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical class Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 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
- 238000011068 loading method Methods 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 the technical field of catalysts, and in particular relates to a catalytic cracking catalyst and a preparation method thereof. According to the catalytic cracking catalyst, phosphorus aluminum glue is used as an adhesive; and in a catalyst preparation process, zinc oxide is added and is used as an auxiliary agent. The catalyst contains the zinc oxide, and the phosphorus aluminum glue is used as the adhesive; and the catalyst has the functions of improving the yield of propylene and increasing the aromatics content in gasoline. Compared with the catalyst which is high in cost and contains chlorine aluminum gel, the catalyst solves the problems of corrosion and discharging of hydrochloric acid gas and does not contain chlorine; the phosphorus aluminum glue is high in adhesion, so that the catalyst is high in abrasion resistance; and the preparation method is simple and feasible and is easy to implement.
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
Industrial used catalytic cracking catalyst generally all is to be made by molecular sieve (active component), matrix clay and binding agent at present, and employed binding agent mostly is boehmite and aluminium colloidal sol.But use aluminium base binding agent, particularly use aluminium colloidal sol can bring serious problem, its contained higher chlorion can produce a large amount of hydrogen chloride gas when spray-drying, thus etching apparatus and cause atmosphere pollution.When catalyst used at device, residual chlorion meeting etching apparatus also affected the activity of catalyst in the catalyst.
In recent years, the phosphorus aluminium glue begins to introduce the preparation of catalytic cracking catalyst as binding agent, and is selective to improve the tear strength of catalyst, and hydrothermal stability, also solved problem of environmental pollution.
CN1076714A discloses a kind of phosphorous hydrocarbon cracking catalyzer of the preparation take phosphorated aluminiferous collosol as binding agent.Used phosphorated aluminiferous collosol is according to CN170384A and the disclosed method preparation of CN170385A.The CN170384A preparation method adds orthophosphoric acid or aluminium dihydrogen phosphate in the colloidal sol containing chloride and aluminium, concentrates through the high temperature depolymerization to make phosphorous and aluminium colloidal sol chlorine.The CN170385A preparation method reacts metallic aluminium, hydrochloric acid (or aluminium salt), phosphoric acid (or aluminium dihydrogen phosphate) under certain condition and through the concentrated phosphorated aluminiferous collosol that makes of high temperature depolymerization.A lot of weak points that the method exists, the one, need the high temperature depolymerization concentrated in the preparation process, the preparation more complicated.The 2nd, for guaranteeing the stable and mobile of phosphorus aluminium glue, the content of phosphorus is lower, and general Al/P weight ratio is greater than 4.The 3rd, the phosphorus aluminium glue of preparation still contains the chlorine of higher amount.
CN1180059C discloses the phosphorous hydrocarbon cracking catalyzer that a kind of phosphorated aluminiferous collosol is the binding agent preparation.Its preparation method is to make not chloride phosphorus aluminium glue with aluminium oxide or aluminium hydroxide and phosphatase reaction first, then mixes use with colloidal sol containing chloride and aluminium.Although the method has been simplified the process of phosphorated aluminiferous collosol, but still just part has substituted chloride aluminium colloidal sol, still can not get rid of corrosion and the environmental issue of chlorine.
USP5194412 discloses a kind of production of cracking catalyst take the phosphorus aluminium glue as binding agent, and used phosphorus aluminium glue makes with aluminium salt and phosphatase reaction, 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 take the phosphorus aluminium glue as binding agent, and used phosphorus aluminium glue makes with metallic aluminium powder and phosphatase reaction, 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 to contain zinc oxide and the molecular sieve type Cracking catalyst take the phosphorus aluminium glue as 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 the phosphorus aluminium glue as binding agent, and adds zinc oxide as auxiliary agent in the process of catalyst preparation.
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, the 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, the Al/P atomic ratio is 0.30～1.0:1 in the phosphorus aluminium glue.
Described phosphorus aluminium glue preparation process is: the aluminium oxide that theobromine is molten or aluminium hydroxide disperse making beating with deionized water, solid content 20～the 40wt.% of slurries, then be warming up to 95～120 ℃, be the ratio of 0.30～1.0:1 in the 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 may further comprise the steps:
(1) with the making beating of clay water evenly, slurry solid content is 15～50wt.%, makes clay slurry;
(2) with the making beating of molecular sieve water evenly, slurry solid content 25～60wt.% makes molecular sieve pulp;
(3) aluminium oxide that theobromine is molten or aluminium hydroxide disperse making beating with deionized water, solid content 20～the 40wt.% of slurries, then be warming up to 95～110 ℃, be the ratio of 0.30～1.0:1 in the Al/P atomic ratio, add phosphoric acid, and keep reaction 0.5～2 hour, until become transparent colloid, make the 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 resulting catalyst slurry spray-drying, roasting.
Described soluble zinc compound is zinc nitrate, zinc chloride or zinc sulfate etc.
The catalyst of the present invention's preparation has following beneficial effect:
Catalyst of the present invention contains zinc oxide and is prepared from take the phosphorus aluminium glue as binding agent, has the performance of the arene content in propylene enhancing and the raising gasoline.The colloidal sol containing chloride and aluminium catalyst high with adopting cost compared, and do not have corrosion and the emission problem of hydrogen chloride gas, and catalyst is substantially not chloride yet; Because phosphorus aluminium glue adhesive property is good, catalyst abrasion intensity therefore of the present invention is high.Preparation method of the present invention is simple, be easy to realize.
The specific embodiment
Below in conjunction with embodiment the present invention is described further.
In the embodiment of the invention, Kaolinite Preparation of Catalyst is raw materials used as follows:
Boehmite: middle aluminium Shandong branch company produces
Kaolin: China Kaolin Co., Ltd produces
Aluminium colloidal sol: catalyst Shandong branch company of China Petrochemical Industry (former Qilu Petrochemical Zhou village catalyst plant)
Aluminium hydrate powder: middle aluminium Shandong branch company produces
Contain rare earth overtemperature Y molecular sieve: catalyst Shandong branch company of China Petrochemical Industry
ZSM-5 molecular sieve: catalyst Shandong branch company of China Petrochemical Industry
Phosphoric acid: chemical plant, the prosperous source of Qingzhou in Shandong province
The analysis and evaluation method is as follows:
Sodium oxide molybdena is measured: flare photometer
Phosphorus detection: colorimetric method
Chlorine monoxid assay: compleximetry
Zinc-content determination: compleximetry
The catalyst abrasion strength detection: the catalyst of 10 gram roastings are placed in the straight tube, blow with the air of the constant gas speed of humidification and ground 5 hours, except first hour, rear four hours average abrasion percentage is called catalyst abrasion intensity.
Heavy oil micro anti-evaluation condition: reaction raw materials is 227～110 ℃ triumph wax oil, and reaction temperature is 490 ℃, 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:
1200 gram aluminium hydroxides (are contained Al
2O
365%) disperse making beating with 6500 gram deionized waters, then be warming up to 100 ± 5 ℃, stirring slowly adds 3918.5 gram SPAs, and keeps reacting 1 hour at 100 ± 5 ℃, until become transparent colloid.This phosphorus aluminium glue contains 7.6%Al by analysis
2O
3, contain 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:
1200 gram boehmites (are contained Al
2O
365%) disperse making beating with 4200 gram deionized waters, then be warming up to 100 ± 5 ℃, stirring slowly adds 2351 gram SPAs, and keeps reacting 2 hours at 100 ± 5 ℃, until become transparent colloid.This phosphorus aluminium glue contains 11.4 % by weight Al by analysis
2O
3, contain 21.2 % by weight P
2O
5, Al/P=0.75.
Embodiment 3
1500 grams (butt) are contained rare earth overtemperature Y molecular sieve and 400 gram (butt) ZSM-5 molecular sieves add 4000 gram water making beating evenly, it is for subsequent use to make molecular sieve pulp.
1700 gram kaolin and the making beating of 4000 water are even, add 1400 grams (with Al
2O
3Meter) aluminium colloidal sol adds Manufactured molecular sieve pulp after the making beating evenly again, and spray-drying behind the homogeneous 650 ℃ of roastings 3 hours, namely makes catalyst A.Its composition and tear strength see Table 1, and the heavy oil micro anti-evaluation the results are shown in Table 2.
Embodiment 4
1500 grams (butt) are contained rare earth overtemperature Y molecular sieve and 4000 gram (butt) ZSM-5 molecular sieves add 4000 gram water making beating evenly, it is for subsequent use to make molecular sieve pulp.
1700 gram (butt) kaolin and the making beating of 4000 water are even, add 1400 grams (with Al
2O
3And P
2O
5The phosphorus aluminium glue of embodiment 1 preparation meter) adds Manufactured molecular sieve pulp after the making beating evenly again, and spray-drying behind the homogeneous 650 ℃ of roastings 3 hours, namely makes catalyst B.Its composition and tear strength see Table 1, and the heavy oil micro anti-evaluation the results are shown in Table 2.
Embodiment 5
1500 grams (butt) are contained rare earth overtemperature Y molecular sieve and 400 gram (butt) ZSM-5 molecular sieves add 4000 gram water making beating evenly, it is for subsequent use to make molecular sieve pulp.
1675 gram (butt) kaolin and the making beating of 4000 water are even, add 1400 grams (with Al
2O
3And P
2O
5The phosphorus aluminium glue of embodiment 1 preparation meter) adds the molecular sieve pulp of making after the making beating evenly, add at last the zinc nitrate of 25 grams (in ZnO), and spray-drying behind the homogeneous 650 ℃ of roastings 3 hours, namely makes catalyst C.Its composition and tear strength see Table 1 heavy oil micro anti-evaluation and the results are shown in Table 2.
Embodiment 6
1500 grams (butt) are contained rare earth overtemperature Y molecular sieve and 400 gram (butt) ZSM-5 molecular sieves add 4000 gram water making beating evenly, it is for subsequent use to make molecular sieve pulp.
1625 gram (butt) kaolin and the making beating of 4000 water are even, add 1400 grams (with Al
2O
3And P
2O
5The phosphorus aluminium glue of embodiment 1 preparation meter) adds the molecular sieve pulp of making again after the making beating evenly, add at last the zinc nitrate of 75 grams (in ZnO), and spray-drying behind the homogeneous 650 ℃ of roastings 3 hours, namely makes catalyst D.Its composition and tear strength see Table 1, and the heavy oil micro anti-evaluation the results are shown in Table 2.
Embodiment 7
1050 grams (butt) are contained rare earth overtemperature Y molecular sieve and 200 gram (butt) ZSM-5 molecular sieves add 2600 gram water making beating evenly, it is for subsequent use to make molecular sieve pulp.
3000 gram (butt) kaolin and the making beating of 7500 water are even, add 750 grams (with Al
2O
3Meter) aluminium colloidal sol adds the molecular sieve pulp of making again after the making beating evenly, spray-drying behind the homogeneous 650 ℃ of roastings 3 hours, namely makes catalyst E.Its composition and tear strength see Table 1.
Embodiment 8
1050 grams (butt) are contained rare earth overtemperature Y molecular sieve and 200 gram (butt) ZSM-5 molecular sieves add 4000 gram water making beating evenly, it is for subsequent use to make molecular sieve pulp.
3000 gram (butt) kaolin and the making beating of 7500 water are even, add 750 grams (with Al
2O
3And P
2O
5The phosphorus aluminium glue of embodiment 2 preparations meter) adds the molecular sieve pulp of making again after the making beating evenly, spray-drying behind the homogeneous 650 ℃ of roastings 3 hours, namely makes catalyst F.Its composition and tear strength see Table 1.
Embodiment 9
1500 grams (butt) are contained rare earth overtemperature Y molecular sieve and 400 gram (butt) ZSM-5 molecular sieves add 4000 gram water making beating evenly, it is for subsequent use to make molecular sieve pulp.
2950 gram kaolin and the making beating of 7500 water are even, add 750 grams (with Al
2O
3And P
2O
5The phosphorus aluminium glue of embodiment 2 preparations meter) adds the molecular sieve pulp of making again after the making beating evenly, add at last the zinc nitrate of 50 grams (in ZnO), and spray-drying behind the homogeneous 650 ℃ of roastings 3 hours, namely makes catalyst G.Its composition and tear strength see Table 1.
Embodiment 10
1500 grams (butt) are contained rare earth overtemperature Y molecular sieve and 400 gram (butt) ZSM-5 molecular sieves add 4000 gram water making beating evenly, it is for subsequent use to make molecular sieve pulp.
2900 gram kaolin and the making beating of 7500 water are even, add 750 grams (with Al
2O
3And P
2O
5The phosphorus aluminium glue of embodiment 2 preparations meter) adds the molecular sieve pulp of making again after the making beating evenly, add at last the zinc nitrate of 100 grams (in ZnO), and spray-drying behind the homogeneous 650 ℃ of roastings 3 hours, namely makes catalyst H.Its composition and tear strength see Table 1.
As can be seen from Table 1, under equal conditions, use the phosphorus aluminium glue to have better tear strength as catalyst B, C, D and F, G, the H of binding agent than the catalyst A and the E that use aluminium colloidal sol.
Table 2 heavy oil micro anti-evaluation is the result can find out, catalyst B, C, D compare with A, and the density of propylene in its yield of liquefied gas and the liquefied gas all is improved, and propene yield increases.Catalyst C, D compare with A, B, and Aromatic Hydrocarbon in Gasoline content improves.
Table 1 and table 2 data result show that the catalyst abrasion intensity of the present invention's preparation is good, have the characteristics of producing more propylene and raising Aromatic Hydrocarbon in Gasoline content.
Table 1 catalyst forms and intensity
The little opposition of table 2 heavy oil is than evaluation result (m%)
Claims (10)
1. catalytic cracking catalyst, comprise active component, carrier and binding agent, wherein active component is molecular sieve, and carrier is clay, it is characterized in that: this catalyst adopts the phosphorus aluminium glue as binding agent, and adds zinc oxide as auxiliary agent in the process of catalyst preparation.
2. catalytic cracking catalyst according to claim 1 is characterized in that described zinc oxide accounts for 0.5～2.0% of total catalyst weight.
3. catalytic cracking catalyst according to claim 1 and 2 is characterized in that described molecular sieve is one or more in Y zeolite, ZSM-5 molecular sieve, the SAPO-11 molecular sieve.
4. catalytic cracking catalyst according to claim 3 is characterized in that described molecular sieve accounts for 15～45% of total catalyst weight.
5. catalytic cracking catalyst according to claim 1 is characterized in that described clay is kaolin, bentonite or montmorillonite, and clay accounts for 25～70% of total catalyst weight.
6. catalytic cracking catalyst according to claim 1 is characterized in that 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.
7. according to claim 1 or 6 described catalytic cracking catalysts, it is characterized in that in the described phosphorus aluminium glue P
2O
5Account for 5～35% of phosphorus aluminium glue gross weight.
8. catalytic cracking catalyst according to claim 7 is characterized in that in the described phosphorus aluminium glue, the Al/P atomic ratio is 0.30～1.0:1.
9. catalytic cracking catalyst according to claim 8, it is characterized in that described phosphorus aluminium glue preparation process is: the aluminium oxide that theobromine is molten or aluminium hydroxide disperse making beating with deionized water, solid content 20～the 40wt.% of slurries, then be warming up to 95～120 ℃, be the ratio of 0.30～1.0:1 in the Al/P atomic ratio, add phosphoric acid and keep reaction 0.5～2 hour, until become transparent colloid.
10. the preparation method of a catalytic cracking catalyst claimed in claim 1 is characterized in that may further comprise the steps:
(1) with the making beating of clay water evenly, slurry solid content is 15～50wt.%, makes clay slurry;
(2) with the making beating of molecular sieve water evenly, slurry solid content 25～60wt.% makes molecular sieve pulp;
(3) aluminium oxide that theobromine is molten or aluminium hydroxide disperse making beating with deionized water, solid content 20～the 40wt.% of slurries, then be warming up to 95～110 ℃, be the ratio of 0.30～1.0:1 in the Al/P atomic ratio, add phosphoric acid, and keep reaction 0.5～2 hour, until become transparent colloid, make the 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 resulting catalyst slurry spray-drying, roasting.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107303479A (en) * | 2016-04-19 | 2017-10-31 | 中国石油化工股份有限公司 | A kind of phosphorus Alumina gel and its preparation method and application and catalytic cracking catalyst and preparation method thereof |
| CN107376887A (en) * | 2016-05-16 | 2017-11-24 | 中国石油化工股份有限公司 | A kind of Ludox and silicon-aluminum sol and preparation method and application and catalytic cracking catalyst and preparation method |
| CN108097303A (en) * | 2017-11-22 | 2018-06-01 | 青岛惠城环保科技股份有限公司 | A kind of preparation method of catalytic diesel oil cracking producing light olefins catalyst |
| 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 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2012
- 2012-11-27 CN CN201210489240.3A patent/CN102974386B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107303479A (en) * | 2016-04-19 | 2017-10-31 | 中国石油化工股份有限公司 | A kind of phosphorus Alumina gel and its preparation method and application and catalytic cracking catalyst and preparation method thereof |
| 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 |
| CN107376887A (en) * | 2016-05-16 | 2017-11-24 | 中国石油化工股份有限公司 | A kind of Ludox and silicon-aluminum sol and preparation method and application and catalytic cracking catalyst and preparation method |
| 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 |
| CN108097303A (en) * | 2017-11-22 | 2018-06-01 | 青岛惠城环保科技股份有限公司 | A kind of preparation method of catalytic diesel oil cracking producing light olefins catalyst |
| 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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