CN102019200B - High-activity catalytic pyrolysis catalyst and preparation method thereof - Google Patents
High-activity catalytic pyrolysis catalyst and preparation method thereof Download PDFInfo
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- CN102019200B CN102019200B CN 201010145461 CN201010145461A CN102019200B CN 102019200 B CN102019200 B CN 102019200B CN 201010145461 CN201010145461 CN 201010145461 CN 201010145461 A CN201010145461 A CN 201010145461A CN 102019200 B CN102019200 B CN 102019200B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- 230000000694 effects Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000007233 catalytic pyrolysis Methods 0.000 title abstract description 14
- 239000010457 zeolite Substances 0.000 claims abstract description 106
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 95
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 94
- 230000003197 catalytic effect Effects 0.000 claims abstract description 39
- 239000011148 porous material Substances 0.000 claims abstract description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 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 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000009826 distribution Methods 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- 239000004927 clay Substances 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims abstract description 9
- 239000000945 filler Substances 0.000 claims abstract description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 7
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 7
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 4
- 238000004227 thermal cracking Methods 0.000 claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 238000012986 modification Methods 0.000 claims description 13
- 230000004048 modification Effects 0.000 claims description 13
- 229910021426 porous silicon Inorganic materials 0.000 claims description 13
- 150000003377 silicon compounds Chemical class 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 239000004411 aluminium Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 9
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 9
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 230000020477 pH reduction Effects 0.000 claims description 3
- 239000010451 perlite Substances 0.000 claims description 3
- 235000019362 perlite Nutrition 0.000 claims description 3
- 238000013459 approach Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 17
- -1 ethylene, propylene Chemical group 0.000 abstract description 10
- 229910021332 silicide Inorganic materials 0.000 abstract description 3
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004005 microsphere Substances 0.000 abstract description 2
- 239000008247 solid mixture Substances 0.000 abstract 3
- 238000007740 vapor deposition Methods 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 description 46
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 42
- 238000000034 method Methods 0.000 description 33
- 238000005336 cracking Methods 0.000 description 25
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 25
- 239000003921 oil Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 21
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 21
- 239000000047 product Substances 0.000 description 20
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- 229930195733 hydrocarbon Natural products 0.000 description 14
- 150000002430 hydrocarbons Chemical class 0.000 description 14
- 150000001336 alkenes Chemical class 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 239000005995 Aluminium silicate Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- 235000012211 aluminium silicate Nutrition 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 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 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000010009 beating Methods 0.000 description 9
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- 239000002283 diesel fuel Substances 0.000 description 8
- 239000003209 petroleum derivative Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000004523 catalytic cracking Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- 239000002808 molecular sieve Substances 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 6
- 238000000197 pyrolysis Methods 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000001694 spray drying Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 229910001593 boehmite Inorganic materials 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002101 lytic effect Effects 0.000 description 3
- 239000011777 magnesium Chemical group 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 3
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- 238000003756 stirring Methods 0.000 description 3
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 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 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 2
- 235000019838 diammonium phosphate Nutrition 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 229910052621 halloysite Inorganic materials 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
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- 150000003254 radicals Chemical class 0.000 description 2
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 208000019901 Anxiety disease Diseases 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical group [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- 229910004116 SrO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
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- 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
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
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- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a high-activity catalytic pyrolysis catalyst and a preparation method thereof, which is characterized in that: the catalytic pyrolysis catalyst is a solid composition which is formed by high-activity phosphorus modified ZSM-5 zeolite, high-activity rare earth modified Y zeolite, an alumina-based bonder, nickel tetracarbonyl vapor deposition modified porous silicide and filler clay, is in multiple pore diameter distribution and has different types of catalytic active centers; the catalytic pyrolysis catalyst has another important characteristic: the pore capacity provided by the mesoporous ZSM-5 zeolite in the catalytic pyrolysis catalyst should be approximately equal to the pore capacity provided by the macroporous Y zeolite, that is to say, the ratio is in a range of 0.9-1.1. The total amount of the zeolite is 30-60% of the total amount of the solid composition by weight; the alumina-based bonder formed by acidified pseudoboehmite and/or alumina sol is 5-30% of the total amount by weight; the porous silicide which is 0.01-0.5% of the nickel tetracarbonyl vapor deposition nickeliferous oxide by weight is 1-20% of the total amount by weight; and the balance is the filler clay. The slurry of the solid composition is spray-dried to form the microsphere catalytic pyrolysis catalyst which has extraordinarily high activity and selectivity when being used in a catalytic pyrolysis device and can effectively transform the heavy feeding and improve the yield of the low-carbon olefins such as ethylene, propylene and the like.
Description
Technical field
The present invention relates to a kind of catalytic thermal cracking catalyst of petrochemical industry and preparation method thereof, the present invention relates to or rather a kind ofly have appearance such as multiple aperture and large mesopore and arrange in pairs or groups and the high activity in dissimilar activated centre and high selectivity catalytic thermal cracking catalyst and preparation method thereof are arranged.
Background technology
The low-carbon alkene such as ethene, propylene is the basic material of petrochemical industry, there are a lot of intermediate products and final products all to obtain take alkene as basic material in the petrochemical industry, its source is mainly obtained by thermal cracking production, to adopt pyrolysis in tubular furnace from the conventional method of petroleum hydrocarbon preparing ethylene, the ethene of its production accounts for more than 95% of world Ethylene output, and propylene also reaches about 70% of World Propylene total output.
The primary raw material of producing in the world ethene is the light petroleum hydrocarbons such as straight distillation light diesel oil of ethane, propane, butane, naphtha or part crude oil, and the tail oil that mink cell focus obtains through hydrocracking or the tail oil of heavy diesel fuel MHUG also can be used as cracking stock.The U.S. has abundant natural gas resource and petroleum refinery's gas, so the raw material of U.S.'s ethylene production, take ethane and liquefied petroleum gas as main, and Europe and the Far East Area, then take feed naphtha as main.The primary raw material that China produces ethene is naphtha and light diesel fuel, hydrocracking tail oil.Anxiety along with the crude resources supply, and China's Petrochemical development increasing sharply to the ethylene requirements amount, to expend a large amount of naphthas and light diesel fuel, simultaneously as the demand of the light-end products such as the vapour of engine fuel, coal, diesel oil also in continuous increase, particularly crude oil in China generally lays particular stress on, the productive rate of naphtha and straight distillation light diesel oil is lower, the source of light petroleum hydrocarbon is greatly limited, the imbalance between supply and demand of ethylene raw becomes increasingly conspicuous, and therefore comes the technique of preparing ethylene and catalyst more and more to come into one's own from heavy petroleum hydrocarbon.
A large amount of methods of petroleum hydrocarbon being carried out the cracking low-carbon alkene with catalyst are arranged in the prior art, employed catalyst roughly has three classes when adopting cracking or cleavage method preparing low-carbon olefins take petroleum hydrocarbon as raw material: a class is the metal load type catalyst take oxide as carrier, be metal load type catalyst take oxide as carrier such as what adopt among USP3541179, USP3647682, DD225135 and the SU1214726, their carrier can be SiO
2, Al
2O
3Or other oxide, the metal of institute's load is selected from IIB, VB, VIIB and VIIB family element.When using this class catalyst, because the dehydrogenation of carried metal causes also corresponding quickening of polymerization coking reaction when carrying out cracking reaction, so this type of catalyst generally is applicable to the light petroleum hydrocarbon of boiling point＜220 ℃.
Employed Equations of The Second Kind catalyst is composite oxides, is with ZrO such as the catalyst of reporting among USP3725495 and the USP3839485
2And/or HfO
2Be main component, be aided with Al
2O
3, CrO
3, MnO
2And/or Fe
2O
3And alkali metal or alkaline earth oxide.Ethylene yield be can improve when adopting alkali metal or alkaline earth oxide catalyst but relatively large CO and CO generated simultaneously
2
Adopted the mixture of metal oxide as catalyst, such as MgO-Al among the USP3624176
2O
3-CaO (contains a small amount of SiO
2, Fe
2O
3, ZrO
2, K
2O, Cr
2O
3) and MgO-SiO
2-ZrO
2(contain a small amount of Nd
2O
3, Al
2O
3, CaO) can improve yield of ethene, and reaction do not have carbon distribution, but still can contain a large amount of CO and CO in the cracked gas
2
USP3767567 has disclosed with containing CaO 11.4 heavy %, BeO 4.3 heavy %, SrO
20.8 heavy % and Al
2O
363.6 the sinter of heavy % is catalyst, under 720 ℃ of reaction temperatures, water-oil factor 3: 1,0.7 second time of staying condition, can obtain 51.7 heavy % ethene and 15.2 heavy % propylene.Alkaline earth oxide is converted at heavy charge to have control raw material hydrocarbon dehydrogenation reaction, suppress heat polymerization, improves the light olefin productive rate in the olefin process, but also contains a large amount of carbon monoxide and carbon dioxide in the pyrolysis product.
It is active component that USP3725494, USP3872179 adopt zirconium or titanyl compound, activated alumina be carrier as catalyst, and add alkaline-earth metal or alkali-metal oxide is generally potassium oxide, to stop the deposition of coke.Though this catalyst can obviously reduce coke content, fails to improve yield of ethene.
USP4087350, USP4111793 adopt manganese dioxide as active component, take refractory material titanium oxide or zirconia as carrier, take wax oil or reduced crude as raw material, under 800～900 ℃ of reaction temperatures, water-oil factor 2.0 above conditions, yield of ethene reaches 17～23 heavy %, reacts after 2 hours without carbon deposit.
Using metal oxide or its mixture carry out cracking reaction, although reached the accommodation of improving raw material, reduce reaction temperature, reduce coking, improve the purpose of yield of ethene, but the shortcoming of this catalyst also is obvious: from product, all generated relatively large carbon monoxide and carbon dioxide, certainly will bring many difficulties to the recovery of olefin product like this, increase the investment of separation of products, reclaimer; From process aspect, reaction temperature so just faces a series of engineering problems such as equipment high temperature, wearing and tearing and solid particle breakage near 800 ℃.
Composite oxides commonly used also have amorphous Si O
2, Al
2O
3, disclosed with amorphous Si O such as DD152356
2, Al
2O
3Be catalyst, take liquid hydrocarbon or various hydrocarbon-fraction (comprising gasoline, kerosene, gas oil or vacuum distillate) as raw material, preparing low-carbon olefins under 600～800 ℃ reaction temperature, C
2 =～C
4 =Productive rate can reach 40～55 heavy %.
A large amount of reported in literature the 3rd class catalyst, the catalyst that namely contains zeolite, adopt the synthesizing flokite of modification such as USP4172816, take lower paraffin hydrocarbon (ethane, propane, butane) or straight run crude oil (boiling point is until 550 ℃) as raw material, first zeolite is applied to the catalytic pyrolysis process.The oxide that adds rare earth metal in the modified mordenite with absorption method or eutectic method, and exchange with silver and to obtain catalyst was 725 ℃ of reaction temperatures, reaction pressure 0.01～2MPa, weight (hourly) space velocity (WHSV) 1.5 hours
-1Under the condition, C
9-14The n-alkane cracking, ethylene selectivity can reach 42.13%, and Propylene Selectivity is 18.79%, and catalyst carbon deposit only is 0.4 heavy %, and if be carried on the Ag-M with the cerium of 0.1 heavy %, the reaction carbon deposit can drop to 0.2 heavy %.
DD248516A adopts the A type zeolite catalyst of calcium, magnesium or manganese ion exchange, take vacuum gas oil (VGO) as raw material, at 500～650 ℃ of reaction temperatures, volume space velocity greater than 20 hours
-1Under the condition, C
2-4Olefins yield is very high.Zeolite (comprising aperture modenite, erionite) with alkaline-earth metal exchange is made catalyst, is that 250～450 ℃ vacuum distillate is made raw material with boiling range, and 650 ℃ of reaction temperatures, volume space velocity was greater than 20 hours
-1And cracking under hydrogen or the steam existence condition, conversion ratio is 83.5%, and gas-selectively is 73.2%, and therein ethylene is 33%, and propylene is 35.2%, butylene is 4.7%.
Containing what use especially in the catalyst of zeolite is to contain have the MFI structural zeolite catalyst of (five-membered ring silica-rich zeolite), is active component as having disclosed with HZSM-5 among the JP60224428, Al
2O
3Carry out the method for cracking petroleum hydrocarbon for the catalyst of carrier, under 600～750 ℃ to C
5～C
25The paraffin hydrocarbon raw material carry out catalytic cracking, C
2 =～C
4 =Productive rate is about 30 heavy %.
Used among the US4980053 with HZSM-5 as active component, the kaolin catalyst as carrier, with the heavy hydrocarbon cracking, product can obtain the C up to 40 heavy % under 500～650 ℃
3 =+ C
4 =, but C
2 =Productive rate is lower.
Selectively often ZSM-5 zeolite is carried out modification in order further to improve, such as the CN1162274A report is to introduce I B group metal in ZSM-5 zeolite, silica alumina ratio 28～300, import the catalyst of alkali metal and/or alkaline-earth metal ions in the middle pore, this catalyst at 500～900 ℃ through hydrothermal treatment consists, take naphtha as raw material, operating condition is 550～750 ℃ of reaction temperatures, hydrocarbon partial pressure 0.1～10 atmospheric pressure, can obtain low-carbon alkene and the mononuclear aromatics such as ethene of higher yields below 1 second time of contact, and its typical product is distributed as ethene 22～25 heavy %, propylene 16～20 heavy %, aromatic hydrocarbons is more than 20 heavy %.
JP06330055 exchanges ZSM-5 zeolite as catalyst, with naphtha or C take HZSM-5 or alkaline-earth metal
2-12Linear paraffin is raw material, in 550～700 ℃ of reaction temperatures, air speed 0.5～20 hour
-1Carry out cracking reaction under the condition.Naphtha reacts at the HZSM-5 zeolite under 680 ℃, and total conversion reaches 96.5%, and therein ethylene is 22.0 heavy %, and propylene is 22.2 heavy %, C
6-8Aromatic hydrocarbons is 26.4 heavy %.Use C
2-12Linear paraffin is raw material, under 680 ℃, reacts at the MgZSM-5 zeolite, and total conversion is 97.6%, and therein ethylene is 22.3 heavy %, and propylene is 20.8 heavy %, C
6-8Aromatic hydrocarbons is 22.8 heavy %.
Be in the catalytic reaction process of raw material adopting heavy hydrocarbon, tend to use simultaneously ZSM-5 zeolite and Y zeolite, as having disclosed take ratio as 1: 10～3: 1 ZSM-5 zeolite among the USP3758403 and large pore zeolite (such as X-type, Y type) can make C as the catalyst of active component in catalytic cracking process when improving octane number
3 =+ C
4 =Productive rate increase to about 10 heavy %.
USP5380690 or CN1093101A have disclosed the catalyst take the five-membered ring silica-rich zeolite of phosphorous and rare earth and y-type zeolite mixture as active component.This catalyst hydrothermal activity stability is high, can improve the octane number of product gasoline in catalytic cracking/cracking process of 500～600 ℃ during the cracking masout feedstock, improves simultaneously C
2 =～C
4 =Productive rate, and wherein with C
3 =And C
4 =Be main.
The ethene processed of the catalytic pyrolysis take heavy petroleum hydrocarbon as raw material of having developed since the nineties last century, the technique of propylene, such as CN1069016A, CN1083092A, CN1218786A, CN1317543A, CN1566267A is described, on the basis of conventional catalyst cracking technology, with wax oil, it is raw material (especially paraffine base crude oil) that wax oil is mixed the heavy oil such as residual oil or reduced crude, also can mix an amount of decompression residuum of refining, in riser reactor, adopt acid molecular sieve catalyst and fluidisation to carry successive reaction-regeneration cycle mode of operation, employing relaxes under the reaction temperature (620～680 ℃) high than catalytic pyrolysis than steam cracking, carry out catalytic pyrolysis, high temperature pyrolysis, shape selective catalysis, olefin-copolymerization, the combined reaction such as disproportionation and aromatisation, the purpose that the realization maximum is produced ethene and propylene.Its ethene, propylene and comprehensive production cost are compared with present naphtha steam cracking has obvious advantage, and the output capacity of alkene is close to naphtha steam cracking.Because it has the olefine selective requirement of more harsh operating condition and Geng Gao than catalytic cracking and Deep Catalytic Cracking process, disclosed successively catalyst and the technology of preparing for catalytic pyrolysis technique the most relevant with the present invention in the prior art for this reason.
The combination of molecular sieve that is used for high output of ethylene and propylene is disclosed such as CN1211469A and CN1211470A, said composition is by the penta-basic cyclic molecular sieve of 85～95 heavy %, and 2～10% heavy phosphorus (in oxide), (in oxide) a kind of alkali metal of 0.3～5 heavy % and/or (in oxide) a kind of transition metal of 0.3～5 heavy % form.Because the ZSM-5 zeolite duct is little, the mixed oxides such as the phosphorus of its modification, magnesium have in fact just formed a mixture with ZSM-5 zeolite, can not selectively produce Beneficial Effect to the cracking of zeolite.
CN1222558A discloses a kind of catalytic thermal cracking catalyst of prepared one-tenth on the phosphorus disclosed in above-mentioned two prior arts, magnesium-modified ZSM-5 zeolite basis, its catalyst take the five-membered ring silica-rich zeolite of phosphorous and aluminium, magnesium or calcium and y-type zeolite as active component improves the productive rate of the low-carbon alkene (especially ethene) of catalyst.Because its modified ZSM-5 zeolite that adopts is a mixture with unformed phosphorus, magnesium oxide, and adopt high silica alumina ratio, SA Y zeolite to reduce the hydrogen transfer activity of catalyst, being subjected to the catalyst strength requirement to limit the total content of zeolite can not be too high, has so just had a strong impact on the overall activity of thermal cracking catalyst.
CN1221015A has used and has contained aluminium cross-linked clay molecular sieve with layer structure and/or contain the five-membered ring silica-rich zeolite, and with the catalytic thermal cracking catalyst of phosphorus, magnesium oxide modification, the heavy hydrocarbon cracking can be obtained the C of 18 heavy % under 680 ℃
2 =Productive rate and 50 heavy %C
2 =～C
4 =Productive rate.But there are the problems such as serious green coke as macropore lytic activity constituent element afterwards because natural laminated clay column is crosslinked, can not use in actual applications always.
CN1660967A has adopted the ZSM-5 zeolite of oxides-containing iron modified RE, and be mixed with into catalytic thermal cracking catalyst with mesoporous silicon aluminum, al binder and kaolin etc., often excessively low as lytic activity constituent element activity by the mesoporous silicon aluminum, be difficult to replace the large pore zeolites such as faujasite, so that the whole conversion capability of this thermal cracking catalyst is not enough, limited its application in practice.
Summary of the invention
For above the deficiencies in the prior art, the purpose of this invention is to provide a kind of high selectivity and highly active catalytic thermal cracking catalyst and preparation method thereof.
The reaction mechanism of catalytic cracking is commonly considered as carbonium ion mechanism, and catalytic pyrolysis technique is the process of a catalytic reaction and thermal response coexistence, its reaction mechanism had both comprised carbonium ion mechanism, relate to again free radical mechanism, catalyst need to have carbonium ion reaction and radical reaction dual catalytic activity, the activated centre that should possess two kinds of different catalysis, i.e. surface acidity center and metal oxide oxidation catalyst activated centre.
Metal oxide is applied in the cracking ethylene preparation catalyst can reduce reaction temperature, reduces coking, improve yield of ethene, and the adaptability of raw material improves also.Metal oxide plays the effect of heat carrier on the one hand in reaction, the more important thing is that the catalyst as reaction plays the effect that promotes the free radical initial reaction, feed stock conversion is increased, thereby the yield of purpose product alkene is improved.But metal oxide tends to affect acid activated centre, needs to reduce the mutual interference effect of two kinds of catalytic active centers, avoids reducing the whole catalytic performance of catalytic thermal cracking catalyst.
The acid centre that zeolite molecular sieve has can make hydro carbons carry out cracking reaction by carbonium ion mechanism, but because the character of carbonium ion, its pyrolysis product is take propylene, butylene as main, ethene is less, and because the impact of the side reactions such as hydrogen migration, the product olefins yield is lower.Therefore the high silica alumina ratio zeolites that adopt in the prior art to reduce acid site density, are controlled hydrogen transfer reaction more, improve the selective of product alkene; Or the zeolite of employing mesopore or aperture, select the shape effect by it and increase ethylene selectivity; Or at zeolite molecular sieve exchange metal ion or metal oxide-loaded, change the distribution of the acid centre on zeolite molecular sieve surface, suppress hydrogen transfer reaction, improving the selective of the alkene such as ethene, but these all greatly reduce activity and the conversion capability of large pore zeolite Y zeolite in the catalytic thermal cracking catalyst.
Adopt the combination of zeolites in multiple aperture, can allow heavy oil at first cracking in macropore, then cracking naphtha cut in mesopore, except requiring high lytic activity and outstanding hydrothermal stability, can bear outside 750 ℃ the harsh hydro-thermal steam condition, above-mentioned graduated response and diffusion transport the capacity collocation of rational aperture also will be arranged, so that can effectively be carried out successively smoothly.
Require to have low hydrogen transfer reaction speed for catalytic thermal cracking catalyst, in order to improve olefin(e) centent in the product; But the activity that high cracking heavy charge is arranged under the reaction temperature of appropriateness again is to keep steadily carrying out of whole conversion process.This just requires have in the zeolite of appreciable impact the acid activated centre hydrogen transfer activity in the duct low on the target product selectivity of light olefin, and the target product selectivity of light olefin is affected the control that acid activated centre on inapparent macropore and the outer surface then needn't be subjected to the hydrogen migration factor.This just requires the acid activated centre in the different ducts different sour structural requirements to be arranged and consist of rational ratio collocation.Discovery is reasonably combined by the different pore size zeolite is carried out pore volume by above-mentioned requirements, be that the pore volumes collocation such as macropore and middle duct can diffuse into smoothly to pyrolysis product in the macropore that to carry out second pyrolysis in the middle duct favourable, add that adopting the distinct methods modification to satisfy to two kinds of zeolites above-mentionedly should have the requirement that high activity again must the low hydrogen transfer performance to catalytic thermal cracking catalyst.
The prepared catalytic thermal cracking catalyst of the present invention has adopted by the binding agent of highly active phosphorous modified ZSM-5 zeolite, highly active rare earth modified Y zeolite, alumina base, porous silicon compound and a kind of multiple aperture distribution that the filler clay consists of and the solid composite with different activities center of nickel carbonyl vapour deposition modification to achieve these goals; Its another key character equate for the pore capacities that provided by the mesopore ZSM-5 zeolite should approach with the pore capacities that is provided by macropore Y zeolite, and namely ratio is in 0.9～1.1 scope; The total amount of zeolite accounts for 30～60 heavy % of solid composite total amount.
The carrier of catalytic thermal cracking catalyst provided by the present invention is characterized as: the alumina base binding agent that is made of acidification pseudo-boehmite and/or aluminium colloidal sol accounts for 5～30 heavy % of total amount; The porous silicon compound that contains nickel oxide 0.01～0.5 heavy % by the nickel carbonyl vapour deposition accounts for 1～20 heavy % of total amount; Surplus is the filler clay.The spray-dried microballoon catalytic thermal cracking catalyst that is shaped to of these solid composite slurries.
With the catalytic thermal cracking catalyst of the method preparation because the capacity such as its multistage aperture and big or middle duct collocation and have dissimilar catalytic active center and distribute, have extra high activity and selectivity when it is used in catalytic heat cracking device, under the reaction condition that relaxes, improved whole conversion capability and the productive rate that has improved the low-carbon alkenes such as ethene, propylene to heavy hydrocarbon charge.
1, the zeolite component of the said highly active catalytic thermal cracking catalyst of the present invention is to be made of highly active ZSM-5 zeolite and two kinds of zeolites of high activity Y zeolite, and should be equated with the pore capacities that is provided by macropore Y zeolite is approaching by the pore capacities that the mesopore ZSM-5 zeolite provides, be ratio in 0.9～1.1 scope, preferably 0.95～1.05.
2, the total amount of two kinds of zeolites accounts for 30～60 of solid composite total amount and weighs % in the said highly active catalytic thermal cracking catalyst of the present invention, preferably 35～45 heavy %;
3, highly active ZSM-5 zeolite is by SiO in the said highly active catalytic thermal cracking catalyst of the present invention
2/ Al
2O
3Mol ratio is 15～50, and preferably mol ratio is 18～25 HZSM-5 or NH
4ZSM-5 zeolite, and press P
2O
5The weight ratio of/zeolite 1～10 heavy %, preferably 2～5 heavy % formed at the outer surface of zeolite dipping and through 400～650 ℃ of roastings with phosphorus-containing compound solution in 0.5～4 hour; Preferred roasting condition is 450～600 ℃ of roastings 1～2.5 hour; Described phosphorus-containing compound solution can be the aqueous solution of phosphoric acid, diammonium hydrogen phosphate or ammonium dihydrogen phosphate (ADP).
4, the high activity Y zeolite in the said highly active catalytic thermal cracking catalyst of the present invention is by HY, NH
4Y, REY, REHY, USY or REUSY zeolite, and by total RE
2O
3The weight ratio of/zeolite 10～30 heavy %, preferably 15～25 heavy % formed at the outer surface of zeolite dipping and through 400～650 ℃ of roastings with earth solution in 0.5～4 hour; Preferred roasting condition is 450～600 ℃ of roastings 1～2.5 hour.
5, the alumina base binding agent in the said highly active catalytic thermal cracking catalyst of the present invention carrier is sour molten boehmite and/or aluminium colloidal sol, with Al
2O
3The amount of meter accounts for 5～40 heavy % of solid composite total amount, preferably 15～30 heavy %.
6, the porous silicon compound that contains nickel oxide 0.01～0.5 heavy % of the nickel carbonyl vapour deposition in the said highly active catalytic thermal cracking catalyst of the present invention accounts for 1～20 heavy % of solid composite total amount, preferably accounts for 5～10 heavy % of total amount; The porous silicon compound is selected from one or more in diatomite, expanded perlite, the white carbon.
7, the nickel oxide content on the modified porous silicide of nickel carbonyl vapour deposition is 0.01～0.5 heavy % in the said highly active catalytic thermal cracking catalyst of the present invention carrier, preferably 0.05～0.2 heavy %.
8, said surplus filler clay is kaolin and/or halloysite in the highly active catalytic thermal cracking catalyst carrier of the present invention.
The step of the said highly active catalytic thermal cracking catalyst of preparation the present invention is:
(1), with ZSM-5 zeolite outer surface dipping and the roasting of phosphorus-containing compound solution at mesopore, mensuration micro pore volume;
(2), flood and roasting the mensuration micro pore volume at the Y of macropore outer surface of zeolite with earth solution;
(3), with the nitrogen that carries micro-nickel carbonyl the porous silicon compound is carried out the vapour deposition modification;
(4), with the acidifying deionized water making beating of boehmite with pH 3;
(5), in the ratio that measures the porous silicon compound of kaolin, nickel oxide modification, ZSM-5 zeolite, rare earth exchanged Y zeolite and the aluminium colloidal sol of phosphorous oxides modification are added mixing making beating and spray-dried formation catalyst microspheres.
Highly active catalytic thermal cracking catalyst provided by the present invention, can also be with different charging sequence drying and mouldings in becoming the glue process, both can add first the porous silicon compound of kaolin and nickel oxide modification, sour molten boehmite binding agent adds zeolite slurry again, adds at last aluminium colloidal sol; Also can add first zeolite slurry, then the porous silicon compound making beating that adds successively sour molten boehmite binding agent, kaolin and nickel oxide modification, then add aluminium colloidal sol, obtain the finished product catalytic thermal cracking catalyst through spray drying forming, washing, pneumatic conveying drying again.
The spray drying forming of described slurries adopts conventional method and condition, and general control is 160～260 ℃ at exhaust temperature, and atomisation pressure is to carry out under the condition of 50～60 atmospheric pressures.The spray-dried microballoon catalytic thermal cracking catalyst that is shaped to of said composition, its specific area 〉=130 meter
2/ gram, pore volume are 0.78～0.92 grams per milliliter for 〉=0.22 ml/g, apparent bulk density; 0～40 micron≤18.0 heavy %, 0～149 micron 〉=90.0 heavy %, average grain diameter 65.0～78.0 heavy % in its size distribution; The heavy % in abrasion index≤2.0.
Catalytic thermal cracking catalyst of the present invention mainly is to use at catalytic heat cracking device, compared with prior art, have extra high activity and selectivity, under the reaction condition that relaxes, improved whole conversion capability and the productive rate that has improved the low-carbon alkenes such as ethene, propylene to heavy hydrocarbon charge.
The specific embodiment
The present invention is described further but not thereby limiting the invention for the following examples.
Chemical composition with X-ray fluorescence spectrometry zeolite and catalyst; Adopt nitrogen absorption under low temperature BET method to measure the pore volume of zeolite and catalyst; Adopting pneumatic-weight method to measure catalyst grain size distributes and tear strength; Little activity test is undertaken by the method for ASTM D-3907, and every detection is referring to (" oil and oil product test method national standard " China Standard Press published 1989).
Embodiment 1
With diammonium hydrogen phosphate (chemical pure, the preparation of the Beijing Chemical Plant's reagent) solution of 500 grams, 10 heavy %, (Zibo is created together chemical company and is produced, SiO with restraining the HZSM-5 zeolites by 600 of butt
2/ Al
2O
3Mol ratio 22) mix, 120 ℃ of dryings under 500 ℃ of roastings 2 hours (A), were measured P after 2 hours
2O
5Content 4.5 heavy %, pore volume is 0.15 ml/g.
With the lanthanum nitrate (chemical pure, the preparation of Beijing Chemical Plant's reagent) of 800 grams, 20 heavy %, with 400 gram HY zeolites (production of Chibi, Hubei chemical company, SiO by butt
2/ Al
2O
3Mol ratio 6, Na
2The heavy % of O 0.12) mix, 120 ℃ of dryings under 550 ℃ of roastings 2 hours (B), were measured rare earth oxide 20.2 heavy % after 2 hours, measured 0.225 ml/g of pore volume.
Zeolite mesopore total pore volume/zeolite macropore total pore volume is 1.0.
Carry nickel carbonyl with nitrogen and flow through and process 20 minutes (C) by 200 gram diatomite (originating from the Changbai) vapour depositions of butt, measure nickel take the content of oxide as 0.09 heavy %.
(Shandong Aluminum Plant produces, Al to add 500 gram boehmites in the acid deionized water of 6 liters of pH 3
2O
363 heavy %) making beating is made slurries and is added by kaolin (productions of Kaolin of Suzhou company) 750 grams of butt, above-mentioned (C), (A) and (B) mix and add 1300 after the making beating again and restrain aluminium colloidal sols (production of the large remarkable scientific ﹠ technical corporation of stone, Al
2O
320 heavy %), make microballoon at small size spray drying machine for laboratory after stirring 30 clocks, obtain again the catalyst of embodiment 1 through washing, drying.
220 meters of its specific areas
2/ gram, pore volume is 0.24 ml/g, apparent bulk density is 0.85 grams per milliliter; In the size distribution 0～40 micron account for 17%, 0～149 micron account for 95%, 75 microns of average grain diameters, abrasion index 1.8 heavy %.
Comparative Examples 1
Prepare Comparative Examples 1 by the described method of Chinese patent CN1660967A.
Comparative Examples 2
Prepare Comparative Examples 2 by the described method of Chinese patent CN1221015A.
Comparative Examples 3
Prepare Comparative Examples 3 by the described method of Chinese patent CN1222558A.
Embodiment 2
With ammonium dihydrogen phosphate (ADP) (chemical pure, the preparation of the Beijing Chemical Plant's reagent) solution of 400 grams, 5 heavy %, with 500 gram NH by butt
4ZSM-5 zeolite (create together chemical company and produce, SiO by Zibo
2/ Al
2O
3Mol ratio 19) mix, 120 ℃ of dryings under 550 ℃ of roastings 2 hours (A), were measured P after 2 hours
2O
5Content 2.5 heavy %, pore volume is 0.16 ml/g.
With the cerous nitrate (chemical pure, the preparation of Beijing Chemical Plant's reagent) of 530 grams, 20 heavy %, with 330 gram NH by butt
4(Chibi, Hubei chemical company produces the Y zeolite, SiO
2/ Al
2O
3Mol ratio 5, Na
2The heavy % of O 0.15) mix, 120 ℃ of dryings under 550 ℃ of roastings 2 hours (B), were measured rare earth oxide 16.2 heavy % after 2 hours, measured 0.245 ml/g of pore volume.
Zeolite mesopore total pore volume/zeolite macropore total pore volume is 0.99.
Carry perlite (the Shanghai Celite company) vapour deposition that nickel carbonyl flows through after processing by the acid washing of 150 grams of butt with nitrogen and process 10 minutes (C), measure nickel take the content of oxide as 0.06 heavy %.
(Shandong Aluminum Plant produces, Al to add 500 gram boehmites in the acid deionized water of 6 liters of pH 3
2O
363 heavy %) making beating is made slurries and is added by halloysite (originating from Xiangtan, Hunan Province) 800 grams of butt, above-mentioned (C), (A) and (B) add 1000 gram aluminium colloidal sols (production of the large remarkable scientific ﹠ technical corporation of stone, Al after mixing making beating again
2O
320 heavy %), make microballoon at small size spray drying machine for laboratory after stirring 30 clocks, obtain again the catalyst of embodiment 2 through washing, drying.
160 meters of its specific areas
2/ gram, pore volume is 0.23 ml/g, apparent bulk density is 0.80 grams per milliliter; In the size distribution 0～40 micron account for 14%, 0～149 micron account for 97%, 80 microns of average grain diameters, abrasion index 1.4 heavy %.
Embodiment 3
With phosphoric acid (chemical pure, the preparation of the Beijing Chemical Plant's reagent) solution of 400 grams, 8 heavy %, with 600 gram NH by butt
4ZSM-5 zeolite (create together chemical company and produce, SiO by Zibo
2/ Al
2O
3Mol ratio 25) mix, 120 ℃ of dryings under 480 ℃ of roastings 2.5 hours (A), were measured P after 2 hours
2O
5Content 3.8 heavy %, pore volume is 0.14 ml/g.
With the mixed chlorinated rare earth (originating from the Baotou, the technical grade preparation) of 800 grams, 20 heavy %, with 420 gram USY zeolites (production of Chibi, Hubei chemical company, SiO by butt
2/ Al
2O
3Mol ratio 10, Na
2The heavy % of O 0.10) mix, 120 ℃ of dryings under 580 ℃ of roastings 1 hour (B), were measured rare earth oxide 19.1 heavy % after 2 hours, measured 0.19 ml/g of pore volume.
Zeolite mesopore total pore volume/zeolite macropore total pore volume is 1.05.
Carry nickel carbonyl with nitrogen and flow through and process 15 minutes (C) by 150 gram white carbon (Qingdao Haiyang company) vapour depositions of butt, measure nickel take the content of oxide as 0.07 heavy %.
(Shandong Aluminum Plant produces, Al to add 500 gram boehmites in the acid deionized water of 6 liters of pH 3
2O
363 heavy %) making beating is made slurries and is added by kaolin (Kaolin of Suzhou company) 900 grams of butt, above-mentioned (C), (A) and (B) add 1000 gram aluminium colloidal sols (production of the large remarkable scientific ﹠ technical corporation of stone, Al after mixing making beating again
2O
320 heavy %), make microballoon at small size spray drying machine for laboratory after stirring 30 clocks, obtain again the catalyst of embodiment 3 through washing, drying.
200 meters of its specific areas
2/ gram, pore volume is 0.25 ml/g, apparent bulk density is 0.78 grams per milliliter; In the size distribution 0～40 micron account for 15%, 0～149 micron account for 93%, 70 microns of average grain diameters, abrasion index 1.6 heavy %.
Embodiment 4
Measure embodiment 1～3 and Comparative Examples 1～3 in the micro-activity after 800 ℃/4 hours and 800 ℃/17 hours burin-in process under the 100 heavy % steam, experiment condition is: 480 ℃ of reaction temperatures, oil ratio 3.2, weight (hourly) space velocity (WHSV) 16
-1, catalyst loading amount 5.0g, oil inlet quantity 1.56g, oil-feed time 70s, feedstock oil is the huge port light diesel fuel, sees the following form 1.
The micro-activity of table 1, embodiment 1～3 and Comparative Examples 1～3
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 |
| 800℃/4h | 82 | 80 | 78 | 59 | 74 | 62 |
| 800℃/17h | 64 | 61 | 60 | 49 | 55 | 51 |
Embodiment 5
Measure embodiment 1～3 and Comparative Examples 1～3 after 800 ℃/17 hours burin-in process under the 100 heavy % steam, in little catalytic pyrolysis selective to low-carbon alkene when estimating of instead carrying out of light oil, experiment condition is: 670 ℃ of reaction temperatures, oil ratio 3.2, weight (hourly) space velocity (WHSV) 16
-1, catalyst loading amount 5.0g, oil inlet quantity 1.56g, oil-feed time 70s, feedstock oil is the huge port light diesel fuel, sees the following form 2.
Table 2, embodiment 1～3 and 1～3 pair of selectivity of light olefin of Comparative Examples
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 |
| Ethylene selectivity | 25.0 | 25.1 | 28.0 | 24.8 | 22.5 | 23.4 |
| Propylene Selectivity | 35.3 | 35.2 | 35.6 | 35.1 | 32.1 | 33.9 |
Embodiment 6
Measure embodiment 1～3 and Comparative Examples 1～3 at small fixed flowing bed-tion reacting device, see Table 3.
Table 3, embodiment 1～3 and Comparative Examples 1～3 reaction result
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 |
| Conversion ratio % | 93.6 | 91.9 | 90.5 | 81.0 | 90.2 | 87.1 |
| Cracked gas productive rate % | 70.2 | 69.6 | 68.7 | 55.3 | 69.1 | 65.9 |
| Ethene % | 21.2 | 20.5 | 20.0 | 17.0 | 18.8 | 19.1 |
| Propylene % | 22.9 | 22.6 | 22.0 | 18.7 | 22.0 | 21.5 |
| Ethylene/propene | 0.93 | 0.91 | 0.91 | 0.91 | 0.86 | 0.89 |
Raw material is Daqing vacuum gas oil, 670 ℃ of reaction temperatures, oil ratio 10, weight (hourly) space velocity (WHSV) 10
-1Catalyst is through 800 ℃/17h, 100% steam burin-in process during test.
Embodiment 7
The performance of the Cracking catalyst that embodiment 1 is made when its practical application of cover riser catalytic cracking process units check, the feedstock property of duration of test sees Table 4, and main operating condition sees Table 5, and the characteristic of equilibrium catalyst sees Table 6, and product distributes and sees Table 7.
Table 4, feed properties
| Project | The propylene scheme | The ethene scheme |
| Density (20 ℃), g/cm 3 | 0.9186 | 0.9124 |
| Viscosity (100 ℃), mm 2/s | 26.08 | 30.64 |
| Pour point, ℃ | 36 | 36 |
| Carbon residue, % | 4.9 | 5.8 |
| Content of beary metal, ppm Fe Ni Cu Na | 5.53 6.75 0.0 3.87 | 5.73 6.80 0.12 4.86 |
| Boiling range, ℃ IBP 10% 50% | 294 397 517 | 300 421 519 |
Table 5, main operating condition
| Testing program | The propylene scheme | The ethene scheme |
| Inlet amount, t/h | 9.73 | 5.90 |
| Intermingled dregs ratio, m% | 55 | 56 |
| Reaction pressure, MPa | 0.08 | 0.08 |
| Reaction temperature, ℃ | 576 | 640 |
| Regeneration temperature, ℃ | 720 | 760 |
| Oil ratio | 14.5 | 21.1 |
The characteristic of table 6, equilibrium catalyst
| Project | The propylene scheme | The ethene scheme |
| Micro-activity, % | 63 | 62 |
| Specific surface, m 2/g | 92 | 80 |
| Pore volume, ml/g | 0.20 | 0.19 |
| Apparent bulk density, g/cm 3 | 0.97 | 0.98 |
| Size distribution, v% | ||
| 0～20μm | 2.9 | 1.2 |
| 0～40μm | 20.4 | 17.5 |
| 0～80μm | 72.9 | 70.1 |
| 0～105μm | 88.4 | 86.5 |
| 0～149μm | 97.4 | 96.8 |
| APS，μm | 60.7 | 62.8 |
| Content of beary metal, ppm | ||
| Fe | 2500 | 2700 |
| Ni | 600 | 900 |
| V | 50 | 58 |
Table 7, product distribute
| Project | The propylene scheme | The ethene scheme |
| Dry gas, m% hydrogen, m% ethane m% ethene, m% | 17.64 0.34 4.39 9.77 | 37.13 0.65 9.64 20.37 |
| LPG, m% propane, m% propylene, m% butane, m% butylene, m% | 43.72 3.30 24.60 2.63 13.19 | 28.46 1.78 18.23 0.93 7.52 |
| Cracking naphtha, m% | 17.84 | 14.82 |
| Cracking light oil, m% | 11.75 | 7.93 |
| Coke, m% | 8.41 | 10.66 |
| Loss, m% | 0.64 | 1.00 |
| C 2 ＝+C 3 ＝+C 4 ＝，m％ | 47.56 | 46.12 |
Claims (8)
1. highly active catalytic thermal cracking catalyst, it is characterized by this catalytic thermal cracking catalyst is by the binding agent of highly active phosphorous modified ZSM-5 zeolite, highly active rare earth modified Y zeolite, alumina base, porous silicon compound and a kind of multiple aperture distribution that the filler clay consists of and the solid composite with dissimilar catalytic active center of nickel carbonyl vapour deposition modification, the pore capacities that is wherein provided by the mesopore ZSM-5 zeolite should approach with the pore capacities that is provided by macropore Y zeolite and equate, namely ratio is in 0.9～1.1 scope; The total amount of zeolite accounts for 30～60 heavy % of solid composite total amount; Consist of 5～30 heavy % that the alumina base binding agent accounts for total amount by acidification pseudo-boehmite and/or aluminium colloidal sol; The porous silicon compound that the nickel carbonyl vapour deposition contains nickel oxide 0.01～0.5 heavy % accounts for 1～20 heavy % of total amount; Surplus is the filler clay; The spray-dried microballoon catalytic thermal cracking catalyst that is shaped to of these solid composite slurries.
2. catalyst according to claim 1, it is characterized in that described zeolite component is to be made of highly active ZSM-5 zeolite and two kinds of zeolites of high activity Y zeolite, and should be equated with the pore capacities that is provided by macropore Y zeolite is approaching by the pore capacities that the mesopore ZSM-5 zeolite provides, described ratio is 0.95～1.05.
3. catalyst according to claim 1 is characterized in that the total amount of two kinds of zeolites described in the catalyst accounts for 35～45 heavy % of solid composite total amount.
4. catalyst according to claim 2 is characterized in that described highly active ZSM-5 zeolite is by SiO
2/ Al
2O
3Mol ratio is 18～25 HZSM-5 or NH
4ZSM-5 zeolite is pressed P
2O
5The weight ratio of/zeolite 2～5 heavy % formed by 450～600 ℃ of roastings at outer surface of zeolite dipping and drying with phosphorus-containing compound solution in 1～2.5 hour.
5. catalyst according to claim 2 is characterized in that described highly active Y zeolite is by HY, NH
4Y, REY, REHY, USY or REUSY zeolite are by total RE
2O
3/ zeolite 15～25 heavy % formed by 450～600 ℃ of roastings at outer surface of zeolite dipping and drying with earth solution in 1～2.5 hour.
6. catalyst according to claim 1 is characterized in that in the described alumina base binding agent with Al
2O
3The amount of meter accounts for 15～30 heavy % of solid composite total amount, and it is selected from acidification pseudo-boehmite and/or aluminium colloidal sol.
7. catalyst according to claim 1, it is characterized in that porous silicon compound that described nickel carbonyl vapour deposition contains nickel oxide 0.01～0.5 heavy % accounts for 5～10 heavy % of solid composite total amount, the porous silicon compound is selected one or more in its diatomite, expanded perlite, the white carbon.
8. catalyst according to claim 7 is characterized in that nickel oxide content is 0.05～0.2 heavy % in the porous silicon compound after the described nickel carbonyl vapour deposition modification.
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| US8895790B2 (en) * | 2013-02-12 | 2014-11-25 | Saudi Basic Industries Corporation | Conversion of plastics to olefin and aromatic products |
| CN103084180B (en) * | 2013-02-28 | 2014-08-20 | 中国矿业大学 | Preparation method of supported ultrafine amorphous metal nickel catalyst for realizing catalytic full hydrogenation of aromatic ring |
| CA2925010A1 (en) | 2013-10-15 | 2015-04-23 | Basf Corporation | Mesoporous fcc catalysts with excellent attrition resistance |
| CN104549458B (en) * | 2013-10-23 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of maximum produces ethylene raw hydrocracking catalyst and preparation method thereof |
| CN105642334B (en) * | 2016-01-29 | 2018-06-29 | 山东多友科技有限公司 | A kind of catalytic cracking catalyst for mixing the fine and close oil of refining and preparation method thereof |
| CN109304222B (en) * | 2017-07-28 | 2021-09-28 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst for cracking coking wax oil to produce more liquefied gas and preparation method thereof |
| CN110479361A (en) * | 2019-09-03 | 2019-11-22 | 四川润和催化新材料股份有限公司 | A kind of drop slurry oil and the auxiliary agent of low-carbon olefines high-output and the preparation method and application thereof |
| CN114130424B (en) * | 2020-09-04 | 2023-10-31 | 中国石油化工股份有限公司 | Hydroalkylation catalyst, preparation method and application thereof |
| WO2024069636A1 (en) | 2022-09-27 | 2024-04-04 | Hindustan Petroleum Corporation Limited | A catalyst composition for catalytic cracking of paraffin rich feed into light olefins |
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| CN1222558A (en) * | 1997-10-15 | 1999-07-14 | 中国石油化工集团公司 | Catalyst for catalytic thermal cracking process to prepare lower olefine |
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