CN105728029A - Nickel cracking resistant catalyst - Google Patents
Nickel cracking resistant catalyst Download PDFInfo
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- CN105728029A CN105728029A CN201410773584.6A CN201410773584A CN105728029A CN 105728029 A CN105728029 A CN 105728029A CN 201410773584 A CN201410773584 A CN 201410773584A CN 105728029 A CN105728029 A CN 105728029A
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- boehmite
- nickel
- alumina
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- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 35
- 238000005336 cracking Methods 0.000 title claims abstract description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 136
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000002808 molecular sieve Substances 0.000 claims abstract description 17
- 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 17
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 8
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 8
- 239000004927 clay Substances 0.000 claims abstract description 7
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 7
- 229910001679 gibbsite Inorganic materials 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 229910001593 boehmite Inorganic materials 0.000 claims description 27
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 27
- 239000005995 Aluminium silicate Substances 0.000 claims description 20
- 235000012211 aluminium silicate Nutrition 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 20
- 238000003756 stirring Methods 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 229910021536 Zeolite Inorganic materials 0.000 claims description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 239000010457 zeolite Substances 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 6
- 229910001648 diaspore Inorganic materials 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 238000001935 peptisation Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 3
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 2
- 229960000892 attapulgite Drugs 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
- 229910052599 brucite 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
- 229910052621 halloysite Inorganic materials 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000571 coke Substances 0.000 abstract description 10
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 6
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 abstract 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- 238000010009 beating Methods 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 239000004005 microsphere Substances 0.000 description 16
- 239000000758 substrate Substances 0.000 description 16
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 11
- 238000001914 filtration Methods 0.000 description 8
- 238000007493 shaping process Methods 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- 239000003643 water by type Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000005696 Diammonium phosphate Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 235000019838 diammonium phosphate Nutrition 0.000 description 6
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052720 vanadium Inorganic materials 0.000 description 6
- 239000004254 Ammonium phosphate Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 5
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 5
- 235000019289 ammonium phosphates Nutrition 0.000 description 5
- 238000004523 catalytic cracking Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 238000006356 dehydrogenation reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 239000012013 faujasite Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000010534 mechanism of action Effects 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000190022 Pilea cadierei Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- -1 faujasite Chemical compound 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention relates to a nickel cracking resistant catalyst, which mainly comprises 0.5-15 wt% of large-grain alumina material according to the dry basis of feeding materials; 5 to 70 wt% of an inorganic oxide binder; 15-60 wt% of a molecular sieve; 5 to 50 wt% of clay; and 0.3 to 2 wt% of phosphorus, wherein the large-grain alumina material has a pseudo-boehmite structure, a monohydrate-boehmite structure or a gibbsite structure, the content of sodium oxide is less than or equal to 0.2 wt%, the content of silicon dioxide is less than or equal to 0.3 wt%, and the grain size is 100 to 1160 nm; the inorganic oxide binder is a mixture of alumina sol and pseudo-boehmite, wherein the alumina from the pseudo-boehmite accounts for 3-40% of the weight of the catalyst, and the alumina from the alumina sol accounts for 4-30% of the weight of the catalyst. The catalyst prepared by the method has excellent nickel pollution resistance and coke selectivity due to the adoption of the special aluminum oxide material and the formula.
Description
Technical field
The present invention relates to a kind of resistance to metal-catalyzed Cracking catalyst, furthermore, be a kind of anti-nickel catalytic cracking catalyst.
Background technology
Along with the heaviness day by day of crude oil, in poor quality, the trend that in fcc raw material, the total amount of heavy metal, carbon residue and the heteroatomic compound such as sulfur, nitrogen is significantly increased, on poising agent, content of beary metal substantially rises, the nickel content of Some Domestic catalytic unit poising agent has reached more than 15000ppm, and performance and cracked product distribution to catalyst cause and have a strong impact on.For ease of the impact of various pollution metal is described concisely, there is people nickel, vanadium etc. are polluted the toxicity of metal and represents together always, but along with going deep into of people's understanding, nickel is entirely different with the mechanism of action of vanadium, and they are also different on the impact of catalyst activity and selectivity.Impact caused by vanadium is the zeolite molecular sieve destroying catalyst, causes that catalyst activity reduces, at present domestic and international anti-vanadium technology comparative maturity.And the impact of nickel is the increase in the generation of coke and hydrogen in raw material, reducing the yield of light oil, product selectivity is deteriorated.Its mechanism of action is: deposition nickel on a catalyst hockets due to reaction and regenerative process, and the valence state of nickel change between 0～+2, and the metallic nickel after being reduced is well to be hydrogenated with and dehydrogenation.When catalytic cracking reaction, nickel acts primarily as dehydrogenation, and it can make part charging and crackate dehydrogenation generate oily polycyclic aromatic hydrocarbon polymer or coke, thus causing that selectivity of catalyst is deteriorated, namely hydrogen and coke yield increase, and liquid yield declines.If it is not the product after dehydrogenation plugs the micropore of catalyst, completely burned off again in regenerative process, the surface area of catalyst will be reduced, thus affecting its cracking activity.Therefore, catalytic cracking catalyst is with greater need for the anti-nickel contamination ability with excellence, to improve catalytic cracking unit product slates further, improves refinery's economic benefit.
DE4324538 discloses a kind of anti-nickel Cracking catalyst, the peptization boehmite of employing sulphuric acid or phosphoric acid modification and Ludox as binding agent, coke tool decrease to some degree.US2003130107, US2003136707, US2003089640, US2010298118 are the effects being realized preventing from heavy metal pollution by the improvement of in-situ crystallization technique, this technology anti-vanadium function is better, but anti-nickel ability is general, in-situ crystallization Catalyst Production technics comparing is complicated simultaneously.EP0228270 and EP0238760 adds the aluminium oxide of a kind of Si modification to improve the structural stability of catalyst, but this technology needs first aluminium oxide to be carried out Si modification, and carries out the process such as roasting, and complex procedures is bigger to catalyst abrasion exponential effect.
CN1068588 discloses a kind of matal deactivator for FCC catalyst, by antimony and or the mixed solution of good fluidity that forms of the hydroxy compounds (I) of bismuth, reaction medium (II) and solubilizing agent (III) three part；CN1294173 is also a kind of water-soluble metal passivator, with antimony, aluminum and Rare Earth Lanthanum (or cerium) for key component, can significantly decrease catalyst poisoning inactivation, improve gasoline and light oil yield, hence it is evident that reduce hydrogen yield；JP1284580 discloses a kind of solution made with the salt of antimony, after adding this solution, can reduce the generation of hydrogen, coke.But containing to environmentally undesirable component, being unfavorable for popularization and application in these metal passivation liquid.
CN88102585, EP303372, US4585545, EP141988, US4504381 add the solid nickel component of the solids such as bismuth, antimony, stannum, phosphorus in catalyst preparation process, improve the heavy oil pyrolysis performance of catalyst, reduce the productivity of hydrogen, coke simultaneously, but, the anti-nickel of this technology is limited in one's ability, and catalyst is relatively costly.
US4522704 and US4504379 is disclosed that the anti-nickel being realized catalyst by technological transformation, between the reactor and regenerator of catalytic cracking unit, special passive area is set, reduce the impact polluting metal pair catalyst, equipment owing to doing is changed bigger, need substantial amounts of investment, up to the present, relevant application report is had no.
All in all, at present, the patent of anti-vanadium Cracking catalyst aspect is more, and Main Means is through adding the component such as rare earth, alkali metal to improve the anti-vanadium performance of catalyst；But the patent of anti-nickel Cracking catalyst is fewer, and the patented technology of anti-nickel is concentrated mainly on matal deactivator and process transformation aspect, there is the unfavorable factors such as investment height, environmental pollution.
Summary of the invention
The present invention provides a kind of new anti-nickel Cracking catalyst.Preparation process is simple, but anti-nickel is effective, and coke and hydrogen yield can be greatly lowered, and improves yield of light oil.
Anti-nickel Cracking catalyst provided by the invention, by the butt that feeds intake, mainly comprises: (1) 0.5～15 big grain oxidation aluminum of weight %；The inorganic oxide binder of (2) 5～70 weight %；The molecular sieve of (3) 15～60 weight %；The clay of (4) 5～50 weight %；The phosphorus of (5) 0.3～2 weight %.
Described big grain oxidation aluminum has structure of similar to thin diaspore, a diaspore structure or gibbsite structure, it is preferable that have boehmite or the alumina material of a diaspore structure.Sodium oxide content≤0.2 weight the % of this big grain oxidation aluminum, dioxide-containing silica≤0.3 weight %, crystallite dimension is at 100～1160nm, it is preferable that at 200～800nm.
The described inorganic oxide binder a kind of or wherein several mixture in Alumina gel, Ludox, boehmite, sial molten (coagulating) glue, modified sial molten (coagulating) glue, the mixture of preferred Alumina gel and boehmite, wherein account for the 3～40% of catalyst weight from the aluminium oxide of boehmite, it is preferable that 3～30%；Aluminium oxide from Alumina gel accounts for the 4～30% of catalyst weight, it is preferable that 8～22%.
Described molecular screening as the mixture of one or more in the zeolite of active component of cracking catalyst and non-zeolite molecular sieve, such as faujasite, has the zeolite of MFI structure, modenite, β zeolite etc. certainly.
Described faujasite is selected from y-type zeolite or/and X-type zeolite, and described Y type molecular sieve is selected from one or more the mixture in HY, REY, REHY, USY, REUSY, REDASY, it is preferred to REUSY zeolite；The described zeolite with MFI structure is selected from ZSM-5, phosphorous or/and the zeolite with MFI structure of rare earth, it is preferable that ZSM-5.
The described clay mixture of one or more in Kaolin, halloysite, montmorillonite, kieselguhr, galapectite, brucite, attapulgite, bentonite, meerschaum, it is preferable that Kaolin.
Described phosphorus is in elemental phosphorous, and its precursor refers to the water soluble compounds such as phosphoric acid, phosphorous acid, phosphoric anhydride and/or phosphate, it is preferable that phosphoric acid and/or diammonium phosphate.
The present invention anti-nickel Cracking catalyst is prepared by following method:
1) in the reactor of heating in water bath, the water measured is added；
2) adding the solid constituent in clay, binding agent, big grain oxidation aluminum, stir, the addition of several host materials does not have strict precedence；
3) with acid aluminum weight ratio be 0.05～0.30 mineral acid acidified, mineral acid can by whole for the solid constituent in binding agent peptizations, and to big grain oxidation aluminum can only small part peptization, mineral acid can only add after binding agent solid constituent adding；
4) 45 DEG C～90 DEG C aging 0.5～4h it are warming up to；
5) liquid-containing binder is added after being cooled to room temperature；
6) molecular sieve pulp is added；
7) spray drying forming, roasting, the phosphorus washing of addition 0.3～2 weight %, drying after mix homogeneously, obtains finished catalyst.
In the method simulation industry poising agent of nickel contamination of the present invention, the content of nickel pollutes: by the aqueous impregnation of nickel nitrate (in catalyst 5000ppmNi) to catalyst, 500～550 DEG C of roasting 1～4h after 120 DEG C of drying, then 800 DEG C, aging 4～6h under 100% water vapor condition, be then evaluated on ACE device.
Catalyst provided by the invention is owing to have employed a kind of big grain oxidation aluminum, after preparing into catalyst, in the process of heavy oil catalytically cracking equipment cracking masout, under high temperature and steam existent condition, can be enriched with by the nickel in raw oil, be substantially reduced its saboteur and sieve the effect of activity.Meanwhile, in catalyst preparation process, owing to this alumina material only has small part and acid reaction peptization, the structure of alumina material self is not corrupted such that catalyst of the present invention has bigger pore volume.Thus, the present invention anti-nickel Cracking catalyst has anti-nickel contamination ability and the coke selectivity of excellence, coke and hydrogen yield is greatly lowered, improves yield of light oil.
Detailed description of the invention
The raw material used in embodiment and character:
1, Kaolin, igloss 15 weight %, China Kaolin Co., Ltd's industrial products；
2, galapectite, igloss 20 weight %, commercially available prod；
3, boehmite, sodium oxide 0.101 weight %, silicon dioxide 0.23 weight %, crystallite dimension 7.6nm, igloss 35 weight %, Shanxi Aluminium Plant product；
4, hydrochloric acid, silver chemical reagent work, analytical pure；
5, RDSY, igloss 10 weight %, Lanzhou Petrochemical catalyst plant product；
6, HRSY-4, igloss 20 weight %, Lanzhou Petrochemical catalyst plant product；
7, ZSM-5, igloss 3 weight %, Lanzhou Petrochemical catalyst plant product；
8, diammonium phosphate, ammonium phosphate, Xi'an chemical reagent work, analytical pure；
9, nickel nitrate, Xi'an chemical reagent work, analytical pure；
10, Alumina gel: aluminium sesquioxide content 21%, takes from Lanzhou Petrochemical catalyst plant；
11, Ludox: dioxide-containing silica 25%, commercially available prod；
12, alumina material a, sodium oxide 0.0865 weight %, silicon dioxide 0.283 weight %, crystallite dimension 80nm, igloss 15.1 weight %, commercially available prod；
13, alumina material b, sodium oxide 0.0849 weight %, silicon dioxide 0.294 weight %, crystallite dimension 100nm, igloss 14.8 weight %, commercially available prod；
14, alumina material c, sodium oxide 0.0901 weight %, silicon dioxide 0.279 weight %, crystallite dimension 420nm, igloss 15.3 weight %, commercially available prod；
15, alumina material d, sodium oxide 0.0886 weight %, silicon dioxide 0.297 weight %, crystallite dimension 1160nm, igloss 15.9 weight %, commercially available prod.
In example, the pore volume of catalyst adopts water droplet method to test, and abrasion index adopts gas lift method to measure, ACE appreciation condition: reaction raw materials is the compound of 70% Xinjiang decompression wide fraction oil and 30% Xinjiang decompression residuum, catalyst loading amount 9g, reaction temperature 530 DEG C, oil ratio 5.
Embodiment 1
In the reactor with heating in water bath, add 4L water, 2347g Kaolin, 1720g boehmite and 33.8g alumina material c, be then slowly added into 200g mixed in hydrochloric acid uniform, after stirring 1 hour, at 75 DEG C of aging 1h, it is subsequently adding 3003 grams of Alumina gel, forms catalyst substrates serosity；
In making beating tank, add 4L water, add 2114 grams of RDSY, 60 grams of ZSM-5, add after making beating 1h in catalyst substrates serosity, after making beating 1h, through spray shaping, by thus obtained microsphere 500 DEG C of roastings 0.5 hour.Take roasting microsphere 4 kilograms, add 30 kilograms of deionized waters and 101 grams of diammonium phosphate, stir, wash 15 minutes at 60 DEG C, filtration drying, be denoted as catalyst S-1.
Catalyst S-1 consists of: Kaolin 34.8 weight %, and the aluminium oxide from boehmite is 19.5 weight %, and the aluminium oxide carrying out self-alumina c is 0.5 weight %, aluminium oxide 11 weight % from Alumina gel, Y type molecular sieve 33.2 weight %, ZSM-5 are 1 weight %, P is 0.6 weight %.
Embodiment 2
In the reactor with heating in water bath, add 4L water, 1996g Kaolin, 424g galapectite, 1235g boehmite and 406g alumina material c, it is then slowly added into 200g mixed in hydrochloric acid uniform, after stirring 1 hour, at 75 DEG C of aging 1h, it is subsequently adding 3003 grams of Alumina gel and forms catalyst substrates serosity；
In making beating tank, add 4L water, add 2114 grams of RDSY, 60 grams of ZSM-5, add after making beating 1h in catalyst substrates serosity, after making beating 1h, through spray shaping, by thus obtained microsphere 500 DEG C of roastings 0.5 hour.Take roasting microsphere 4 kilograms, add 30 kilograms of deionized waters and 115 grams of ammonium phosphate, stir, wash 15 minutes at 60 DEG C, filtration drying, be denoted as catalyst S-2.
Catalyst S-2 consists of: Kaolin 29 weight %, galapectite 5.8 weight %, and the aluminium oxide from boehmite is 14 weight %, the aluminium oxide carrying out self-alumina c is 6 weight %, from the aluminium oxide 11 weight % of Alumina gel, Y type molecular sieve 33.2 weight %, ZSM-5 is 1 weight %, P is 0.6 weight %.
Embodiment 3
In the reactor with heating in water bath, add 4L water, 2347g Kaolin, 441g boehmite and 1015g alumina material c, be then slowly added into 200g mixed in hydrochloric acid uniform, after stirring 1 hour, at 75 DEG C of aging 1h, it is subsequently adding 2523 grams of Ludox and forms catalyst substrates serosity；
In making beating tank, add 4L water, add 2378 grams of HRSY-4,60 grams of ZSM-5, add after making beating 1h in catalyst substrates serosity, after making beating 1h, through spray shaping, by thus obtained microsphere 500 DEG C of roastings 0.5 hour.Take roasting microsphere 4 kilograms, add 30 kilograms of deionized waters and 101 grams of diammonium phosphate, stir, wash 15 minutes at 60 DEG C, filtration drying, be denoted as catalyst S-3.
Catalyst S-3 consists of: Kaolin 34.8 weight %, and the aluminium oxide from boehmite is 5 weight %, and the aluminium oxide carrying out self-alumina c is 15 weight %, and from the silicon oxide 11 weight % of Ludox, Y type molecular sieve 33.2 weight %, ZSM-5 are 1 weight %, P is 0.6 weight %.
Embodiment 4
In the reactor with heating in water bath, add 4L water, 2347g Kaolin, 1720g boehmite and 33.6g alumina material b, be then slowly added into 200g mixed in hydrochloric acid uniform, after stirring 1 hour, at 75 DEG C of aging 1h, it is subsequently adding 3003 grams of Alumina gel and forms catalyst substrates serosity；
In making beating tank, add 4L water, add 2114 grams of RDSY, 60 grams of ZSM-5, add after making beating 1h in catalyst substrates serosity, after making beating 1h, through spray shaping, by thus obtained microsphere 500 DEG C of roastings 0.5 hour.Take roasting microsphere 4 kilograms, add 30 kilograms of deionized waters and 115 grams of ammonium phosphate, stir, wash 15 minutes at 60 DEG C, filtration drying, be denoted as catalyst S-4.
Catalyst S-4 consists of: Kaolin 34.8 weight %, and the aluminium oxide from boehmite is 19.5 weight %, and the aluminium oxide carrying out self-alumina b is 0.5 weight %, aluminium oxide 11 weight % from Alumina gel, Y type molecular sieve 33.2 weight %, ZSM-5 are 1 weight %, P is 0.6 weight %.
Embodiment 5
In the reactor with heating in water bath, add 4L water, 1996g Kaolin, 424g galapectite, 1235g boehmite and 409g alumina material d, it is then slowly added into 200g mixed in hydrochloric acid uniform, after stirring 1 hour, at 75 DEG C of aging 1h, it is subsequently adding 2523 grams of Ludox and forms catalyst substrates serosity；
In making beating tank, add 4L water, add 2378 grams of HRSY-4,60 grams of ZSM-5, add after making beating 1h in catalyst substrates serosity, after making beating 1h, through spray shaping, by thus obtained microsphere 500 DEG C of roastings 0.5 hour.Take roasting microsphere 4 kilograms, add 30 kilograms of deionized waters and 101 grams of diammonium phosphate, stir, wash 15 minutes at 60 DEG C, filtration drying, be denoted as catalyst S-5.
Catalyst S-5 consists of: Kaolin 29 weight %, galapectite 5.8 weight %, and the aluminium oxide from boehmite is 14 weight %, the aluminium oxide carrying out self-alumina d is 6 weight %, from the silicon oxide 11 weight % of Ludox, Y type molecular sieve 33.2 weight %, ZSM-5 is 1 weight %, P is 0.6 weight %.
Comparative example 1
In the reactor with heating in water bath, add 4L water, 1996g Kaolin, 424g galapectite, 1235g boehmite and 405g alumina material a, it is then slowly added into 200g mixed in hydrochloric acid uniform, after stirring 1 hour, at 75 DEG C of aging 1h, it is subsequently adding 3003 grams of Alumina gel and forms catalyst substrates serosity；
In making beating tank, add 4L water, add 2114 grams of RDSY, 60 grams of ZSM-5, add after making beating 1h in catalyst substrates serosity, after making beating 1h, through spray shaping, by thus obtained microsphere 500 DEG C of roastings 0.5 hour.Take roasting microsphere 4 kilograms, add 30 kilograms of deionized waters and 115 grams of ammonium phosphate, stir, wash 15 minutes at 60 DEG C, filtration drying, be denoted as catalyst S-2.
Catalyst S-2 consists of: Kaolin 29 weight %, galapectite 5.8 weight %, and the aluminium oxide from boehmite is 14 weight %, the aluminium oxide carrying out self-alumina c is 6 weight %, from the aluminium oxide 11 weight % of Alumina gel, Y type molecular sieve 33.2 weight %, ZSM-5 is 1 weight %, P is 0.6 weight %.
Comparative example 2
In the reactor with heating in water bath, add 4L water, 1996g Kaolin, 424g galapectite, 1764g boehmite, be then slowly added into 200g mixed in hydrochloric acid uniform, after stirring 1 hour, at 75 DEG C of aging 1h, it is subsequently adding 3003 grams of Alumina gel and forms catalyst substrates serosity；
In making beating tank, add 4L water, add 2114 grams of RDSY, 60 grams of ZSM-5, add after making beating 1h in catalyst substrates serosity, after making beating 1h, through spray shaping, by thus obtained microsphere 500 DEG C of roastings 0.5 hour.Take roasting microsphere 4 kilograms, add 30 kilograms of deionized waters and 115 grams of ammonium phosphate, stir, wash 15 minutes at 60 DEG C, filtration drying, be denoted as catalyst D-2.
Catalyst D-2 consists of: Kaolin 29 weight %, galapectite 5.8 weight %, and the aluminium oxide from boehmite is 20 weight %, and from the aluminium oxide 11 weight % of Alumina gel, Y type molecular sieve 33.2 weight %, ZSM-5 are 1 weight %, P is 0.6 weight %.
Comparative example 3
In the reactor with heating in water bath, add 4L water, 1996g Kaolin, 424g galapectite, 265g boehmite and 1150g alumina material c, it is then slowly added into 200g mixed in hydrochloric acid uniform, after stirring 1 hour, at 75 DEG C of aging 1h, it is subsequently adding 3003 grams of Alumina gel and forms catalyst substrates serosity；
In making beating tank, add 4L water, add 2114 grams of RDSY, 60 grams of ZSM-5, add after making beating 1h in catalyst substrates serosity, after making beating 1h, through spray shaping, by thus obtained microsphere 500 DEG C of roastings 0.5 hour.Take roasting microsphere 4 kilograms, add 30 kilograms of deionized waters and 101 grams of diammonium phosphate, stir, wash 15 minutes at 60 DEG C, filtration drying, be denoted as catalyst D-3.
Catalyst D-3 consists of: Kaolin 29 weight %, galapectite 5.8 weight %, and the aluminium oxide from boehmite is 3 weight %, the aluminium oxide carrying out self-alumina c is 17 weight %, from the aluminium oxide 11 weight % of Alumina gel, Y type molecular sieve 33.2 weight %, ZSM-5 is 1 weight %, P is 0.6 weight %.
Embodiment 1-5, comparative example 1-3 catalyst, its pore volume and abrasion index are listed in table 1.
Table 1 catalyst pore volume and abrasion index
| Catalyst | Pore volume, ml/g | Abrasion index, ω %h-1 |
| S-1 | 0.38 | 1.4 |
| S-2 | 0.41 | 1.8 |
| S-3 | 0.45 | 2.8 |
| S-4 | 0.37 | 1.2 |
| S-5 | 0.42 | 2.9 |
| D-1 | 0.36 | 1.0 |
| D-2 | 0.36 | 0.8 |
| D-3 | 0.49 | 3.9 |
Embodiment 6
This example demonstrates that method provided by the invention prepares catalyst evaluation after nickel contamination, the evaluation result on ACE is in Table 2.
Table 2 catalyst evaluation result on ACE device
Claims (5)
1. an anti-nickel Cracking catalyst, by the butt that feeds intake, specifically includes that (1) 0.5～15 big grain oxidation aluminum of weight %；The inorganic oxide binder of (2) 5～70 weight %；The molecular sieve of (3) 15～60 weight %；The clay of (4) 5～50 weight %；The phosphorus of (5) 0.3～2 weight %, wherein, described big grain oxidation aluminum has structure of similar to thin diaspore, a diaspore structure or gibbsite structure, sodium oxide content≤0.2 weight the % of this big grain oxidation aluminum, dioxide-containing silica≤0.3 weight %, crystallite dimension is at 100～1160nm；Described inorganic oxide binder is the mixture of Alumina gel and boehmite, wherein accounts for the 3～40% of catalyst weight from the aluminium oxide of boehmite, and the aluminium oxide from Alumina gel accounts for the 4～30% of catalyst weight；Described phosphorus is in elemental phosphorous；Described catalyst is prepared by following method:
1) in the reactor of heating in water bath, the water measured is added；
2) adding the solid constituent in clay, binding agent, big grain oxidation aluminum, stir, the addition of several host materials does not have strict precedence；
3) with acid aluminum weight ratio be 0.05～0.30 mineral acid acidified, mineral acid can by whole for the solid constituent in binding agent peptizations, and to big grain oxidation aluminum can only small part peptization, mineral acid can only add after binding agent solid constituent adding；
4) 45 DEG C～90 DEG C aging 0.5～4h it are warming up to；
5) liquid-containing binder is added after being cooled to room temperature；
6) molecular sieve pulp is added；
7) spray drying forming, roasting, the phosphorus washing of addition 0.3～2 weight %, drying after mix homogeneously, obtains finished catalyst.
2. the anti-nickel Cracking catalyst of one according to claim 1, it is characterised in that described big grain oxidation aluminum is the alumina material with boehmite or a diaspore structure, and crystallite dimension is 200～800nm.
3. the anti-nickel Cracking catalyst of one according to claim 1, it is characterised in that described inorganic oxide binder is the mixture of Alumina gel and boehmite, wherein accounts for the 3～30% of catalyst weight from the aluminium oxide of boehmite；Aluminium oxide from Alumina gel accounts for the 8～22% of catalyst weight.
4. the anti-nickel Cracking catalyst of one according to claim 1, it is characterised in that described molecular screening is certainly as the mixture of one or more in the zeolite of active component of cracking catalyst and non-zeolite molecular sieve.
5. the anti-nickel Cracking catalyst of one according to claim 1, it is characterised in that the described clay mixture of one or more in Kaolin, halloysite, montmorillonite, kieselguhr, galapectite, brucite, attapulgite, bentonite, meerschaum.
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| CN109833918A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | Preparation method of carrier silica gel |
| CN109833859A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | Preparation method of silica gel carrier for olefin catalyst |
| WO2023051588A1 (en) * | 2021-09-30 | 2023-04-06 | 中国石油化工股份有限公司 | Metal pollution-resistant catalyst and preparation method therefor |
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| CN101134905A (en) * | 2006-08-30 | 2008-03-05 | 中国石油天然气股份有限公司 | Method for improving solid content of catalytic cracking catalyst slurry |
| CN101357771A (en) * | 2008-09-09 | 2009-02-04 | 武汉理工大学 | Hydrothermal method for preparing high specific surface area pseudo boehmite microsphere |
| CN102050476A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Preparation methods of fibroid boehmite and activated aluminum oxide |
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| CN101134905A (en) * | 2006-08-30 | 2008-03-05 | 中国石油天然气股份有限公司 | Method for improving solid content of catalytic cracking catalyst slurry |
| CN101357771A (en) * | 2008-09-09 | 2009-02-04 | 武汉理工大学 | Hydrothermal method for preparing high specific surface area pseudo boehmite microsphere |
| CN102050476A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Preparation methods of fibroid boehmite and activated aluminum oxide |
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| CN109833918A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | Preparation method of carrier silica gel |
| CN109833859A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | Preparation method of silica gel carrier for olefin catalyst |
| CN109833859B (en) * | 2017-11-28 | 2022-01-25 | 中国石油天然气股份有限公司 | Preparation method of silica gel carrier for olefin catalyst |
| CN109833918B (en) * | 2017-11-28 | 2022-01-25 | 中国石油天然气股份有限公司 | Preparation method of carrier silica gel |
| WO2023051588A1 (en) * | 2021-09-30 | 2023-04-06 | 中国石油化工股份有限公司 | Metal pollution-resistant catalyst and preparation method therefor |
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