CN1382768A - Phosphorus-contained gamma-type zeolite as cracking catalyst and its preparing process - Google Patents
Phosphorus-contained gamma-type zeolite as cracking catalyst and its preparing process Download PDFInfo
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- CN1382768A CN1382768A CN 01115621 CN01115621A CN1382768A CN 1382768 A CN1382768 A CN 1382768A CN 01115621 CN01115621 CN 01115621 CN 01115621 A CN01115621 A CN 01115621A CN 1382768 A CN1382768 A CN 1382768A
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- phosphorus
- type zeolite
- zeolite
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- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 199
- 239000010457 zeolite Substances 0.000 title claims abstract description 199
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 238000005336 cracking Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims description 39
- 230000008569 process Effects 0.000 title description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 67
- 239000011574 phosphorus Substances 0.000 claims abstract description 67
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 62
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 61
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 54
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 30
- 239000010703 silicon Substances 0.000 claims abstract description 30
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 28
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- 239000011230 binding agent Substances 0.000 claims abstract description 17
- 239000004927 clay Substances 0.000 claims abstract description 15
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000000243 solution Substances 0.000 claims description 50
- 238000002360 preparation method Methods 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 238000010335 hydrothermal treatment Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- -1 ammonium fluorosilicate Chemical compound 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 239000003921 oil Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 238000010009 beating Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims description 10
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 10
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 10
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- 235000019353 potassium silicate Nutrition 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 229920002545 silicone oil Polymers 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003570 air Substances 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 claims description 5
- 239000004254 Ammonium phosphate Substances 0.000 claims description 4
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000002210 silicon-based material Substances 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 3
- 239000011261 inert gas Substances 0.000 claims 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims 1
- CCDWGDHTPAJHOA-UHFFFAOYSA-N benzylsilicon Chemical compound [Si]CC1=CC=CC=C1 CCDWGDHTPAJHOA-UHFFFAOYSA-N 0.000 claims 1
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 1
- 239000001569 carbon dioxide Substances 0.000 claims 1
- 229910052570 clay Inorganic materials 0.000 claims 1
- 230000001066 destructive effect Effects 0.000 claims 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims 1
- 235000019838 diammonium phosphate Nutrition 0.000 claims 1
- 229940104869 fluorosilicate Drugs 0.000 claims 1
- 235000019837 monoammonium phosphate Nutrition 0.000 claims 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims 1
- 235000011007 phosphoric acid Nutrition 0.000 claims 1
- 125000002743 phosphorus functional group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 239000000295 fuel oil Substances 0.000 abstract description 8
- 238000009826 distribution Methods 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 28
- 241000196324 Embryophyta Species 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 239000011734 sodium Substances 0.000 description 13
- 238000007598 dipping method Methods 0.000 description 12
- 238000005342 ion exchange Methods 0.000 description 12
- 239000005995 Aluminium silicate Substances 0.000 description 11
- 235000012211 aluminium silicate Nutrition 0.000 description 11
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 11
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 230000032683 aging Effects 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000004411 aluminium Substances 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 7
- VWDWKYIASSYTQR-YTBWXGASSA-N sodium;dioxido(oxo)azanium Chemical compound [Na+].[O-][15N+]([O-])=O VWDWKYIASSYTQR-YTBWXGASSA-N 0.000 description 7
- 239000002002 slurry Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- 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 5
- 239000002808 molecular sieve Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 238000004939 coking Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229940070337 ammonium silicofluoride Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical group [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 239000011799 hole material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
一种含磷Y型沸石裂化催化剂含有含磷Y型沸石、铝粘结剂,含或不含粘土,以催化剂总重量为基准,所述含磷Y型沸石的含量为10－60重%、以氧化铝计,所述铝粘结剂的含量为10－60重%,所述粘土的含量为0－75重%,所述含磷Y型沸石含有一种磷组分、一种硅组分和一种稀土组分,所述硅组分是用硅化合物溶液浸渍沸石的方法负载上去的,以含磷Y型沸石重量为基准,以SiO2计,所述硅组分的含量为1－15重%,以P2O5计,所述磷组分的含量为0.1－15重%,以稀土氧化物计,所述稀土组分的含量为0.2－15重%。该催化剂具有更强的重油转化能力和更好的产品分布。A phosphorus-containing Y-type zeolite cracking catalyst contains phosphorus-containing Y-type zeolite, an aluminum binder, and contains or does not contain clay. Based on the total weight of the catalyst, the content of the phosphorus-containing Y-type zeolite is 10-60% by weight, Calculated by alumina, the content of the aluminum binder is 10-60% by weight, the content of the clay is 0-75% by weight, and the phosphorus-containing Y-type zeolite contains a phosphorus component, a silicon component and a rare earth component, the silicon component is loaded by impregnating the zeolite with a silicon compound solution, based on the weight of phosphorus-containing Y-type zeolite, calculated as SiO 2 , the content of the silicon component is 1 -15% by weight, based on P 2 O 5 , the content of the phosphorus component is 0.1-15% by weight, and based on rare earth oxides, the content of the rare earth component is 0.2-15% by weight. The catalyst has stronger heavy oil conversion capacity and better product distribution.
Description
The invention relates to a kind of hydrocarbon cracking catalyzer that contains faujusite and preparation method thereof.More particularly, be about a kind of P-contained Y-zeolite hydrocarbon cracking catalyzer and preparation method thereof.
Phosphorus is introduced the catalytic performance that molecular sieve can improve catalyzer.
EP252,761A2 disclose a kind of hydrocarbon cracking catalyzer, and this catalyzer contains (a) a kind of nonzeolite inorganic oxide matrix and (b) a kind of superstable gamma-type crystalline zeolite.Described zeolite has carried out pre-treatment, and pretreated method is that described zeolite is contacted the sufficiently long time with a kind of P contained compound, makes the described zeolite-loaded phosphorus of going up significant quantity.
EP397 discloses a kind of composition in 183, and said composition contains Na
2O content is the ion-exchange NaY zeolite of the heavy % of 2-5 and with P
2O
5Meter, the phosphorus of the heavy % of 0.1-4.0.The preparation method of said composition comprises that (a) carries out ion-exchange and washing with a kind of NaY zeolite, obtains a kind of Na
2O content is the exchange y-type zeolite of the heavy % of 1-5, (b) will exchange y-type zeolite and a kind of phosphorus compound solution hybrid reaction, and described phosphorus compound is selected from one group that is made up of phosphoric acid, Secondary ammonium phosphate, primary ammonium phosphate, SODIUM PHOSPHATE, MONOBASIC, (c) reclaims with P
2O
5The meter phosphorus content is the P-contained Y-zeolite product of the heavy % of 0.1-4.
In the phosphorus modifying method of molecular sieve, flood y-type zeolite separately with P contained compound solution, carrying out hydrothermal treatment consists then, to obtain phosphorus containing molecular sieve be common y-type zeolite phosphorus main methods of modification.By such processing, can remove the aluminium in the part y-type zeolite lattice and the structure cell of y-type zeolite is dwindled, improve the hydrothermal stability of y-type zeolite, phosphorus is combined with y-type zeolite more effectively, make the selectivity of catalyst that contains this kind P-contained Y-zeolite also obtain to a certain degree improvement.But y-type zeolite is after the phosphorus modification, its degree of crystallinity but has obvious decline, this not only causes a large amount of losses of zeolite, and influential to the stability and the activity of y-type zeolite, and further causes the cracking catalyst heavy oil conversion performance and the product that contain this P-contained Y-zeolite to distribute relatively poor.
The objective of the invention is to overcome prior art P-contained Y-zeolite catalyzer heavy oil conversion performance and the relatively poor shortcoming of product distribution, provide a kind of and have stronger heavy oil conversion performance and have phosphorus-contained gamma-type zeolite as cracking catalyst of better products distribution and preparation method thereof.
Catalyzer provided by the invention contains P-contained Y-zeolite, al binder, contain or argillaceous not, wherein, with the total catalyst weight is benchmark, the content of described P-contained Y-zeolite is the heavy % of 10-60, in aluminum oxide, the content of described al binder is the heavy % of 10-60, the heavy % of the content 0-75 of described clay, described P-contained Y-zeolite contains a kind of phosphorus component, a kind of silicon components and a kind of rare earth component, described silicon components is to get on the method load of silicon compound solution dipping zeolite, with zeolite weight is benchmark, with SiO
2Meter, the content of described silicon components are the heavy % of 1-15, with P
2O
5Meter, the content of described phosphorus component are the heavy % of 0.1-15, and in rare earth oxide, described rare earth components contents is the heavy % of 0.2-15.
Preparation of catalysts method provided by the invention comprises mixes making beating with P-contained Y-zeolite, clay, al binder and deionized water, dry, washing and after drying, wherein, the consumption of P-contained Y-zeolite, clay, al binder makes the P-contained Y-zeolite that contains the heavy % of 10-60 in the final catalyzer, in aluminum oxide, the clay of the al binder of the heavy % of 10-60 and the heavy % of 0-75; The preparation method of described P-contained Y-zeolite comprises with a kind of raw material y-type zeolite of a kind of solution impregnation of phosphorus compound, and drying wherein also comprises the solution impregnation y-type zeolite with silicon compound, with SiO
2Meter, the consumption of described silicon compound solution make and contain the heavy % of silicon components 1-15 in the P-contained Y-zeolite that obtains, with P
2O
5Meter, the consumption of described P contained compound solution makes and contains the heavy % of phosphorus component 0.1-10 in the P-contained Y-zeolite that obtains, and described raw material y-type zeolite is the y-type zeolite that contains rare earth, is benchmark with the gross weight of P-contained Y-zeolite, in the oxide compound of rare earth, the content of described rare earth is the heavy % of 0.2-15.
According to catalyzer provided by the invention, with the total catalyst weight is benchmark, the content of described P-contained Y-zeolite is the heavy % of 10-60, be preferably the heavy % of 15-60, in aluminum oxide, the content of described al binder is the heavy % of 10-60, be preferably the heavy % of 15-55, the heavy % of the content 0-75 of described clay is preferably the heavy % of 0-60.
According to catalyzer provided by the invention, the content of the silicon components in the described P-contained Y-zeolite is the heavy % of 1-15, is preferably the heavy % of 5-15, the content of described phosphorus component is the heavy % of 0.1-15, be preferably the heavy % of 2-10, described rare earth components contents is the heavy % of 0.2-15, the heavy % of preferred 1-10.
Described silicon components is to get on the method load of silicon compound solution dipping zeolite, described silicon compound solution is selected from the aqueous solution of silicon compound or organic solution and this as in the silicon compound of liquid one or more, as silicon sol, water glass, the silicofluoride aqueous solution, in silicoorganic compound and their solution one or more, preferred silicon compound solution is selected from silicon sol, water glass, the silicofluoride aqueous solution, dimethyl silicone oil, in the polymethylphenyl siloxane fluid one or more, more preferred silicon compound solution is selected from silicon sol, water glass, the ammonium silicofluoride aqueous solution, polymethylphenyl siloxane fluid 255, polymethylphenyl siloxane fluid 250, polymethylphenyl siloxane fluid 274, in the dimethyl silicone oil one or more.Particularly preferred silicon compound solution is selected from one or more in silicon sol, water glass and the ammonium silicofluoride aqueous solution.
According to catalyzer provided by the invention, described P-contained Y-zeolite is through 550～850 ℃ of hydrothermal treatment consists after 15 minutes to 5 hours, its relative crystallinity is not less than 70%, said relative crystallinity is the percent value of the degree of crystallinity of P-contained Y-zeolite provided by the invention and the degree of crystallinity of NaY raw material (defining its degree of crystallinity is 100%) among the present invention, the measuring method of this relative crystallinity is referring to " (petrochemical complex analytical procedure (RIPP test method) " (volume such as Yang Cuiding, Science Press, 414-415, nineteen ninety publishes).
The used P-contained Y-zeolite of catalyzer provided by the invention has following pore distribution, and after 550-850 ℃ of hydrothermal treatment consists was after 15 minutes to 5 hours, the pore volume of this P-contained Y-zeolite second hole accounted for 15～75% of total pore volume.Described second hole refers to that the bore dia except that molecular sieve intracrystalline micropore is the hole of 20～1000 .Total pore volume adopts low-temperature nitrogen adsorption method to measure, referring to " petrochemical complex analytical procedure (RIPP test method) ", (volume such as Yang Cuiding, Science Press, 424-426, nineteen ninety publishes).Determine the micro pore volume of molecular sieve from adsorption isothermal line according to the T graphing method, total pore volume is deducted micro pore volume obtain the second hole volume.
Described rare earth is selected from one or more in the lanthanide series rare-earth elements, as being selected from lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, the lutetium one or more.Wherein, the mishmetal of preferred lanthanum, cerium or rich lanthanum or rich cerium.Owing to being purchased easily, the mixed rare earth compound of rich lanthanum or rich cerium gets, therefore, and the mishmetal of more preferably rich lanthanum of described rare earth or rich cerium.
According to catalyzer provided by the invention, described clay is selected from one or more in the cracking catalyst clay commonly used, as kaolin, and halloysite, polynite, diatomite, tired in the soil one or more, the preferred kaolin of taking off.Described al binder is selected from cracking catalyst al binder commonly used, preferred pseudo-boehmite and/or aluminium colloidal sol.
According to Preparation of catalysts method provided by the invention, though the described y-type zeolite that contains rare earth can be rare earth Y type zeolite REY, among rare earth hydrogen Y zeolite REHY and the hyperastable Y-type RE zeolite REUSY one or more, but, the employing sodium oxide content is that the y-type zeolite that contains rare earth of the heavy % of 3-10 more helps reaching purpose of the present invention, and its reason is discussed hereinafter.Therefore, when the not enough 3-10% of the sodium oxide content in the described y-type zeolite that contains rare earth is heavy, preferably carry out ion-exchange with a kind of sodium salt solution and make the sodium oxide that contains the heavy % of 3-10 in the y-type zeolite that contains rare earth, the sodium ion switching technology is conventional technology, does not do detailed description at this.
With the step of silicon-containing compound dipping y-type zeolite can be before soaking the phosphorus step, carry out afterwards or simultaneously, in order to reduce operation steps, preferably with a kind of solution impregnation rare earth Y type zeolite that contains phosphorus compound and silicon compound simultaneously, the step of promptly flooding phosphorus and silicon compound is carried out simultaneously.
The described y-type zeolite that contains rare earth can be commercially available, and also can use NaY zeolite, NH
4Y zeolite, HY zeolite, overstable gamma zeolite and the solution that contains rare earth ion carry out ion-exchange, or obtain with the above-mentioned y-type zeolite of the solution impregnation that contains rare earth ion.The described content that contains the y-type zeolite middle-weight rare earths of rare earth should make and contain the heavy % of 0.2-15 in the P-contained Y-zeolite that finally obtains, the rare earth oxide of the heavy % of preferred 1-10.The technology of carrying out ion-exchange with rare earth ion also is conventional technology, does not do detailed description at this.
Described P contained compound is selected from this area various phosphorus compounds commonly used, as in phosphoric acid, Secondary ammonium phosphate, primary ammonium phosphate, the ammonium phosphate one or more.Described silicon-containing compound is described in front.The concentration of P contained compound and silicon compound solution is unimportant, as long as phosphorus compound and silicon compound can be immersed on the y-type zeolite equably,, can also repeatedly flood if strength of solution is lower, but preferred single-steeping.
According to method provided by the invention, after dipping phosphorus and silicon compound, all right, and preferably having the step that a hydrothermal treatment consists dipping is gone up the rare earth Y type zeolite of phosphorus and silicon compound, this step comprises, at 550-850 ℃, be preferably under 600-750 ℃ the temperature, described rare earth Y type zeolite is contacted with a kind of steam-laden atmosphere, be at least duration of contact 10 minutes, preferred 15 minutes to 5 hours.Described steam-laden atmosphere can be 100% water vapour, also can be to contain the water vapour of at least 10 body % water vapour and the gas mixture of rare gas element.Here, described rare gas element refers in the hydrothermal treatment consists process zeolite not had the gas of destruction, as the gas of neutral element in air, nitrogen, oxygen, carbon dioxide, the periodic table of elements etc.Wherein, one or more in preferred air, nitrogen and the carbonic acid gas.In the hydrothermal treatment consists process, zeolite generation dealuminzation phenomenon, owing to contain silicon components in the used P-contained Y-zeolite of catalyzer provided by the invention, wherein the part Siliciumatom migrates in the room of y-type zeolite dealuminzation formation, zeolite is mended silicon, though the zeolite that sodium oxide content is lower also can use, but in the zeolite of high oxidation sodium content, the existence of sodium oxide can slow down the dealuminzation speed of zeolite, the speed that makes Siliciumatom enter the dealuminzation room is accelerated relatively, thereby sodium oxide content is that the rare earth Y type zeolite of the heavy % of 3-10 is preferred.Mending the silicon effect is maintained skeleton structure of zeolite, therefore, hydrothermal treatment consists not only makes zeolite produce many second holes, and phosphorus and zeolite are combined better, and owing to the benefit silicon effect of silicon components to zeolite, make skeleton structure of zeolite complete, have the degree of crystallinity higher, overcome the prior art P-contained zeolite through the lower shortcoming of hydrothermal treatment consists post crystallization degree than prior art.The raising of relative crystallinity means that zeolite changes the minimizing of amorphous silicon aluminum portions into, i.e. the minimizing of wastage of material.
According to Preparation of catalysts method provided by the invention, the drying of slurries adopts existing the whole bag of tricks, as oven dry, dries methods such as spraying drying.The exsiccant temperature can be preferably room temperature to 120 ℃ from room temperature to 700 ℃.Drying after the washing also adopts conventional method, and the exsiccant temperature can be preferably room temperature to 120 ℃ from room temperature to 300 ℃.
The purpose of described washing is the foreign ion of removing in the catalyzer, and the method for described washing is conventionally known to one of skill in the art.For example described washing can be used deionized water wash, also can be successively with concentration be the heavy % of 0.8-1.2 hydrochloric acid soln, contain the heavy % of ammoniacal liquor 0.5-0.8 ammonia soln, contain ammonia soln and the deionized water wash of the heavy % of ammoniacal liquor 0.1-0.5, when washing at every turn the liquid consumption be solid 10-20 doubly.
Owing to used this special zeolite, catalyzer provided by the invention has than the better catalytic performance of prior art, shows that catalyzer provided by the invention has stronger heavy oil conversion performance and better product distribution.For example, 500 ℃ of temperature of reaction, agent-oil ratio is 6, and air speed is 16 hours
-1Condition under, the cracking reaction of catalysing tube oil transportation in small fixed flowing bed, adopt the catalyzer that contains P-contained zeolite 38.0 heavy % provided by the invention to compare with the catalyzer that employing contains the existing phosphorous rare earth Y type zeolite of same amount, transformation efficiency, yield of light oil and yield of gasoline have improved 3.7%, 7.2%, 8.9% respectively, and coking yield has then reduced by 22.4%.
The following examples will the present invention is described further, but not thereby limiting the invention.
Example 1
The preparation of the used P-contained Y-zeolite of catalyzer provided by the invention.
1. with 100 grams (dry basis), lattice constant is that the NaY type zeolite (sodium oxide content 14 heavy %, the Shandong catalyst plant is produced) of 2.473 nanometers is the (NH of 5 heavy % with 2 liters of concentration
4)
2SO
4The aqueous solution carried out ion-exchange 0.5 hour in 60 ℃, filtered, and to there not being acid group, 120 ℃ of oven dry obtain NH with the deionized water wash filter cake
4NaY type zeolite.
With 90 the gram (dry basis) above-mentioned preparations NH
4NaY type zeolite is at 2 liters of RECl that contain rare earth oxide 0.8 heavy %
X(Baotou rare earth factory in the Inner Mongol produces, and based on lanthanum, rare earth oxide content is 46 heavy %, and wherein, the percentage ratio that each oxide compound accounts for total oxide weight is La
2O
353.2%, CeO
213.0%, Pr
6O
1113.0%, Nd
2O
320.8%) in the solution, carry out ion-exchange 0.5 hour under 90 ℃, filter, to there not being acid group, 120 ℃ of oven dry obtain containing the NH of rare earth with the deionized water wash filter cake
4NaY type zeolite records its Na
2O content is 4.2 heavy %.
3. 80 gram (dry basis) above-mentioned preparations are contained rare earth NH
4(Changhong chemical plant, Beijing commerical prod contains 12%SiO for NaY type zeolite and 100 gram silicon sol
2) and 28 grams contain P
2O
5Solution behind the ammonium dibasic phosphate solution mixing of 15 heavy % mixes, and 120 ℃ of oven dry obtain the used P-contained Y-zeolite A of catalyzer provided by the invention.The phosphorus of P-contained Y-zeolite A, silicone content and content of rare earth are as shown in table 1, and dipping silicon wherein and phosphorus content are by calculating, and content of rare earth adopts x-ray fluorescence spectrometry.
Example 2
The preparation of the used P-contained zeolite of catalyzer provided by the invention.
1. the NaY type zeolite (sodium oxide content 14 heavy %, the Shandong catalyst plant is produced) that with 100 gram (dry basis) lattice constants is 2.473 nanometers is the (NH of 10 heavy % with 2 liters of concentration
4)
2SO
4The aqueous solution carried out ion-exchange 0.5 hour in 60 ℃, filtered, and to there not being acid group, 120 ℃ of oven dry obtain NH with the deionized water wash filter cake
4NaY type zeolite.
With 95 the gram (dry basis) above-mentioned preparations NH
4NaY type zeolite is at 2 liters of RECl that contain rare earth oxide 0.4 heavy %
XIn (with example 1) solution, carry out ion-exchange 0.5 hour under 90 ℃, filter, to there not being acid group, 120 ℃ of oven dry obtain containing the NH of rare earth with the deionized water wash filter cake
4NaY type zeolite records its Na
2O content is 3.6 heavy %.
With 90 the gram (dry basis) above-mentioned preparations the NH that contains rare earth
4(Shandong catalyst plant product contains SiO for NaY type zeolite and 90 gram water glass
215%, modulus 3.3) and 38 grams contain P
2O
59.5 the solution behind the ammonium dibasic phosphate solution mixing of heavy % mixes, 120 ℃ of oven dry obtain the zeolite B of the used phosphorous and rare earth of catalyzer provided by the invention.The phosphorus of P-contained zeolite B, silicone content and content of rare earth are as shown in table 1, and dipping silicon wherein and phosphorus content are by calculating, and content of rare earth adopts x-ray fluorescence spectrometry.
Comparative Examples 1
The preparation of reference P-contained Y-zeolite.
1. prepare Na by 1 and 2 method in the example 2
2O content is the NH that contains rare earth of 3.6 heavy %
4The NaY zeolite.
2. 6.0 gram Secondary ammonium phosphates are dissolved in the 120 gram deionized waters, with the Na of ammonium dibasic phosphate solution dipping 90 gram (dry basis) the above-mentioned preparations that obtain
2O content is the NH that contains rare earth of 3.6 heavy %
4Behind the NaY zeolite 1 hour, 120 ℃ of oven dry obtain reference P-contained Y-zeolite B1.Phosphorus content and content of rare earth among the reference P-contained Y-zeolite B1 are listed in the table 1.
Example 3
The preparation of the used P-contained Y-zeolite of catalyzer provided by the invention.
1. the NaY type zeolite (sodium oxide content 14 heavy %, the Shandong catalyst plant is produced) that with 100 gram (dry basis) lattice constants is 2.473 nanometers is the (NH of 3.0 heavy % with 2 liters of concentration
4)
2SO
4The aqueous solution carried out ion-exchange 0.5 hour in 60 ℃, filtered, and to there not being acid group, obtained NH with the deionized water wash filter cake after the drying
4NaY type zeolite.
With 90 the gram (dry basis) above-mentioned preparations NH
4NaY type zeolite is at 2 liters of RECl that contain 1.2 heavy % rare earth oxides
XIn (with example 1) solution, under 90 ℃, carry out ion-exchange 0.5 hour, filter, to there not being acid group, obtain containing the NH of rare earth after the drying with the deionized water wash filter cake
4NaY type zeolite records its Na
2O content is 4.3 heavy %.
3. 9.0 gram Secondary ammonium phosphates are dissolved in the 25 gram water, the ammonium silicofluoride (chemical pure of the ammonium dibasic phosphate solution that obtains and 120 milliliter of 1.0 mol, concentration is greater than 99%, Beijing Chemical Plant's product) solution mixes, with the NH that contains rare earth of mixing solutions dipping 80 gram (dry basis) the above-mentioned preparations that obtain
4NaY type zeolite, 120 ℃ of oven dry obtain the used P-contained Y-zeolite C of catalyzer provided by the invention.Phosphorus among the P-contained Y-zeolite C, rare earth and dipping silicone content are listed in the table 1.
Example 4
The preparation of the used P-contained zeolite of catalyzer provided by the invention.
1, be extremely steady y-type zeolite of rare earth (REUSY, the Na of 2.448 nanometers with 100 gram (dry basis) lattice constants
2O content is 1.2 heavy %, and rare earth oxide content is 1.5 heavy %, wherein, and La
2O
3Content is 0.8 heavy %, CeO
2Content is 0.2 heavy %, and other rare-earth oxide content are 0.5 heavy %, and the Shandong catalyst plant is produced) and 2 liters of Na that concentration are 5 heavy %
2SO
4Aqueous solution was carried out ion-exchange 0.5 hour in 60 ℃, filtered, and to there not being acid group, 120 ℃ of oven dry obtain containing Na with the deionized water wash filter cake
2The REUSY zeolite of O 4.9 heavy %.
2, with 90 gram (dry basis) above-mentioned Na that contain
2(Changhong chemical plant, Beijing commerical prod contains 12%SiO for the REUSY zeolite of O 4.9 heavy % and 100 gram silicon sol
2) and 28 grams contain P
2O
5The mixing solutions of the ammonium dibasic phosphate solution of 15 heavy % mixes, and 120 ℃ of oven dry obtain the used P-contained Y-zeolite D of catalyzer provided by the invention.Table 1 has provided the content of phosphorus, rare earth and dipping silicon among the P-contained Y-zeolite D.
Example 5
The preparation of the used P-contained Y-zeolite of catalyzer provided by the invention.
With 90 gram (dry basis) lattice constants is the REHY zeolite (Na of 2.465 nanometers
2O content 4.5 heavy %, RE
2O
3Content 3.4 heavy %, wherein, La
2O
3Content is 1.8 heavy %, CeO
2Content is 0.4 heavy %, and other rare-earth oxide content are 1.2 heavy %, and the Shandong catalyst plant is produced) (Changhong chemical plant, Beijing commerical prod contains 12%SiO with 80 gram silicon sol
2) and 38 grams contain P
2O
56.0 the solution that the ammonium dibasic phosphate solution of heavy % obtains after mixing mixes, 120 ℃ of oven dry obtain the used P-contained Y-zeolite E of catalyzer provided by the invention.The phosphorus of P-contained Y-zeolite E, silicon and content of rare earth are listed in the table 1.
Comparative Examples 2
The preparation of reference P-contained Y-zeolite.
Restrain REHY zeolite (with example 5) and 100 grams that (dry basis) lattice constants are 2.465 nanometers with 90 and contain P
2O
52.0 the ammonium dibasic phosphate solution of heavy % mixes, 120 ℃ of oven dry obtain reference P-contained Y-zeolite E1.Phosphorus and content of rare earth among the reference P-contained Y-zeolite E1 are listed in the table 1.
Table 1
| Example number | The zeolite numbering | Phosphorus content, heavy % is (with P 2O 5Meter) | Content of rare earth, heavy % (in rare earth oxide) | The dipping silicone content, heavy % is (with SiO 2Meter) |
| ????1 | ????A | ????4.4 | ????6.0 | ????12.4 |
| ????2 | ????B | ????3.4 | ????3.1 | ????12.6 |
| Comparative Examples 1 | ????B1 | ????3.4 | ????3.3 | ????- |
| ????3 | ????C | ????5.3 | ????9.6 | ????7.8 |
| ????4 | ????D | ????4.0 | ????1.2 | ????11.3 |
| ????5 | ????E | ????2.2 | ????2.8 | ????9.4 |
| Comparative Examples 2 | ????E1 | ????2.2 | ????3.0 | ????- |
Example 6-10
Following example explanation is through the character of the used P-contained Y-zeolite of the catalyzer provided by the invention of hydrothermal treatment consists.
The P-contained Y-zeolite that example 1-5 is prepared the different time of roasting in steam atmosphere, with x-ray diffraction method mensuration their relative crystallinity and lattice constant, is measured their specific surface, pore volume with cryogenic nitrogen absorption BET method under different temperature respectively.The results are shown in Table 2.
Comparative Examples 3
This Comparative Examples illustrates after hydrothermal treatment step, the character of reference P-contained Y-zeolite.
Method by example 7 is carried out hydrothermal treatment consists to zeolite, be used zeolite be the reference P-contained Y-zeolite B1 of Comparative Examples 1 preparation, the results are shown in Table 2.
Comparative Examples 4
This Comparative Examples illustrates after hydrothermal treatment step, the character of reference P-contained Y-zeolite.Method by example 10 is carried out hydrothermal treatment consists to zeolite, be used zeolite be the reference P-contained Y-zeolite E1 of Comparative Examples 2 preparation, the results are shown in Table 2.
Table 2
| Example number | ????6 | ????7 | Comparative Examples 3 | ????8 | ????9 | ????10 | Comparative Examples 4 |
| The zeolite numbering | ????A | ????B | ????B1 | ????C | ????D | ????E | ????E1 |
| The hydrothermal treatment consists temperature, ℃ | ????600 | ????650 | ????650 | ????700 | ????750 | ????700 | ????700 |
| The hydrothermal treatment consists time, minute | ????30 | ????60 | ????60 | ????90 | ????120 | ????120 | ????120 |
| Steam atmosphere | 100% water vapour | 100% water vapour | 100% water vapour | 50% water vapour | 100% water vapour | 100% water vapour | 100% water vapour |
| Relative crystallinity, % | ????75 | ????72 | ????58 | ????72 | ????70 | ????73 | ????60 |
| Lattice constant, dust | ????24.62 | ????24.58 | ????24.58 | ????24.56 | ????24.48 | ????24.52 | ????24.52 |
| Specific surface, rice 2/ gram | ????625 | ????598 | ????559 | ????582 | ????576 | ????592 | ????555 |
| Total pore volume, milliliter/gram | ????0.358 | ????0.352 | ????0.360 | ????0.348 | ????0.342 | ????0.353 | ????0.350 |
| The second hole volume, milliliter/gram | ????0.093 | ????0.109 | ????0.113 | ????0.116 | ????0.135 | ????0.128 | ????0.125 |
| Second hole accounts for total pore volume percentage ratio | ????26.0 | ????31.0 | ????31.4 | ????33.3 | ????39.5 | ????36.3 | ????35.7 |
From the result of table 2 as can be seen, after high-temperature water thermal treatment, compare with existing P-contained Y-zeolite, the relative crystallinity of the used P-contained Y-zeolite of catalyzer provided by the invention is greatly enhanced, after hydrothermal treatment consists, its relative crystallinity all is not less than 70%, and other physico-chemical property does not then have difference substantially.For example, with the used P-contained Y-zeolite B of catalyzer provided by the invention roasting after 60 minutes in 650 ℃ of 100% water vapour, relative crystallinity is 72%, and the identical reference P-contained Y-zeolite B1 of phosphorus content of employing prior art for preparing, after under similarity condition, handling, its relative crystallinity has only 58%, and the used zeolite relative crystallinity of catalyzer provided by the invention has improved 24.1% than reference zeolite.Again for example, the used P-contained zeolite E of catalyzer roasting after 120 minutes in 700 ℃ of 100% water vapour will be the invention provides, relative crystallinity is 73%, and the identical reference P-contained zeolite E1 of phosphorus content of employing prior art for preparing, after under similarity condition, handling, its relative crystallinity has only 60%, the used zeolite relative crystallinity of catalyzer provided by the invention has improved 21.7% than reference zeolite, this means that compared with prior art the present invention has lost 24.1% and 21.7% zeolite respectively less.
Example 11
This example illustrates catalyzer provided by the invention and preparation thereof.
90 gram pseudo-boehmites (are contained Al
2O
334.8 heavy %, Shandong Aluminum Plant produces) and 90 gram deionized waters mixing making beating, adding 26 gram concentration again is the hydrochloric acid of 37 heavy %, stirs, and is warming up to 70 ℃, aging 1.5 hours, obtains aged pseudo-boehmite slurries.
The P-contained Y-zeolite A of 50 gram (dry basis) examples, 1 preparation is carried out hydrothermal treatment consists with the method for example 6, (contain Al with 50 gram aluminium colloidal sols then
2O
321 heavy %, the Shandong catalyst plant is produced) and above-mentioned aged pseudo-boehmite mix.500 ℃ of dryings weigh % and NH with 20 times of weight in the HCl 0.84 that contains of butt sample after 2 hours successively
3.H
2The solution of the heavy % of O 0.62, contain NH
3.H
2The ammonia soln of O 0.17 heavy % and deionized water mix making beating, washing, filter, and obtain containing catalyzer provided by the invention after 120 ℃ of oven dry, are designated as C1.The composition of C1 is listed in the table 3.The catalyzer composition is got by calculating.
Example 12
This example illustrates catalyzer provided by the invention and preparation thereof.
70 gram pseudo-boehmites (are contained Al
2O
334.8 heavy %, Shandong Aluminum Plant produces) and 70 gram deionized waters mixing making beating, adding 20 gram concentration again is the hydrochloric acid of 37 heavy %, stirs, and is warming up to 70 ℃, aging 1.5 hours, obtains aged pseudo-boehmite slurries.
The P-contained Y-zeolite B of 50 gram (dry basis) examples, 2 preparations is carried out hydrothermal treatment consists with the method for example 7, (contain Al with 30 gram aluminium colloidal sols then
2O
321 heavy %, the Shandong catalyst plant is produced), 60 gram kaolin (solid content 85 heavy %, kaolin company in Suzhou produces) and above-mentioned aged pseudo-boehmite mix.500 ℃ of dryings weigh % and NH with 20 times of weight in the HCl 0.84 that contains of butt sample after 2 hours successively
3.H
2The solution of the heavy % of O 0.62, contain NH
3.H
2The ammonia soln of O 0.17 heavy % and deionized water mix making beating, washing, filter, and obtain catalyzer provided by the invention after 120 ℃ of oven dry, are designated as C2.
Comparative Examples 5
This Comparative Examples explanation reference catalyst and preparation thereof.
Method by example 12 prepares catalyzer, and the different reference P-contained Y-zeolite B1 that just prepare with Comparative Examples 3 replace P-contained Y-zeolite B, obtain reference catalyst CB2.The composition of CB2 is listed in the table 3.
Example 13
This example illustrates catalyzer provided by the invention and preparation thereof.
90 gram pseudo-boehmites (are contained Al
2O
334.8 heavy %, Shandong Aluminum Plant produces) and 90 gram deionized waters mixing making beating, adding 26 gram concentration again is the hydrochloric acid of 37 heavy %, stirs, and is warming up to 70 ℃, aging 1.5 hours, obtains aged pseudo-boehmite slurries.
The P-contained Y-zeolite C of 50 gram (dry basis) examples, 3 preparations is carried out hydrothermal treatment consists with the method for example 8, (contain Al with 50 gram aluminium colloidal sols then
2O
321 heavy %, the Shandong catalyst plant is produced), 70 gram kaolin (solid content 85 heavy %, kaolin company in Suzhou produces) and above-mentioned aged pseudo-boehmite mix.480 ℃ of dryings weigh % and NH with 20 times of weight in the HCl 0.84 that contains of butt sample after 2 hours successively
3.H
2The solution of the heavy % of O 0.62, contain NH
3.H
2The ammonia soln of O 0.17 heavy % and deionized water mix making beating, washing, filter, and obtain catalyzer provided by the invention after 120 ℃ of oven dry, are designated as C3.The composition of C3 is listed in the table 3.
Example 14
This example illustrates catalyzer provided by the invention and preparation thereof.
90 gram pseudo-boehmites (are contained Al
2O
334.8 heavy %, Shandong Aluminum Plant produces) and 90 gram deionized waters mixing making beating, adding 26 gram concentration again is the hydrochloric acid of 37 heavy %, stirs, and is warming up to 70 ℃, aging 1.5 hours, obtains aged pseudo-boehmite slurries.
The P-contained Y-zeolite D of 50 gram (dry basis) examples, 4 preparations is carried out hydrothermal treatment consists with the method for example 9, (contain Al with 30 gram aluminium colloidal sols then
2O
321 heavy %, the Shandong catalyst plant is produced), 54 gram kaolin (solid content 85 heavy %, kaolin company in Suzhou produces) and above-mentioned aged pseudo-boehmite mix.550 ℃ of dryings weigh % and NH with 20 times of weight in the HCl 0.84 that contains of butt sample after 2 hours successively
3.H
2The solution of the heavy % of O 0.62, contain NH
3.H
2The ammonia soln of O 0.17 heavy % and deionized water mix making beating, washing, filter, and obtain catalyzer provided by the invention after 120 ℃ of oven dry, are designated as C4.The composition of C4 is listed in the table 3.
Example 15
This example illustrates catalyzer provided by the invention and preparation thereof.
70 gram pseudo-boehmites (are contained Al
2O
334.8 heavy %, Shandong Aluminum Plant produces) and 70 gram deionized waters mixing making beating, adding 20 gram concentration again is the hydrochloric acid of 37 heavy %, stirs, and is warming up to 70 ℃, aging 1.5 hours, obtains aged pseudo-boehmite slurries.
The P-contained Y-zeolite E of 50 gram (dry basis) examples, 5 preparations is carried out hydrothermal treatment consists with the method for example 9, (contain Al with 30 gram aluminium colloidal sols then
2O
321 heavy %, the Shandong catalyst plant is produced), 54 gram kaolin (solid content 85 heavy %, kaolin company in Suzhou produces) and above-mentioned aged pseudo-boehmite mix.500 ℃ of dryings weigh % and NH with 20 times of weight in the HCl 0.84 that contains of butt sample after 2 hours successively
3.H
2The solution of the heavy % of O 0.62, contain NH
3.H
2The ammonia soln of O 0.17 heavy % and deionized water mix making beating, washing, filter, and obtain catalyzer provided by the invention after 120 ℃ of oven dry, are designated as C5.The composition of C5 is listed in the table 3.
Comparative Examples 6
This Comparative Examples explanation reference catalyst and preparation thereof.
Method by example 15 prepares the different reference P-contained Y-zeolite E1 replacement P-contained Y-zeolite E that just prepares with Comparative Examples 2 of catalyzer, obtains reference catalyst CB5.The composition of CB5 is listed in the table 3.
Table 3
| Example number | The catalyzer numbering | Catalyzer is formed, heavy % | ||
| P-contained zeolite | Al binder (in aluminum oxide) | Kaolin | ||
| ????11 | ????C1 | ????45.5 | ????54.5 | ????- |
| ????12 | ????C2 | ????38.0 | ????23.3 | ????38.7 |
| Comparative Examples 5 | ????CB2 | ????38.0 | ????23.3 | ????38.7 |
| ????13 | ????C3 | ????33.0 | ????27.7 | ????39.3 |
| ????14 | ????C4 | ????29.3 | ????25.8 | ????44.9 |
| ????15 | ????C5 | ????39.5 | ????24.2 | ????36.3 |
| Comparative Examples 6 | ????CB5 | ????39.5 | ????24.2 | ????36.3 |
Example 16
This example illustrates the catalytic performance of catalyzer provided by the invention.The catalyzer C2 of example 12 preparations was worn out 4 hours with 100% water vapour at 800 ℃, was raw material with the oil transportation of pipe shown in the table 4, estimated the catalytic performance of aging rear catalyst on small fixed flowing bed-tion reacting device, and reaction conditions and reaction result are listed in the table 5.
Wherein, transformation efficiency=dry gas yield+yield of liquefied gas+yield of gasoline+coking yield
Yield of light oil=yield of gasoline+diesel yield.
Comparative Examples 7
The catalytic performance of this Comparative Examples explanation reference catalyst.
Catalyzer is worn out and the catalyzer after aging is estimated by the method for example 16, different is replaces catalyzer C2 with the reference catalyst CB2 of Comparative Examples 5 preparations, and reaction conditions and reaction result are listed in the table 5.
Table 4
| Title | The pipe oil transportation |
| Density (20 ℃), g/cm 3 | ????0.9044 |
| Kinematic viscosity, mm 2/s ????50℃ ????????100℃ | ????57.69 ????9.96 |
| Zero pour, ℃ | ????40.0 |
| Carbon residue, m% | ????2.97 |
| Molecular weight (actual measurement) | ????390 |
| ????C 7Insolubles | ????0.37 |
| ????C，m％ | ????85.98 |
| ????H，m％ | ????12.86 |
| ????S，m％ | ????0.55 |
| Alkali nitrogen, ppm | ????1000 |
| Boiling range, ℃ initial boiling point 5% 10% 30% 50% 70% 90% | ????243 ????294 ????316 ????395 ????429 ????473 ????530 |
Table 5
| Example number | ????16 | Comparative Examples 5 |
| Catalyzer | ????C2 | ????CB2 |
| Temperature of reaction, ℃ | ????500 | ????500 |
| Agent-oil ratio | ????6 | ????6 |
| Air speed, hour -1 | ????16 | ????16 |
| Transformation efficiency, heavy % | ????73.6 | ????71.0 |
| Yield of light oil, heavy % | ????77.4 | ????72.2 |
| Product is formed, heavy % H 2-C 2Liquefied gas gasoline, diesel heavy oil coke | ????1.4 ????11.9 ????55.8 ????21.6 ????4.8 ????4.5 | ????1.8 ????12.2 ????51.2 ????21.0 ????8.0 ????5.8 |
From the result of table 5 as can be seen, adopt the catalyzer that contains P-contained zeolite 38.0 heavy % provided by the invention to compare with the catalyzer that employing contains the existing phosphorous rare earth Y type zeolite of same amount, transformation efficiency, yield of light oil and yield of gasoline have improved 3.7%, 7.2%, 8.9% respectively, and coking yield has then reduced by 22.4%.
Example 17
This example illustrates the catalytic performance of catalyzer provided by the invention.
The catalyzer C5 of example 15 preparations was worn out 4 hours with 100% water vapour at 800 ℃, was raw material with the oil transportation of pipe shown in the table 4, estimated the catalytic performance of aging rear catalyst on small fixed flowing bed-tion reacting device, and reaction conditions and reaction result are listed in the table 6.
Comparative Examples 7
The catalytic performance of this Comparative Examples explanation reference catalyst.
Catalyzer is worn out and the catalyzer after aging is estimated by the method for example 17, different is replaces catalyzer C5 with the reference catalyst CB5 of Comparative Examples 6 preparations, and reaction conditions and reaction result are listed in the table 6.
Table 6
| Example number | ????17 | Comparative Examples 7 |
| Catalyzer | ????C5 | ????CB5 |
| Temperature of reaction, ℃ | ????500 | ????500 |
| Agent-oil ratio | ????6 | ????6 |
| Air speed, hour -1 | ????16 | ????16 |
| Transformation efficiency, heavy % | ????74.7 | ????73.1 |
| Yield of light oil, heavy % | ????77.1 | ????74.3 |
| Product is formed, heavy % H 2-C 2Liquefied gas gasoline, diesel heavy oil coke | ????1.5 ????12.2 ????56.3 ????20.8 ????4.5 ????4.7 | ????1.7 ????13.5 ????52.9 ????21.4 ????5.5 ????5.0 |
Result from table 5 and table 6 compares with prior art catalyzer (reference catalyst) as can be seen, under same reaction conditions, adopts catalyzer provided by the invention to have higher transformation efficiency, yield of light oil, yield of gasoline and lower coking yield.This illustrates that catalyzer provided by the invention has higher heavy oil conversion performance and better product distribution.
Claims (21)
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| US11052381B2 (en) | 2017-02-21 | 2021-07-06 | China Petroleum & Chemical Corporation | Modified Y-type molecular sieve, preparation thereof and catalyst comprising the same |
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| TWI760436B (en) * | 2017-02-22 | 2022-04-11 | 大陸商中國石油化工科技開發有限公司 | Catalytic cracking catalyst and preparation method thereof |
| TWI784075B (en) * | 2017-10-31 | 2022-11-21 | 大陸商中國石油化工科技開發有限公司 | Phosphorus-containing molecular sieve and its preparation method and application |
| US11524281B2 (en) | 2017-10-31 | 2022-12-13 | China Petroleum & Chemical Corporation | Phosphorus-containing molecular sieve, its preparation and application thereof |
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