CN1298426C - Modified double-component molecular sieve and catalytic cracking catalyst - Google Patents
Modified double-component molecular sieve and catalytic cracking catalyst Download PDFInfo
- Publication number
- CN1298426C CN1298426C CNB031459196A CN03145919A CN1298426C CN 1298426 C CN1298426 C CN 1298426C CN B031459196 A CNB031459196 A CN B031459196A CN 03145919 A CN03145919 A CN 03145919A CN 1298426 C CN1298426 C CN 1298426C
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- double elements
- catalyst
- modification
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 185
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 184
- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000012986 modification Methods 0.000 claims description 39
- 230000004048 modification Effects 0.000 claims description 39
- 238000002425 crystallisation Methods 0.000 claims description 27
- 230000008025 crystallization Effects 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 24
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 22
- 239000004411 aluminium Substances 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 229910021536 Zeolite Inorganic materials 0.000 claims description 15
- 239000010457 zeolite Substances 0.000 claims description 15
- 238000010335 hydrothermal treatment Methods 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000005995 Aluminium silicate Substances 0.000 claims description 8
- 235000012211 aluminium silicate Nutrition 0.000 claims description 8
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- 229910001593 boehmite Inorganic materials 0.000 claims description 7
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001640 fractional crystallisation Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 238000010306 acid treatment Methods 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 14
- 239000003502 gasoline Substances 0.000 abstract description 13
- 208000012839 conversion disease Diseases 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 16
- 238000004231 fluid catalytic cracking Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- 239000002131 composite material Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000006837 decompression Effects 0.000 description 8
- 239000000499 gel Substances 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000012010 growth Effects 0.000 description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- 239000000320 mechanical mixture Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 4
- 230000005496 eutectics Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- -1 4-propyl bromide Chemical compound 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000001282 iso-butane Substances 0.000 description 3
- 235000013847 iso-butane Nutrition 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 230000007115 recruitment Effects 0.000 description 2
- 210000003660 reticulum Anatomy 0.000 description 2
- 210000002966 serum Anatomy 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-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
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 150000003863 ammonium salts Chemical group 0.000 description 1
- 230000003698 anagen phase Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000033001 locomotion Effects 0.000 description 1
- 238000009992 mercerising Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Substances [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- HADKRTWCOYPCPH-UHFFFAOYSA-M trimethylphenylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C1=CC=CC=C1 HADKRTWCOYPCPH-UHFFFAOYSA-M 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a modified bi-component molecular sieve and a catalytic cracking catalyst, wherein the modified bi-component molecular sieve is obtained by modifying the bi-component molecular sieve, and the modified bi-component molecular sieve is obtained by Na in percentage by weight20.1 to 2.5% of O and RE2O30-4% of modified molecular sieve; the catalytic cracking catalyst comprises, by weight, 25-40% of a modified bi-component molecular sieve, 0-10% of a modified Y-type molecular sieve, 30-40% of amorphous silicon-aluminum and 25-35% of a binder. When the catalyst is applied to an FCC process, the yield of rich gas can be increased, and the octane number of gasoline can be improved; compared with the catalyst prepared by adopting the mechanically mixed bi-component molecular sieve, the catalyst has higher hydrothermal stability and can improve the reaction conversion rate, namely compared with the conventional catalyst containing the ZSM-5 molecular sieve, the catalyst has the functions of increasing the yield and the rich gas and improving the octane number of gasoline, and simultaneously has the function of improving the total liquid yield.
Description
Technical field
The present invention relates to a kind of modification double elements molecular sieve and catalytic cracking catalyst, be specially adapted in the FCC technology, the rich gas productive rate is increased, improve octane number simultaneously.
Background technology
The double elements molecular sieve belongs to composite molecular sieve or is referred to as porous road structure molecular screen, and it is a class novel molecular sieve material that grows up recent years.This type of material mainly is to adopt the specific molecule sieve synthetic technology synthetic technology of skill (or be referred to as), rather than use binding agent, to have different pore passage structures, pore-size distribution and acid molecular sieve be grouped together (eutectic, symbiosis, coating or be connected), have the interaction of chemical bond between the different structure, have the duct of intercommunication; The crystal grain possibility random distribution of different structure perhaps forms nucleocapsid structure, thereby obtains the new material of dissimilar molecular sieve performance complementations, and this type of new material has stability preferably.
In fact the eutectic growth of two kinds of molecular sieves is a phenomenon that is known already in molecular sieve is synthetic.The essence that this phenomenon occurs is that development and these molecular sieves that medium helps these molecular sieves is in a kind of metastable state.At nucleation or growth phase, several seeds may occur and develop simultaneously, the final like this generation that causes mixed molecular sieve.The development that these mixtures are general all is according to the OSWALD rule, therefore can predict all these systems and finally develop into stable state after through intermediate state or metastable state; The some time by stopping this reaction, can make mixed molecular sieve isolate out, these mixed molecular sieves all have its clearly form, and all microscope tests and defining of these forms.If crystallization process can develop the sufficiently long time, the metastable state material changes, and has only unique stable state molecular sieve to exist in medium.
In molecular sieve is synthetic, also has a kind of intergrowth phenomenon in addition.It coordinates the growth of variety classes crystal, and molecular sieve B sporadicly appears at the crystallization system of molecular sieve-4 A in this growth course.Microscope can not be found this intergrowth usually, and this sign is the existence of finding molecular sieve B by the fault of construction of microdiffraction research molecular sieve-4 A.The foremost example of this intergrowth phenomenon is exactly that molecular sieve T is produced by the intergrowth of potassium molecular sieve and hair molecular sieve.Because intergrowth has caused the perturbation of composition and hole and duct size, so molecular sieve-4 A B has different character with simple two kinds of molecular sieves.
At present, no matter be eutectic growth or intergrowth, spontaneous mixed molecular sieve also is not suitable for the product of commercial Application, and combined molecular sieve these two kinds of phenomenons that to be people utilize in the molecular sieve growth system, uses some skills and artificial synthetic.The combined molecular sieve of these novelties shows some better industrial application prospect.
U.S. Pat 4,803,185, US4,861,739 disclose a kind of core-shell type molecular sieve with same structure, and its kernel is AlPO-11, and shell is SAPO-11.People such as Pellet adopt the earlier synthetic AlPO-11 molecular sieve of distribution crystallization method, then will synthesize good AlPO-11 molecular sieve and be transferred to another crystallization system, finally synthesize the SAPO-11/AlPO-11 core-shell type molecular sieve.This molecular sieve is used for fluid catalytic cracking (FCC) as octane-enhancing additive, and to compare octane number higher with simple SAPO-11 molecular sieve, and isoparaffin/n-alkane ratio is bigger; Compare with ZSM-5 and to have higher gasoline selective, and isoparaffin/n-alkane ratio is bigger.
U.S. Pat 4,847,224, US 4,946,580 disclose a kind of combined double elements molecular sieve, and its method is that the nucleation gel that will contain the molecular sieve-4 A crystal seed joins and helps in the synthetic fresh gel of molecular sieve B, crystallization under the synthesis condition of molecular sieve B obtains containing the product of two kinds of molecular sieves of AB.Molecular sieve-4 A, B have identical construction unit, and molecular sieve B is enclosed in the outside of molecular sieve-4 A, have the effect of chemical bond between the two, and mechanical property also is improved.A comprises potassium molecular sieve and Ω molecular sieve, and B comprises Ω molecular sieve and mercerising molecular sieve.They and Y molecular sieve or rare earth modified Y molecular sieve are used for catalytic cracking after composite, and the result shows under the suitable situation of conversion ratio, can improve yield of gasoline, and coke yield descends simultaneously.
U.S. Pat 5,888,921, US 5,972, and 205 disclose a kind of sandwich construction, and each layer has the hud typed bimolecular sieve of different structures, acidity and composition.The mentality of designing of this bimolecular sieve is: shell acidity is weak (as ALPO-5), and kernel acidity is strong (ZSM-5).It can be used as additive and uses, and molecule bigger in the Y zeolite product is a little less than the cracking on the shell ALPO-5, and isomerization is strong; And littler molecular energy enters kernel and the short chain isomerization takes place on strong acidic site.This bimolecular sieve is used for fluid catalytic cracking (FCC) as additive, compares with the ALPO-5 molecular sieve, can improve light olefin (C with mechanical mixture ZSM-5
4, C
5) productive rate, and gasoline yield loss is little.
Exxon Chemical Patents Inc. has applied for a series of patents, comprises WO 96-16004, WO97-45384, and US 5,460,796, and US 5,665,325, and US 5,933, patents such as 642.In these patents, by crystallization in a certain proportion of NaOH and template solution bondd the molecular sieve extrudate of silica or the silica binder in the spraying granule, prepared molecular sieve bonding molecular sieve molecular sieve (Zeolite Bound Zeolite), second kind of molecular sieve symbiosis on first kind of molecular sieve, some or all of covering on first kind of molecular sieve, form hud typed structure, can regulate inside and outside different acidity so as required.Reduce surface acidity and can reduce the accessory substance that the non-selective catalysis because of the surface causes.The condition of synthetic this Adhesive-free Molecular Sieve is that first kind and second kind of molecular sieve are molecular sieves of the same type, and perhaps they will mate on crystal structure.It has better intensity and integrality, has overcome the shortcoming of amorphous binding agent.Can be used for hydrocarbon conversion reactions, comprise that the cracking of naphtha, the isomerization of alkylaromatic hydrocarbon, the disproportionation of toluene, transalkylation and alkylation, the naphtha reforming of aromatic hydrocarbons are the oxidation conversion that aromatic hydrocarbons, alkane or alkene are converted into aromatic hydrocarbons and hydrocarbon product.U.S. Pat 5,933 discloses in 642 and has been MFI type molecular sieve inside and outside synthetic, and the kernel silica alumina ratio is 80: 1, and shell is 900: 1, and its selectivity and resistive connection charcoal ability all are improved in disproportionated reaction.
European patent EP 0,293,937 to disclose a kind of serve as deposition bottom and be outer field composite molecular sieve with SAPO-37 with the Y-82 molecular sieve.This composite molecular sieve is earlier the Y-82 molecular sieve to be carried out the ammonium salt exchange, makes its Na
2O reaches certain scope, and handles the molecular sieve surface with TMAH, then mixes crystallization with the SAPO-37 molecular sieve gel that has prepared by a certain percentage and makes.Use it in the catalytic cracking, compare with simple use Y-82 or SAPO-37 molecular sieve and have better gasoline selective, gas still less and coke yield; The arene content of particularly comparing this composite molecular sieve with simple use Y-82 or SAPO-37 molecular sieve is few, simultaneously because of having increased cycloalkane and alkene, thereby the end product octane number is increased.Therefore this molecular sieve is expected to develop a kind of cracking and octane number selectivity bifunctional catalyst.
Introduced a kind of synthetic method of mesoporous-microporous composite molecular sieve in the Chinese patent application 02100452.8 of Petroleum Univ., reaction mixture gel with the synthetic first kind of micro porous molecular sieve of prior art preparation, carry out the phase I crystallization under certain condition, behind the crystallization certain hour, the template agent (perhaps crystal seed) that adds synthetic another kind of micro porous molecular sieve, and the suitable scope of acid-base value to of adjustment reactant mixture, carry out the hydrothermal crystallizing of second stage then at a certain temperature, behind the crystallization certain hour, obtain the combined molecular sieve of this micropore.Above the template agent (perhaps crystal seed) of said another kind of molecular sieve also can before the phase I crystallization or in the crystallization process, add, when synthetic second kind of molecular sieve, also can add and add silicon and aluminum source.
Fluid catalytic cracking (FCC) is because of the octane number height of, clean or white yield height strong to the adaptability of raw material, gasoline, and low, the advantages such as operating condition relaxes relatively, small investment of device pressure rating, is most important secondary operations means in the oil plant always.Especially true in China, the gasoline of China 80% is produced by FCC apparatus according to statistics, and therefore as the core of FCC technology, it is particularly important that the development of FCC catalyst seems.It is reported that present FCC activity of such catalysts component 98% is a Y zeolite,, also have some shape-selective molecular sieves (as ZSM-5 series, beta-molecular sieve etc.) in addition mainly based on rare-earth Y molecular sieve and the high silicon ultra-steady Y molecular sieve of dealuminzation.But different types of molecular sieve is added respectively in catalyst preparation process in the catalyst at present, be fixed among the catalyst particles by binding agent/matrix, in most cases, different zeolite crystals is separate in the catalyst particles, the mass transfer (transmission of reactant/product molecule, motion) of different molecular sieve intergranule must through lying across in during the duct of binding agent/matrix could realize.In this course, the reaction that is taken place is unmanageable (or even some unwanted side reactions).In this case, realize effects such as shape selective catalysis, function catalysis collaborative between the variety classes molecular sieve, efficient is lower.People such as T.F.Degnan once reported, ZSM-5 and Y zeolite do not find to have between them synergy to exist respectively in same catalyst granules the time.And the composite molecular sieve material is the molecular sieve that has two or more among a particle, promptly at the dissimilar molecular sieve eutectic growths of granule interior or interconnect in some way, and the duct is interconnected.Will help mass transfer and synergy between different apertures and the acid molecular sieve that distributes like this.
In publication of publishing and patent documentation, do not find modification, and be prepared into the report that is used for FCC technology behind the catalyst the combined double elements molecular sieve of Y/ZSM-5.
Summary of the invention
The object of the present invention is to provide a kind of modification double elements molecular sieve and catalytic cracking catalyst, this combined double elements molecular sieve shows good stable after handling through modified technique; If this molecular sieve is made catalytic cracking catalyst to be applied in the FCC technology, the rich gas productive rate is increased, improve octane number simultaneously; Double elements molecular sieve than mechanical mixture shows than high hydrothermal stability, can improve reaction conversion ratio, promptly compare with the catalyst that routine contains the ZSM-5 molecular sieve, catalyst of the present invention removes the volume increase rich gas, improves the function of octane number, has simultaneously and improves the effect that total liquid is received.
The present invention has introduced a kind of modification double elements molecular sieve and has comprised the catalyst of this modification double elements molecular sieve.
A kind of modification double elements molecular sieve is meant the double elements molecular sieve handled through modification to obtain, by weight percentage, and Na
2O is 0.1～2.5%, RE
2O
3It is 0～4% modified molecular screen; Wherein the double elements molecular sieve is a micropore double elements molecular sieve, is by fractional crystallization, synthetic Y zeolite, and then will contain that the method for synthetic another micro porous molecular sieve of mixed liquor of Y molecular sieve makes.
Described wherein another micro porous molecular sieve is ZSM-5 preferably, and the X-ray diffraction peak of double elements molecular sieve comprises the diffraction maximum of Y and two kinds of molecular sieves of ZSM-5 at this moment.
Double elements molecular sieve of the present invention is meant by fractional crystallization, utilizes the zeolite mixed liquor that contains of synthetic faujasites to synthesize micropore double elements molecular sieve.As introducing in the Chinese patent 02100452.8 that University of Petroleum applied for, obtain: in a reactor, prepare Y zeolite earlier or claim faujasite, the template agent (perhaps crystal seed) that adds synthetic another kind of micro porous molecular sieve (as ZSM-5) then, and the acid-base value of adjustment reactant mixture is to pH=9.0～12.0 (preferred pH=9.5～11.5), 120～240 ℃ of following intensification crystallization 2～96 hours, obtain the double elements molecular sieve then.Above the template agent (perhaps crystal seed) of said another kind of molecular sieve also can before the phase I crystallization or in the crystallization process, add, when synthesizing second kind of molecular sieve, its silicon and aluminum source can be fully from the reactant mixture of first kind of molecular sieve, also can add to add silicon and aluminum source.The aluminium source can be aluminum sulfate, sodium aluminate, aluminium hydroxide, boehmite etc.; The silicon source can be sodium metasilicate, Ludox, silica gel, white carbon etc.; The template agent is: ethanol, isopropyl alcohol, primary amine (ethamine, n-propylamine, n-butylamine etc.) secondary amine (dipropylamine, dibutylamine etc.) and quaternary ammonium salt (tetraethylammonium bromide, 4-propyl bromide, TBAB etc.) and composition thereof or their hydroxide (alkali); Crystal seed is ZSM-4, ZSM-5, ZSM-11 molecular sieve powder (its silica alumina ratio is 30,50,500 etc., perhaps pure silicon ZSM-5), β zeolite powder etc.In other words, the double elements molecular sieve that utilizes Chinese patent application 02100452.8 to obtain all can satisfy among the present invention the requirement to the double elements molecular sieve.
Do not limit the modification processing method of double elements molecular sieve among the present invention, through Na after the modification
2O is 0.1～2.5%, RE
2O
3Be 0～4% to get final product, Na particularly
2O is 0.3～1.5%, RE
2O
3Be 0～3% o'clock better.
1), with containing H the modified technique of general molecular sieve mainly comprises two kinds of processing procedures:
+, NH
4 +Or and RE
3+The exchange solution-treated; 2), hydrothermal treatment consists.These two kinds of processes can adopt once combination, also can adopt repeatedly combination, preferably adopt the combination modified technique of twice exchange and twice hydrothermal treatment consists among the present invention.Concrete grammar can be: earlier with containing H
+, NH
4 +Or and RE
3+The exchange solution-treated, after the filtration, carry out hydrothermal treatment consists one time; Again with containing H
+, NH
4 +The exchange solution-treated, carry out hydrothermal treatment consists again one time.
The present invention is preferably with containing H
+, NH
4 +Or and RE
3+The condition of exchange solution-treated be:
H
+=0.0001～0.01mol/L, NH
4 +Concentration expressed in percentage by weight is 2～15%, carries out when rare earth modified, and the RE3+ concentration expressed in percentage by weight of use is 0.01～1.0%, and system temperature is 40～100 ℃, and molecular sieve is 1: 6～14 with the ratio of solution weight, and the solution-treated time is 0.5～2 hour.
Anion is to be selected from Cl in the exchange solution
-, SO
4 2-, NO
3 -And CO
3 2-In one or more.
The condition of the preferred hydrothermal treatment consists of the present invention is: water-flowing amount is 100～400mL/h, 550～650 ℃ of temperature, time 1～3h.
Comparing of modification double elements molecular sieve of the present invention with traditional Modified Zeolite Y, the two groups of this modification
Unit's molecular sieve shows good stable.
The present invention also provides a kind of catalyst that comprises this modification double elements molecular sieve.
A kind of catalyst that contains modification double elements molecular sieve is a benchmark with the percentage by weight of catalyst, and modification double elements molecular sieve accounts for 25～40%, Modified Zeolite Y accounts for 0～10%, amorphous silicon aluminium accounts for 30～40%, binding agent accounts for 25～35%.Consist of preferably wherein that modification double elements molecular sieve accounts for 28～36%, Modified Zeolite Y accounts for 0～8%, amorphous silicon aluminium accounts for 33～37%, binding agent accounts for 30～35%.
The used amorphous silicon aluminium of catalyst that contains modification double elements molecular sieve of the present invention is preferably kaolin or modified kaolin, binding agent is preferably one or both in aluminium colloidal sol, acid treatment boehmite, the Ludox, and Modified Zeolite Y is preferably the REY molecular sieve.
The method for preparing catalyst that contains modification double elements molecular sieve of the present invention is not limited, can adopt common preparation method to get final product, can be as the preparation method for after modification double elements molecular sieve equimolecular sieve and amorphous silicon aluminium are ground respectively, mix and make it with binding agent and stir, oven dry, roasting promptly gets catalyst.
When the catalyst that contains modification double elements molecular sieve of the present invention is applied to FCC technology, the rich gas productive rate is increased, improve octane number simultaneously; Catalyst than the double elements molecular sieve that adopts mechanical mixture is made shows higher catalyst hydrothermal stability.
Catalyst of the present invention is that the FCC technology of Xinjiang decompression long distillate wax oil and Xinjiang decompression residuum can make the rich gas productive rate increase by 0.5～4 unit being used for feedstock oil, and wherein the increase of propylene and iso-butane accounts for more than 70% of total rich gas recruitment; Octane number increases by 1～2 unit in the gasoline.
Description of drawings
Fig. 1 is the X-ray diffraction peak figure of used double elements molecular sieve in the embodiment of the invention 2, can observe out the diffraction maximum that comprises Y and two kinds of molecular sieves of ZSM-5 in its X-ray diffraction peak.
The specific embodiment
The invention will be further described below by embodiment.
1. the specifications of raw materials of using in embodiment, the Comparative Examples is:
(1), NaY: industrial goods, degree of crystallinity ≯ 90, SiO2/Al2O3 ≯ 4.8;
(2), ZSM-5: industrial goods, degree of crystallinity ≯ 85, SiO2/Al2O3 ≯ 300;
(3), NH
4Cl salt: industrial goods, analyze pure;
(4), earth solution: industrial goods, RE
2O
3=197g/l;
(5) kaolin: Suzhou kaolin company;
(6) aluminium colloidal sol: Lanzhou catalyst plant;
(7) boehmite: Shandong boehmite company;
(8) molecular sieve REY: Lanzhou catalyst plant;
(9) the fixed fluidized bed evaluation feedstock oil of catalyst is Xinjiang decompression wide fraction wax oil and Xinjiang decompression residuum, and character sees Table 7.
2. the physicochemical property evaluation method of molecular sieve, catalyst is as shown in table 6, and wherein x-ray diffraction (XRD) adopts D/MAX-3C type X-ray diffractometer to analyze.
3. evaluating catalyst method:
(1) micro fixed-bed reactor.Appreciation condition: the 5g catalyst of packing under 460 ℃ of reaction temperatures, feeds 1.56g huge port light diesel fuel (No. 0 standard diesel oil) and carries out cracking reaction, oil ratio 3.21, air speed 16h in the 70s
-1
(2) fixed fluidized bed, earlier fresh catalyst was worn out 10 hours with 100% steam at 800 ℃ before measuring.Feedstock oil is Xinjiang decompression wide fraction wax oil and Xinjiang decompression residuum, and blending residual oil ratio is 30% (mass percent).500 ℃ of reaction temperatures, catalystoil ratio are 3.75, catalyst charge weight 150g, oil inlet quantity 40g, air speed 16h
-1
Embodiment 1
The method preparation for preparing the NaY directed agents that is proposed in the U.S. Pat 3,639,009 is adopted in the preparation of directed agents, and it is as follows specifically to fill a prescription: 15SiO
2: Al
2O
3: 16Na
2O: 320H
2O (mol ratio).
At first prepare the double elements molecular sieve: (wt% refers to percentage by weight, and is as follows)
17.30 gram waterglass with deionized water 13.46 gram dilutions, are under agitation added 50wt% 18 water aluminum sulfate hydrate solution 1.31 grams then successively, directed agents 3.89 grams, low alkali sodium aluminate (solution (Al
2O
3Be 16.2wt%, Na
2O is 12.3wt%) 5.25 grams and 3.77 sulfuric acid solutions that restrain 3 mol are made into gel, stir the reactor of after 30 minutes gel being put into 100 milliliters of inner liner polytetrafluoroethylenes in 100 ℃ of crystallization 24 hours, after the cooling, add tetraethylammonium bromide 0.68 gram and 4-propyl bromide 1.06 grams, stirred 10 minutes, transfer mixed serum pH values with sulfuric acid solution 6.20 gram of 3 mol then, stir on 30 minutes bonnets reactor in 140 ℃ of crystallization 40 hours.After reaction finishes, product after filtration, washing, dry combined double elements molecular sieve-4 A.This double elements molecular sieve-4 A identifies to have ZSM-5 characteristic peak and NaY characteristic peak, no P type stray crystal through XRD.
Getting 100 gram (butt) molecular sieve-4 As pours into 800 milliliters of exchange solution (NH that contain 8.05wt% is housed
4Cl salt) in the swap tank, at 90 ℃ of exchange 1h, control solution PH=3.3～3.7 simultaneously in exchange process, filter the exchange back, washing; Behind 600 ℃ of following roasting 2h, calcining matter poured into 800 milliliters of exchange solution (NH that contain 5.88wt% are housed
4Cl salt) in the swap tank, at 90 ℃ of exchange 1h, and control solution PH=3.3～3.7 in exchange process, filter the exchange back, and washing at 600 ℃ of following roasting 2h, makes modification double elements molecular sieve-4 A 1 of the present invention.The rerum natura of molecular sieve-4 A 1 sees Table 1.
Comparative Examples 1
In the ratio of NaY and ZSM-5 in the molecular sieve-4 A among the embodiment 1, take by weighing NaY, ZSM-5 molecular sieve and the amorphous silicon aluminium material that total amount is 100g (butt) and make it mechanical mixture even, obtain molecular sieve B.
Adopt the method for modifying of embodiment 1 that molecular sieve B is handled, make modified molecular screen B1.
Table 1 has been listed the physicochemical property of modified molecular screen A1, B1, and before and after 800 ℃, 100% steam, 4 hours are aging, (5,5 in the molecular sieve X-ray diffractogram, 5) variation of peak height, therefrom the degree of crystallinity retention rate height (being good stability) of combined as can be seen double elements molecular sieve.
The physicochemical property of table 1 modified molecular screen A1 and modified molecular screen B1 relatively
| Project | Embodiment 1 | Comparative Examples 1 |
| A1 | B1 | |
| (5,5,5) peak height, mm | 82 | 76 |
| (5,5,5) peak height (800 ℃, 100% steam, 4h), mm | 50 | 38 |
| The degree of crystallinity retention rate, % | 60.98 | 50.00 |
| Na 2O m％ | 0.48 | 0.48 |
Embodiment 2
The directed agents preparation is with embodiment 1.
15.81 gram waterglass with deionized water 13.94 gram dilutions, are under agitation added 50wt% 18 water aluminum sulfate hydrate solution 1.31 grams then successively, directed agents 4.32 grams, low alkali aluminium acid sodium solution (Al
2O
3Be 16.2wt%, Na
2O is 12.3wt%) 6.30 grams and 3.79 sulfuric acid solutions that restrain 3 mol are made into gel, stir the reactor of after 30 minutes gel being put into 100 milliliters of inner liner polytetrafluoroethylenes in 100 ℃ of crystallization 24 hours, after the cooling, the 1wt% that presses butt adds the ZSM-5 crystal seed, stirred 20 minutes, transfer mixed serum pH value with sulfuric acid solution 6.25 grams of 3 mol then, stir on 30 minutes bonnets reactor in 160 ℃ of crystallization 24 hours, after reaction finishes, product after filtration, washing, dry combined double elements molecular sieve-4 A '.This double elements molecular sieve-4 A ' identify to have ZSM-5 characteristic peak and NaY characteristic peak through XRD, as shown in Figure 1.
Get the molecular sieve-4 A that 100 grams make among (butt) embodiment 1 ', pour into 1100 milliliters of exchange solution (NH that contain 4.31wt% be housed
4Cl salt and 0.19wt%RE
2O
3) swap tank in, at 90 ℃ of exchange 1h, in exchange process, control simultaneously solution PH=3.3～3.7, filter the exchange back, washing behind 600 ℃ of following roasting 2h, is poured calcining matter into 1100 milliliters of exchange solution (NH that contain 3.33wt% is housed
4(the NH of Cl salt and 5.0wt%
4)
2SO
4Salt) in the swap tank, at 90 ℃ of exchange 1h, and control solution PH=3.3～3.7 in exchange process, filter the exchange back, and washing at 600 ℃ of following roasting 2h, makes modification double elements molecular sieve-4 A 2 of the present invention.The rerum natura of molecular sieve-4 A 2 sees Table 2, RE
2O
3Be 1.29m%.
Comparative Examples 2
Get 100 gram (butt) industrial NaY molecular sieves, press the method for modifying of embodiment 2 described molecular sieves and handle, make modified molecular screen C1.
Comparative Examples 3
In the ratio of NaY and ZSM-5 in the molecular sieve-4 A among the embodiment 1, take by weighing total amount and be NaY and the ZSM-5 molecular sieve of 100g (butt) and make it mechanical mixture even, obtain molecular sieve D.Press the method for modifying of embodiment 2 described molecular sieves and handle, make modified molecular screen D1.
Table 2 has been listed modified molecular screen A2, C1, the character of D1 and the degree of crystallinity retention rate data before and after the different molecular sieve modification processing, therefrom also can reflect combined double elements molecular sieve good stable, and Na exchanges easily in the molecular sieve.
The physicochemical property contrast of the different modified molecular screens of table 2
| Project | Embodiment 2 | Comparative Examples 2 | Comparative Examples 3 |
| A2 | C1 | D1 | |
| Degree of crystallinity retention rate % | 63.60 | 60.87 | 61.17 |
| Na 2O m％ | 0.37 | 0.66 | 0.45 |
Embodiment 3
Resulting modified molecular screen A1 (butt) 35g prepares catalyst among the employing embodiment 1.Percentage by weight with catalyst is benchmark (as follows), and molecular sieve-4 A 1 accounts for 35%, kaolin accounts for 50%, aluminium colloidal sol accounts for 15%.Its preparation method is for after grinding molecular sieve and kaolin respectively, mixes and make it stirring with aluminium colloidal sol, dries down at 120 ℃, makes 20～40 purpose granules after 2 hours through 600 ℃ of roastings again, promptly gets catalyst H1 of the present invention.Adopt micro fixed-bed reactor that catalyst is estimated.Table 3 has been listed catalyst H1 through 800 ℃, the activity change after 100% steam, different time wear out.
Embodiment 4
Resulting modified molecular screen A2 (butt) 1000g prepares catalyst among the employing embodiment 2.Molecular sieve-4 A 2 proportions are 35% in the catalyst, also have 35% kaolin, 20% acidification pseudo-boehmite, 10% aluminium sol adhesive in addition in the catalyst.Its preparation method fully mixes kaolin and boehmite for elder generation, and after carrying out acidification, fully mixes with molecular sieve and binding agent again, makes 40～130 purpose particles by spray thing drying at last, promptly gets catalyst H2 of the present invention.Adopt and fixed fluidized bed catalyst is estimated.Table 4 has been listed the selectivity of catalyst H2.
Embodiment 5
Adopt that prepared modified molecular screen A2 (butt) 1000g and high activity molecular sieve REY carries out composite (compound proportion is 5: 1) among the embodiment 2, the molecular sieve proportion in catalyst after composite is 35%, and all the other are formed with embodiment 4.Adopt the method for embodiment 4 to prepare catalyst, promptly make catalyst H3 of the present invention.Adopt and fixed fluidized bed catalyst is estimated.
Table 5 has been listed the selectivity of catalyst H3 and catalyst before and after 800 ℃, 100% steam, 10 hours are aging, (5,3,3) the peak retention rate in the X-ray diffractogram.
Comparative Examples 4
Replace modified molecular screen A1 with resulting modified molecular screen B1 in the Comparative Examples 1, be prepared into catalyst K1 by composition, the method for embodiment 3.Adopt micro fixed-bed reactor that catalyst is estimated.Table 3 has been listed catalyst H1 and K1 through 800 ℃, the activity change after 100% steam, 4 hours and 10 hours are aging.
The micro-activity of table 3 catalyst after different time is aging changes
| Project | Embodiment 3 | Comparative Examples 4 |
| H1 | K1 | |
| Micro-activity (800 ℃, 100% steam, 4 hours), % | 65 | 63 |
| Micro-activity (800 ℃, 100% steam, 10 hours), % | 60 | 55 |
Comparative Examples 5
Replace modified molecular screen A2 with resulting modified molecular screen C1 in the Comparative Examples 2, be prepared into catalyst K2 by composition, the method for embodiment 4.Adopt the fixed fluidized bed catalyst selectivity evaluation of carrying out.Table 4 has contrasted the selectivity of catalyst H2 and K2.
The selectivity contrast of table 4 different catalysts
| Project | Embodiment 4 | Comparative Examples 5 | |
| H2 | K2 | ||
| Dry gas m% | 1.82 | 1.66 | |
| Rich gas m% | 21.34 | 18.49 | |
| Rich gas is formed | Propylene m% | 5.89 | 4.98 |
| Iso-butane m% | 6.77 | 5.68 | |
| Other m% | 8.68 | 7.83 | |
| Gasoline m% | 50.24 | 51.43 | |
| Diesel oil m% | 15.14 | 15.54 | |
| Heavy oil m% | 5.10 | 5.21 | |
| Coke m% | 5.83 | 5.75 | |
| Conversion ratio m% | 79.23 | 77.33 | |
| The character of gasoline | N-P | 3.69 | 3.79 |
| I-P | 33.96 | 32.52 | |
| O | 26.10 | 24.32 | |
| N | 9.22 | 8.18 | |
| A | 27.03 | 31.18 | |
| RON | 93.2 | 91.2 | |
As can be seen from Table 4, adopt the catalyst H2 that contains modification double elements molecular sieve-4 A 2 of the present invention, can make 1～2 unit of octane number rising, the rich gas productive rate significantly rises simultaneously, and wherein the increase of propylene and iso-butane accounts for more than 70% of total rich gas recruitment.
Comparative Examples 6
Replace modified molecular screen A2 with modified molecular screen D1 prepared in the Comparative Examples 3, be prepared into catalyst K3 by composition, the method for embodiment 5.Adopt and fixed fluidized bed catalyst is estimated.
Table 5 has contrasted the selectivity of catalyst H3 and K3 and catalyst through 800 ℃, before and after 100% steam, 10 hours are aging, and (5,3,3) the peak retention rate in the X-ray diffractogram.
The selectivity contrast of table 5 different catalysts
| Project | Embodiment 5 | Comparative Examples 6 | |
| H3 | K3 | ||
| (5,3,3) peak retention rate (8000C, 100% steam 10h) mm | 54 | 40 | |
| Dry gas m% | 2.27 | 2.32 | |
| Rich gas m% | 17.69 | 17.28 | |
| Gasoline m% | 46.41 | 41.38 | |
| Diesel oil m% | 18.27 | 19.46 | |
| Heavy oil m% | 7.10 | 11.51 | |
| Coke m% | 7.18 | 7.34 | |
| Total liquid is received m% | 82.37 | 78.12 | |
| Conversion ratio m% | 73.55 | 68.32 | |
| The character of gasoline | N-P | 4.47 | 4.56 |
| I-P | 38.27 | 32.74 | |
| O | 17.03 | 18.62 | |
| N | 8.10 | 7.47 | |
| A | 32.13 | 36.22 | |
| MON | 82.7 | 82.7 | |
| RON | 95.6 | 95.5 | |
From the evaluation result of table 5 as seen, compare with the catalyst that adopts the preparation of mechanical mixture molecular sieve, the catalyst that contains the double elements molecular sieve, its rich gas productive rate and octane number be no significant difference, but total liquid is received significantly increase, and the heavy oil transformation rate increases simultaneously, thereby this result improves relevant with the higher reaction conversion ratio of catalyst that makes of composite molecular screen stability, this point also can the retention rate situation of (5,3, the 3) peak height the X-ray diffractogram obtain proof after both steam are handled.
Main analysis and assessment method that table 6 the present invention relates to
| Project | Method | Standard No. |
| Y molecular sieve degree of crystallinity | X-ray diffraction method | Q/SH018·0172-93 |
| Na 2O | Flame spectrometry | Q/SH018·0144-91 |
| RE 2O 3 | Colorimetric method | Q/SH018·0175-93 |
| Catalyst activity | The microreactor method | Q/SH0180846 |
| Catalyst selectivity | The small fixed flowing bed method | Q/SH018·0516-91 |
| Octane number | Chromatography | Q/SH018·0133-90 |
Table 7 catalyst selectivity is evaluated raw materials used oil nature
| Project | Xinjiang decompression wide fraction wax oil | Xinjiang decompression residuum | |
| Carbon residue m% | 0.285 | 9.76 | |
| Elementary analysis | N m％ | 0.054 | 0.57 |
| C m％ | 86.82 | 86.71 | |
| H m％ | 13.16 | 12.17 | |
| Heavy metal is analyzed | Cuμg/g | 0.14 | 0.87 |
| Pbμg/g | 0.15 | 0.89 | |
| Feμg/g | 8.90 | 21.55 | |
| Niμg/g | 0.58 | 26.64 | |
| Vμg/g | 0.22 | 4.67 | |
| PONA analysis | Saturated hydrocarbons m% | 86.7 | 45.7 |
| Aromatic hydrocarbons m% | 12.8 | 47.3 | |
| Colloid m% | 0.5 | 5.7 | |
| Molecular weight | 323 | 882 | |
Claims (14)
1. modification double elements molecular sieve is meant that the double elements molecular sieve is handled through modification to obtain, by weight percentage, and Na
2O is 0.1～2.5%, RE
2O
3It is 0～4% modified molecular screen; Wherein the double elements molecular sieve is a micropore double elements molecular sieve, be by fractional crystallization, earlier synthetic Y zeolite, and then in containing the mixed liquor of Y molecular sieve, add template agent or the crystal seed that synthesizes ZSM-5, and the acid-base value of adjustment reactant mixture, crystallization obtains again; The silicon source of synthetic ZSM-5 and aluminium source be fully from the reactant mixture of first kind of molecular sieve, or add silicon source, aluminium source again.
2. modification double elements molecular sieve according to claim 1, it is characterized in that the double elements molecular sieve is by prepare Y zeolite earlier in a reactor, the template agent or the crystal seed that add synthetic ZSM-5 then, and the acid-base value of adjusting reactant mixture to pH be 9.0～12.0, obtained in 2～96 hours 120～240 ℃ of following intensification crystallization then.
3. modification double elements molecular sieve according to claim 2, it is characterized in that the double elements molecular sieve is by adding the synthetic required silicon of Y zeolite source, aluminium source and directed agents earlier in a reactor, mixing the back obtains high-crystallinity 90～120 ℃ of following crystallization 10～48 hours Y zeolite; The template agent or the crystal seed that add ZSM-5 then, and the acid-base value of adjusting reactant mixture with phosphoric acid obtained 120～240 ℃ of following intensification crystallization then to pH=9.0～12.0 in 2～96 hours.
4. modification double elements molecular sieve according to claim 1, it is characterized in that the double elements molecular sieve is by adding the synthetic required silicon of Y zeolite source, aluminium source and directed agents earlier in a reactor, mixing the back obtains high-crystallinity 90～120 ℃ of following crystallization 10～48 hours Y zeolite; And then the synthetic ZSM-5 of crystallization; And the template agent of ZSM-5 or crystal seed are to add before the phase I crystallization or in the crystallization process.
5. modification double elements molecular sieve according to claim 1, the silicon source that it is characterized in that the double elements molecular sieve be in sodium metasilicate, Ludox, silica gel, the white carbon one or more.
6. modification double elements molecular sieve according to claim 1, the aluminium source that it is characterized in that the double elements molecular sieve be in aluminum sulfate, sodium aluminate, aluminium hydroxide, the boehmite one or more.
7. modification double elements molecular sieve according to claim 1 is characterized in that making the used template agent of double elements molecular sieve and is: ethanol, isopropyl alcohol, primary amine, secondary amine and quaternary ammonium salt and composition thereof or their hydroxide.
8. according to described any one the modification double elements molecular sieve of claim 1 to 7, the modification that it is characterized in that the double elements molecular sieve is handled and is meant the combination modified technique that adopts twice exchange and twice hydrothermal treatment consists: earlier with containing H
+, NH
4 +Or and RE
3+The exchange solution-treated, after the filtration, carry out hydrothermal treatment consists one time, again with containing H
+, NH
4+The exchange solution-treated, carry out hydrothermal treatment consists again one time.
9. modification double elements molecular sieve according to claim 8 is characterized in that twice exchange of double elements molecular sieve institute warp and the modification processing procedure of twice hydrothermal treatment consists are:
(1). with containing H
+, NH
4 +Or and RE
3+Exchange solution-treated double elements molecular sieve, system temperature is 40～100 ℃, the solution-treated time is 0.5～2 hour;
(2) carry out hydrothermal treatment consists, 550～650 ℃ of temperature, 1～3 hour time;
(3) with containing H
+, NH
4 +The exchange solution-treated, system temperature is 40～100 ℃, the solution-treated time is 0.5～2 hour;
(4) carry out hydrothermal treatment consists again one time, the first time, hydrothermal treatment consists was the condition of (2) to its treatment conditions together.
10. catalytic cracking catalyst that includes the described modification double elements of claim 1 molecular sieve, it is characterized in that the percentage by weight with catalyst is a benchmark, modification double elements molecular sieve accounts for 25～40%, Modified Zeolite Y accounts for 0～10%, amorphous silicon aluminium accounts for 30～40%, binding agent accounts for 25～35%.
11. catalytic cracking catalyst according to claim 10, it is characterized in that the percentage by weight with catalyst is a benchmark, modification double elements molecular sieve accounts for 28～36%, Modified Zeolite Y accounts for 0～8%, amorphous silicon aluminium accounts for 33～37%, binding agent accounts for 30～35%.
12., it is characterized in that amorphous silicon aluminium is kaolin or modified kaolin according to claim 10 or 11 described catalytic cracking catalysts.
13., it is characterized in that binding agent is one or both in aluminium colloidal sol, acid treatment boehmite, the Ludox according to claim 10 or 11 described catalytic cracking catalysts.
14., it is characterized in that Modified Zeolite Y is the REY molecular sieve according to claim 10 or 11 described catalytic cracking catalysts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031459196A CN1298426C (en) | 2003-07-17 | 2003-07-17 | Modified double-component molecular sieve and catalytic cracking catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031459196A CN1298426C (en) | 2003-07-17 | 2003-07-17 | Modified double-component molecular sieve and catalytic cracking catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1570030A CN1570030A (en) | 2005-01-26 |
| CN1298426C true CN1298426C (en) | 2007-02-07 |
Family
ID=34471551
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031459196A Expired - Fee Related CN1298426C (en) | 2003-07-17 | 2003-07-17 | Modified double-component molecular sieve and catalytic cracking catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1298426C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104014359B (en) * | 2014-06-04 | 2016-03-16 | 湛江天成投资有限公司 | A kind of preparation method of cracking catalyst for petroleum hydrocarbon |
| CN108745410B (en) * | 2018-06-11 | 2021-01-22 | 山东多友科技有限公司 | Preparation method of phosphorus-containing hierarchical pore ZSM-5/Y composite molecular sieve |
| CN113816394A (en) * | 2020-06-19 | 2021-12-21 | 中国科学院大连化学物理研究所 | Synthesis method of ZSM-5/ZSM-11 cocrystallized molecular sieve |
| CN115055205A (en) * | 2022-05-20 | 2022-09-16 | 大连理工大学 | Synthesis of ZSM-5/Y composite molecular sieve and preparation method of heavy oil catalytic cracking catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0230005A2 (en) * | 1985-12-23 | 1987-07-29 | W.R. Grace & Co.-Conn. | Cracking catalyst |
| EP0293937A2 (en) * | 1987-06-04 | 1988-12-07 | Uop | Microporous crystalline composite compositions and processes for making them |
| CN1393403A (en) * | 2001-06-29 | 2003-01-29 | 中国石油天然气股份有限公司 | Fractional crystallization synthesis method of medium-micropore composite molecular sieve composition |
| CN1393404A (en) * | 2001-06-29 | 2003-01-29 | 中国石油天然气股份有限公司 | Synthesis method of medium-micropore composite molecular sieve composition |
-
2003
- 2003-07-17 CN CNB031459196A patent/CN1298426C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0230005A2 (en) * | 1985-12-23 | 1987-07-29 | W.R. Grace & Co.-Conn. | Cracking catalyst |
| EP0293937A2 (en) * | 1987-06-04 | 1988-12-07 | Uop | Microporous crystalline composite compositions and processes for making them |
| CN1393403A (en) * | 2001-06-29 | 2003-01-29 | 中国石油天然气股份有限公司 | Fractional crystallization synthesis method of medium-micropore composite molecular sieve composition |
| CN1393404A (en) * | 2001-06-29 | 2003-01-29 | 中国石油天然气股份有限公司 | Synthesis method of medium-micropore composite molecular sieve composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1570030A (en) | 2005-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102822124B (en) | Method for making a catalyst comprising a phosphorus modified zeolite to be used in a MTO process | |
| CN100450617C (en) | Kaolin-based composite molecular sieve and preparation method thereof | |
| CN110523428B (en) | Catalytic cracking catalyst containing NaY molecular sieve composite material and preparation method thereof | |
| CN102372277B (en) | Preparation method of binder-free ZSM-5/beta coexisting molecular sieve | |
| CN1194891C (en) | Combined molecular sieve and preparation method thereof | |
| CN1957070A (en) | Catalyst compositions comprising metal phosphate bound zeolite and methods of using same to catalytically crack hydrocarbons | |
| CN101767034B (en) | Preparation method of catalysis material containing ZSM-5/Y type composite molecular sieve | |
| KR20070121811A (en) | A cracking catalyst and its preparation | |
| CN1611299A (en) | MFI structure molecular sieve containing phosphor and metal component and its use | |
| CN101618333B (en) | Y/silicate compound molecular sieve and method for preparing same | |
| WO2011090121A1 (en) | Catalyst for use in production of monocyclic aromatic hydrocarbon, and process for production of monocyclic aromatic hydrocarbon | |
| CN100522812C (en) | Method for preparing ZSM-5/mercerization zeolite symbiosis molecular screen | |
| CN104437613A (en) | Binderless ZSM-5/beta symbiotic molecular sieve catalyst and preparation method thereof | |
| CN104437611A (en) | Binderless nano ZSM-5/beta symbiotic zeolite molecular sieve catalyst | |
| CN106830003A (en) | SSZ-13/SCM-9 composite molecular screens and its synthetic method | |
| CN1049406C (en) | Phosphorus and RE containing molecular sieve with MFI structure | |
| CN101585546B (en) | Composite zeolite molecular sieve preparing method containing Y and Beta zeolite structures | |
| CN101348260B (en) | Preparation of binderless MFI/FAU composite zeolite molecular sieve | |
| CN102050466B (en) | Method for in-suit synthesis of Y-type molecular sieve by taking silicon-aluminum as base material | |
| CN1298426C (en) | Modified double-component molecular sieve and catalytic cracking catalyst | |
| CN1232862A (en) | All-white clay catalyst for fluid catalytic cracking and its preparation | |
| CN1099788A (en) | Cracking catalyst of rich producing olefines | |
| CN107955639A (en) | The method of six alkane cracking of carbon | |
| CN102464334B (en) | Method for preparing mordenite/ZSM-5 composite molecular sieve | |
| CN102050465B (en) | Method for preparing Y-type molecular sieve through solid-phase in-situ synthesis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070207 Termination date: 20210717 |