CN1177642C - Semi-synthesized olefins conversion catalyst containing modified nano aluminium oxide - Google Patents
Semi-synthesized olefins conversion catalyst containing modified nano aluminium oxide Download PDFInfo
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- CN1177642C CN1177642C CNB031020453A CN03102045A CN1177642C CN 1177642 C CN1177642 C CN 1177642C CN B031020453 A CNB031020453 A CN B031020453A CN 03102045 A CN03102045 A CN 03102045A CN 1177642 C CN1177642 C CN 1177642C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 title abstract description 13
- 150000001336 alkenes Chemical class 0.000 title 1
- 239000002808 molecular sieve Substances 0.000 claims abstract description 21
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 16
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 16
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004927 clay Substances 0.000 claims abstract description 10
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 10
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 9
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 9
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims abstract description 7
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract 2
- 230000004048 modification Effects 0.000 claims description 13
- 238000012986 modification Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 7
- 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 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- 239000004113 Sepiolite Substances 0.000 claims description 4
- 239000000440 bentonite Substances 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229910052624 sepiolite Inorganic materials 0.000 claims description 4
- 235000019355 sepiolite Nutrition 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000012013 faujasite Substances 0.000 claims description 2
- -1 galapectite Chemical compound 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007767 bonding agent Substances 0.000 claims 2
- 229910021647 smectite Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 229910052759 nickel Inorganic materials 0.000 abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 abstract description 6
- 238000005336 cracking Methods 0.000 abstract description 5
- 239000000295 fuel oil Substances 0.000 abstract description 5
- 238000005299 abrasion Methods 0.000 abstract description 4
- 238000001694 spray drying Methods 0.000 abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 3
- 229930195733 hydrocarbon Natural products 0.000 abstract description 3
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 238000009740 moulding (composite fabrication) Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 5
- 238000004523 catalytic cracking Methods 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910001680 bayerite Inorganic materials 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- RLLPVAHGXHCWKJ-UHFFFAOYSA-N permethrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 RLLPVAHGXHCWKJ-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
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- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a semi-synthesized hydrocarbon conversion catalyst containing modified nanometer level alumina, which is characterized in that artificially synthesized molecular sieves and modified nanometer level alumina containing the elements of cerium, zirconium and magnesium are dispersed in inorganic oxide clay and natural aluminium silicate clay to form into slurry by mix, and the semi-synthesized hydrocarbon conversion catalyst is manufactured after the operation of spray-drying forming, washing and drying. Because the modified nanometer level alumina is added in the catalyst of the present invention, the heavy oil cracking activity and the abrasion resistance of the catalyst are improved, and the selectivity of cracking reaction is simultaneously improved; the present invention is particularly suitable for processing heavy feed stock containing Ni and V.
Description
Technical field
The present invention relates to the petroleum hydrocarbon reforming catalyst, more particularly catalyst is a kind of semisynthetic hydrocarbon cracking catalyzer that contains the modified Nano grade aluminum oxide.
Background technology
The development heavy oil degree of depth transforms, and increases light-end products, produces clean fuel, and is all closely related with the performance of catalytic cracking (FCC) catalyst.
Catalytically cracked material contains heavy metal Ni, V, and they pollute catalyst.In regenerator, the V-arrangement on the catalyst becomes vanadic anhydride, can cause the irreversible destruction of zeolite crystal structure under steam atmosphere, causes catalyst surface area and active decline, and gasoline selective descends.Ni on the catalyst, as the deoxidation constituent element, it can make catalytic cracking reaction increase H
2And coke, the productive rate of costly products such as reduction gasoline, the working ability of restriction catalytic cracking unit.
A large amount of reports are arranged in the recent period: add aluminium oxide in the FCC catalyst, anti-Ni, V ability are greatly improved.
USP, 5173,174 reports and in the FCC catalyst formed by molecular sieve, macropore boehmite and aluminium oxide and rare earth, reduced the Ni that deposits and V to catalyst activity and adverse effect optionally.
Day, patent 84/1088 of the present disclosure was introduced a kind of adding gibbsite, δ-Al
2O
3With the FCC catalyst of bayerite, when the vacuum gas oil (VGO) of processing branch Witter oxygenation desulfurization, to reducing coke and hydrogen, effect is obvious especially.
EP0385246A1 introduces and contains the plan boehmite in the molecular sieve catalyst, bayerite, three water aluminium and η-Al
2O
3Be used for processing the raw material that contains Ni.
Summary of the invention
The purpose of this invention is to provide a kind of semi-synthetic Hydrocarban coversion catalysts that contains useful cerium, zirconium, magnesium-modified alumina in Nano level, to improve FCC catalyst heavy oil cracking activity and wearability.
The modified Nano aluminium oxide that contains of the present invention is (hereinafter to be referred as modification n-mAl
2O
3) the composition and the weight percentage of semi-synthetic Hydrocarban coversion catalysts:
Contain 1-40% by cerium, zirconium, magnesium-modified n-mAl
2O
3, 10-30% inorganic oxide binder, the artificial synthesis of molecular sieve of 5-50% and 10-60% natural aluminium silicate clay.
The preparation of the nano aluminium oxide of the present invention method that patent application provides with reference to CN1342609A.
Modification n-mAl of the present invention
2O
3Be with a kind of, two or three inorganic salt solution dipping n-mAl in cerium, zirconium, the magnesium
2O
3, filter then, oven dry, roasting make.Inorganic salts are nitrate, sulfate or chloride.Described modification n-mAl
2O
3In cerium content be 0.1-15%, zirconium content 0.1-20% content of magnesium 0.1-10%.
Inorganic oxide binder of the present invention is a silicate gel, alumina silicate colloidal sol, silica sol, one or more in the colloidal sol of aluminium.
Artificial synthesis of molecular sieve of the present invention comprises one or more mixtures of the molecular sieve that molecular sieve, β and L with faujasite structure zeolite structured molecular sieve, ZSM-5 are zeolite structured.
Natural aluminium silicate clay of the present invention comprises the artifactitious a kind of of the natural aluminium silicate clay of kaolin galapectite, bentonite, illiteracy bentonite, sepiolite or them, two or more mixture.
Preparation of catalysts method of the present invention comprises following process:
Earlier molecular sieve and modified Nano aluminium oxide are dispersed in the binding agent, the natural aluminium silicate clay with dilute with water is mixed into slurries then, spray-dried moulding, washs, is drying to obtain catalyst prod.
Advantage of the present invention and effect:
Key of the present invention is the n-mAl that adds modification in the FCC catalyst
2O
3, improve activity of such catalysts and wearability, and improve the anti-Ni of catalyst, V pollution capacity.
N-mAl
2O
3Have big outer surface and spacious duct, can pounce on and catch vanadium compounds and nickel compound in the feedstock oil, aluminium oxide and V, Ni can form the mineralising structure, thereby suppress the illeffects of V, Ni.Cerium, zirconium, the magnesium that adds all helps stablizing the microcellular structure of aluminium oxide, helps aluminium and plays a role, and simultaneously, cerium, zirconium, magnesium itself also have the effect that forms the mineralising structure with V, Ni.Therefore, catalyst of the present invention can improve stability, wearability and the preventing from heavy metal ability of its activity effectively.See by table 3, added the n-mAl of modification in the catalyst
2O
3After, its specific area has improved 10-20%, and pore volume increases 10%, and abrasion index has reduced 2-3 unit.The preventing from heavy metal evaluation result, during product distributed, coke reduced 17-18%.(0.5-0.7 percentage point), and the conversion ratio of heavy oil has improved 0.9 percentage point.
The specific embodiment
Further specify characteristics of the present invention below by concrete enforcement:
Example 1
To 23529g, the mixed solution that adds 65L cerium chloride, zirconium chloride, magnesium chloride in the n-m aluminium oxide, cerium chloride content is 21.5g/l in the solution, zirconium chloride is 12g/l, and density of magnesium chloride 142g/l soaked 1.5 hours, filters then, oven dry obtains modified Nano grade aluminum oxide A, wherein containing Ce is 4.0%, Zr2.0%, Mg1%.
Example 2
To 23529g n-mAl
2O
3The middle solution 65L that contains cerium chloride 42.5g/L that adds soaked 1.5 hours, and filtration, flood are done, and 400 ℃ of following roastings 2 hours, add the solution 65L of sulfur acid magnesium 12.8g/l again, soaked filtration, oven dry 1.5 hours.The modification n-mAl that obtains
2O
3Ce content is 8.0% among the B, and Mg content is 3.5%.
Example 3
To 23529g n-mAl
2O
3The middle solution 80L that adds sulfur acid zirconium solution 42.5g/L soaked 1.5 hours, filtered, dried, and among the modified Nano grade aluminum oxide C that obtains, Zr content is 12%.
Example 4
Add 3087g with the 5716gNay molecular sieve, the kaolin 8712g of ρ-aluminium oxide and dilute with water and 8800g Ludox mix or slurries are spray dried to catalyst.The composition of catalyst: Ny:20%, Al
2O
3: 20%, SiO
2: 20% and kaolin 40%.This catalyst is carried out ion-exchange, remove sodium ion, flood is done, and in 540 ℃ of following roastings 2 hours, obtains reference catalyst D again, and its composition sees Table 3.
Example 5
Add 3087g modification n-mAl with the 5716gNay molecular sieve
2O
3Be dispersed in the lump in the 8800g Ludox, the kaolin with the 8712g dilute with water is mixed into slurries again, carries out spray-drying, ion-exchange, and oven dry, under 540 ℃, roasting 2 hours obtains containing modified Nano level catalyst E again, and its composition sees Table 3.Described modification n-mAl
2O
3Middle Ce contains 3%, and Zr contains 4%, Mg1.5%.
Example 6
The super steady y type molecular sieve USY of 11990g, the 630gZSM-5 molecular sieve, composite soil (the kaolin: 60% that adds 4569g three hydroxyl aluminium faces and dilute with water, refining showplace emperor's soil 20%, 20% refining sepiolite) 5445g and 6400g aluminium colloidal sol are mixed into slurries, spray-drying makes reference catalyst F, and its composition sees Table 3.
Example 7
The super steady y molecular sieve of 11990g, 630gZSM-5 molecular sieve and 4569g modification n-mAl
2O
3Aluminium oxide A is distributed in the 6400g aluminium colloidal sol in the lump, composite soil (kaolin 60%, refining bentonite 20%, the 20% refining sepiolite that covers) 5445g with dilute with water is mixed into slurries again, spray-drying obtains containing modified Nano grade aluminum oxide catalyst G, and its composition sees Table 3.
Example 8
The catalyst of above-mentioned examples preparation and reference agent deposit the Ni of 3000ppm and the V of 4000ppm, pass through the gas of 90% steam and 10% air again under 813 ℃ of normal pressures, and hydrothermal aging 5 hours makes final catalyst and carries out catalytic cracking reaction.The cracking activity of catalyst carries out reaction evaluating on small fixed flowing bed.Reaction condition: 512 ℃ of weight space velocities 20, oil ratio 3, reaction temperature.Raw materials used oil nature sees Table 2.The physico-chemical property of catalyst and reaction result are all listed table 3 in.
Catalyst abrasion index CCAI in the table 3 measures:
Catalyst and reference catalyst claim sample 45 grams to put into developmental tube 600 ℃ of following roastings 2 hours.The developmental tube diameter is 38mm, and three diameters are arranged at the bottom is the nozzle of 0.1mm, is blown into air, and air mass flow is 0.425m
3/ hr blew mill through 42 hours.Get and blow the fine powder collected in 12 hours of mill and be weighed as W1, get that to blow the fine powder total amount of collecting in 42 hours be W2, definition CCAI is an abrasion index, concrete calculating:
Table 1 modified Nano grade aluminum oxide performance
| Modified aluminas | A | B | C | |
| Ce，wt％ | 3.9 | 7.8 | 0 | |
| Zr，wt％ | 1.9 | 0 | 12 | |
| MgO，wt％ | 1.6 | 5.7 | 0 | |
| SiO 2，wt％ | ≤0.013 | ≤0.013 | ≤0.013 | |
| Fe 2O 3，wt％ | ≤0.02 | ≤0.02 | ≤0.02 | |
| Na 2O，wt％ | 0.33 | 0.28 | 0.29 | |
| Average grain diameter, nm | ≤80 | ≤80 | ≤80 | |
| Pore structure | Specific surface (BET) m2/g | 250 | 240 | 260 |
| Pore volume (N 2) ml/g | 0.68 | 0.69 | 0.70 | |
| Average pore size A | 54 | 58 | 54 | |
Table 2 feedstock oil performance
| Density (20 ℃), g/cm 2 | 0.9221 |
| Viscosity (80 ℃), mm 2/s | 36.74 |
| Carbon residue, m% | 5.1 |
Table 3 catalyst physical and chemical performance and evaluation result
| Catalyst | D | E | F | G | N |
| Chemical composition (m%): | |||||
| Al 2O 3 | 41.3 | 41.2 | 51.0 | 50.8 | 44.5 |
| Na 2O | 0.18 | 0.17 | 0.12 | 0.13 | 0.18 |
| Re 2O 3 | 1.3 | 2.0 | 0 | 0.9 | 1.4 |
| MgO | 0 | 0.5 | 0 | 0.3 | 0.2 |
| ZrO | 0 | 0.9 | 0 | 0.5 | 0.4 |
| Physical and chemical performance: | |||||
| SA，m 2/g | 170 | 210 | 290 | 320 | 181 |
| PV，ml/g | 0.31 | 0.34 | 0.36 | 0.40 | 0.32 |
| CCAI | 7 | 5 | 9 | 6 | 5 |
| MTA | 68 | 71 | 70 | 75 | 67 |
| Pollution metal (ppm): | |||||
| Ni | 3010 | 2990 | 2970 | 3020 | 2980 |
| V | 4030 | 4020 | 3990 | 3980 | 4010 |
| The preventing from heavy metal reaction evaluating: | |||||
| Conversion ratio, % | 52.3 | 53.2 | 67.4 | 68.3 | 52.2 |
| Gasoline, % | 35.8 | 37.4 | 45.4 | 48.7 | 37.1 |
| Diesel oil, % | 25.8 | 25.9 | 17.0 | 15.2 | 26.8 |
| Liquefied gas, % | 9.9 | 10.8 | 14.2 | 15.1 | 10.1 |
| Coke, % | 3.9 | 3.2 | 2.9 | 2.5 | 3.2 |
| ＜C 2，％ | 2.0 | 1.8 | 2.1 | 2.0 | 1.8 |
| Heavy oil, % | 21.9 | 20.9 | 17.4 | 16.5 | 21.0 |
Claims (4)
1. semi-synthetic Hydrocarban coversion catalysts that contains the modified Nano grade aluminum oxide, it is characterized in that dividing the material of content: artificial synthesis of molecular sieve 5-50% by following weight, the alumina in Nano level 1-40% of modification, inorganic oxide binder 10-30%, natural aluminium silicate clay 10-60%, make by following process: the alumina in Nano level with artificial synthesis of molecular sieve and modification is dispersed in the inorganic oxide bonding agent earlier, natural aluminium silicate clay with dilute with water is mixed into slurries then, spray-dried moulding, washing, be drying to obtain the product of required catalyst, the alumina in Nano level of described modification is to use cerium, zirconium, a kind of in the magnesium, two or three inorganic salt mixt dipping alumina in Nano level, oven dry then, roasting makes, cerium in the alumina in Nano level of described modification, zirconium, the weight percentage of magnesium is respectively 0.1-15%, 0.1-20%, 0.1-10%, described inorganic salts comprise nitrate, sulfate or chloride.
2. according to the described catalyst of claim 1, it is characterized in that described natural aluminium silicate clay comprises the natural aluminium silicate clay of kaolin, galapectite, bentonite, smectite, sepiolite or a kind of, two or more mixture of their artificial highly finished product.
3. according to the described catalyst of claim 1, it is characterized in that described artificial synthesis of molecular sieve comprises a kind of, two or more the mixture of the molecular sieve that molecular sieve, β and L with faujasite structure zeolite structured molecular sieve, ZSM-5 are zeolite structured.
4. according to the described catalyst of claim 1, it is characterized in that described inorganic oxide bonding agent is selected from one or both in the colloidal sol of silicate gel, alumina silicate colloidal sol, silica sol, aluminium.
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|---|---|---|---|
| CNB031020453A CN1177642C (en) | 2003-01-29 | 2003-01-29 | Semi-synthesized olefins conversion catalyst containing modified nano aluminium oxide |
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|---|---|---|---|
| CNB031020453A CN1177642C (en) | 2003-01-29 | 2003-01-29 | Semi-synthesized olefins conversion catalyst containing modified nano aluminium oxide |
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| Publication Number | Publication Date |
|---|---|
| CN1438297A CN1438297A (en) | 2003-08-27 |
| CN1177642C true CN1177642C (en) | 2004-12-01 |
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