CN100443407C - High silicon aluminium ratio small crystal NaY molecular sieve - Google Patents
High silicon aluminium ratio small crystal NaY molecular sieve Download PDFInfo
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- CN100443407C CN100443407C CNB2004100971079A CN200410097107A CN100443407C CN 100443407 C CN100443407 C CN 100443407C CN B2004100971079 A CNB2004100971079 A CN B2004100971079A CN 200410097107 A CN200410097107 A CN 200410097107A CN 100443407 C CN100443407 C CN 100443407C
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- molecular sieve
- nay molecular
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 84
- 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 84
- 239000013078 crystal Substances 0.000 title claims abstract description 59
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000010703 silicon Substances 0.000 title claims abstract description 54
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 54
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 48
- 239000004411 aluminium Substances 0.000 title claims description 47
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 76
- 238000002425 crystallisation Methods 0.000 claims abstract description 63
- 230000008025 crystallization Effects 0.000 claims abstract description 63
- 239000011541 reaction mixture Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000002360 preparation method Methods 0.000 claims abstract description 29
- 230000003068 static effect Effects 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 18
- 230000032683 aging Effects 0.000 claims description 17
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 15
- 238000003483 aging Methods 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 105
- 238000000034 method Methods 0.000 abstract description 52
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 51
- 239000000377 silicon dioxide Substances 0.000 abstract description 48
- 239000002994 raw material Substances 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000010457 zeolite Substances 0.000 description 42
- 229910021536 Zeolite Inorganic materials 0.000 description 40
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 35
- 239000011734 sodium Substances 0.000 description 29
- 239000000243 solution Substances 0.000 description 26
- 239000000499 gel Substances 0.000 description 24
- 229910052708 sodium Inorganic materials 0.000 description 18
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 16
- 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 15
- 235000019353 potassium silicate Nutrition 0.000 description 15
- 235000011121 sodium hydroxide Nutrition 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 230000002194 synthesizing effect Effects 0.000 description 9
- 238000010792 warming Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000007796 conventional method Methods 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 238000012856 packing Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- -1 preparation method Substances 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000009415 formwork Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000012163 sequencing technique Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 230000000295 complement effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229940037003 alum Drugs 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 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 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229910016523 CuKa Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 101000777220 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 3 Proteins 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 102100031287 Ubiquitin carboxyl-terminal hydrolase 3 Human genes 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 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 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229940070337 ammonium silicofluoride Drugs 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The present invention provides a NaY molecular sieve with high silicon-aluminum ratio and small crystal grain. The Raney silica-alumina ratio of the NaY molecular sieve, specifically the molar ratio of SiO2 to Al2O3 is within the range from 6.0 to 7.0, and the average crystal grain is within the range from 300 to 800 nm. The NaY molecular sieve can be prepared with the method of direct synthesis by non-template agents, and has the following specific steps: crystallized guiding agents are prepared after the non-template agents are agitated at the temperature of 15 to 60 DEG C and aged for 0.5 to 48 hours in advance, reaction mixture is then prepared from the guiding agents, water, silicon sources and aluminum sources, and the reaction mixture is crystallized in two steps after being agitated uniformly. The first step comprises dynamic crystallization, and the second step comprises static crystallization. The NaY molecular sieve with high silicon-aluminum ratio and small crystal grain, which has the relative crystallinity higher than 80%, is prepared after the processes of filtration, washing and drying. The molecular sieve has the advantages of favorable structural stability, good catalytic activity, easy raw material sources for the preparation method, no environment pollution and wide industrial application perspective.
Description
Technical field
The present invention relates to a kind of high silicon aluminium ratio small crystal NaY molecular sieve, particularly a kind of direct synthetic high silicon aluminium ratio small crystal NaY molecular sieve.
Background technology
Y zeolite is as catalyst activity constituent element or support of the catalyst and be widely used in the oil refining process such as catalytic cracking, hydrocracking and isomerization.Ordinary method synthetic Y zeolite generally has the grain-size about 1000nm.The Y zeolite of little grain-size is owing to have bigger outer surface area and higher intracrystalline rate of diffusion, at aspects such as secondary cracking that improves the macromole ability that transforms, minimizing product and the cokings of reduction catalyzer, show the performance more more superior than the Y zeolite of conventional grain-size, but for the FCC catalyzer, because working conditions and regeneration condition are very harsh, are not that the particle diameter of molecular sieve is the smaller the better.The molecular sieve particle diameter is more little, and its thermostability, hydrothermal stability are poor more, and the stabilizing active of catalyzer is low more, is difficult to adapt to the reaction and the aging condition of FCC apparatus harshness.For the close NaY molecular sieve of degree of crystallinity, its structural stability mainly is subjected to the influence of particle diameter and two factors of framework si-al ratio.Structural stability reduces and reduces with particle diameter, improves along with the raising of silica alumina ratio, and be both coefficient results.Want to produce existing good activity and product selectivity, again the FCC catalyzer of higher stabilizing active arranged, the particle diameter of molecular sieve should be controlled within certain scope, should have higher silica alumina ratio simultaneously.
Silica alumina ratio (the SiO of Y zeolite
2/ Al
2O
3Mol ratio) ratio with cracking/hydrogen transfer activity has direct relation, improves framework si-al ratio, rationally reduces Al center density, improves the relative intensity in acid site, helps to change the ratio of cracking/hydrogen transfer activity, reduces catalysis Jiao's generation.Because the molecular sieve of high silica alumina ratio has good hydrothermal stability and thermostability, can bear reaction-regeneration condition harsh in the catalytic cracking process, and the cracking selectivity is better in addition, coke yield is lower, is suitable for the catalytic cracking of heavy oil.
With the silica alumina ratio of ordinary method synthetic Y zeolite about 5.0.Be high-Si Y-type molecular sieve [describing] with silica alumina ratio greater than 6.0 at present as USP4714601.High silica alumina ratio Y type (USY the is referred to as super steady Y) molecular sieve current, that the active component of the catalyst for cracking heavy oil of widespread use generally adopts the method for aftertreatments such as dealuminzation or dealumination complement silicon to make, lattice constant 24.50 to
About.Preparation USY zeolite mainly adopts the post treatment method of NaY molecular sieve, comprising: high temperature hydrothermal method [USP3449370], high temperature gas-phase reaction method [USP4701313, USP4297335, USP4438178, DE3132380], ammonium silicofluoride liquid phase reaction method [catalysis journal, 1993,14 (4): 300-306] and organic complexing agent facture [USP4093560] etc.Though these methods respectively have superiority, and some uses industrial, but all exist deficiency, and these methods all are at first synthetic common NaY molecular sieves, adopt various chemistry or physical method to carry out dealuminzation then, or dealumination complement silicon promptly " secondary is synthetic " improve silica alumina ratio, have that preparation process is numerous and diverse, the zeolite crystallinity loss is big, a preparation technology's flow process more complicated, shortcoming such as yield is low and environmental pollution is serious.Prepare the deficiency that the high silica alumina ratio Y zeolite can remedy aforesaid method to a certain extent by direct synthetic method.
Direct synthesis technique is meant the method that need not pass through aftertreatment, but " once synthetic " directly prepares the high silica alumina ratio Y zeolite.As everyone knows, prepare specific zeolite and need consider many factors, for example: the preparation of the composition of reaction mixture, preparation method, reactant source, directed agents, whether stir, gel potential of hydrogen, crystallization condition etc.Usually when the preparation y-type zeolite, silica alumina ratio is low more, easy more preparation, and silica alumina ratio is high more, and condition is harsh more, difficult more preparation.Directly the method for synthesizing high-silicon aluminum ratio NaY molecular sieve mainly comprises in the invention disclosed patent: a kind of is to add the quaternary ammonium salt of carbon one to carbon four in gel, organic formwork agent synthesizing Si-Als such as quaternary ammonium hydroxide are than the high silica alumina ratio faujusite [USP5549881 between 6.0-30.0, USP5116590, USP4965059, USP4931267, USP4714601, EP0887310, CN1145278, CN1226875], or in gel, add crown ether such as 15-crown ether-5, hexaoxacyclooctadecane-6-6 or its mixture are as organic formwork agent synthesizing high-silicon aluminum ratio faujusite [Zeolites, 1990; 10:546-552, Zeolites, 1992; 12:160-166.], silica alumina ratio with the Y zeolite of organic formwork agent method preparation is higher, but its cost height, raw materials used very expensive as TPAOH or 15-crown ether-5 price, need long crystallization time generally to need more than 7 days, the cost of synthesis of molecular sieve obviously improves like this, is unfavorable for industrial application.Another kind is that U.S. Pat P4333859, USP4309313 propose to add the directed agents that cesium salt makes as inorganic template and conventional method in reaction gel, between the silica alumina ratios 5.0～7.0 such as synthetic faujasites CSZ-1, CSZ-3.But the cesium ion in this kind method product is difficult for removing, and need repeatedly exchange and roasting [describing as USP4714601], and crystal seed must adopt specific method for preparing.In addition, the silica alumina ratio of raw material requires up to 65～135 when feeding intake, but the utilization ratio of silicon is lower, and the silicon waste liquid of a large amount of high densitys is discharged from.Therefore the direct synthesizing high-silicon aluminum ratio of any template Y zeolite is not used in research, is one and well selects.
During the direct synthesizing high-silicon aluminum ratio of non-template agent method Y zeolite, promptly in gel, do not add template, but by changing silicon source or aluminium source, adjust the proportioning of silicon source, aluminium source, alkali, water in the reactant gel, adjust crystallization condition simultaneously, and the preparation method of directed agents or crystal seed, thereby improve the silica alumina ratio of synthetic y-type zeolite.
Breck thinks (USP3,130,007) with comparatively cheap silicon source such as water glass, silica gel, silicic acid etc., and difficulty makes the high silica alumina ratio Y zeolite.
Japanese Patent clear 61091013 prepares the crystal seed of y-type zeolite in advance, this crystal seed is joined by a certain percentage make the faujusite of silica alumina ratio than higher (5.2-6.0) in the reactant gel then.They are at used raw material: white carbon black or silica gel is as the silicon source, sodium aluminate, sodium hydroxide and distilled water.Silicon source wherein be water-soluble or drying regime all to require the particle diameter of silicon be more than the 8mu, preferably more than the 15mu.Concrete preparation process is: with aluminum oxide, sodium oxide and distilled water heating for dissolving are mixed with certain density sodium aluminate solution, this solution slowly is added dropwise in sodium hydroxide solution and the distilled water, add an amount of Y type crystal seed again, after mixing, this mixed solution slowly is added drop-wise in white carbon black or the silica gel with suction pipe, stir fast and generate the homogeneous gel, then this gel was positioned in 25 ℃ the water-bath ageing 3～24 hours, change over to again in the reactor temperature be 100 ℃ of following crystallization 5～20 days to form crystal, filter, washing, 110 ℃ made down silica alumina ratio in dry several hours is 5.5～6.0 Y zeolite.
Utilized the mother liquor after crystallization finishes in the Russ P (RuP2090502), and the crystal seed that in reaction mixture, adds 2～5wt% to prepare silica alumina ratio be 5.5～7.5 NaY molecular sieve.Its preparation process is: earlier mother liquor is mixed, adds sodium metaaluminate, distilled water and sodium hydroxide then with silicon source (silica gel or white carbon black or silicon sol), the add-on of each raw material should satisfy prescription: (2.4～3.0) Na
2O: Al
2O
3: (10～12) SiO
2: (250～300) H
2The requirement of O, the crystal seed that adds 2～5wt% after evenly more to be mixed stirred after ten minutes, with mixture gel crystallization 36～72 hours under 95～100 ℃ temperature, filter (mother liquor is stand-by), washing, dry must product.
Synthetic method report about small crystal grain NaY molecular sieve is more, concludes to get up to mainly contain:
1 improve the basicity of NaY when synthetic, add directed agents (USP3,755,538).Crystal grain diameter with this method is 0.06 micron, and lattice constant is 2.466 nanometers, and silica alumina ratio is 5.1.
2 by control directed agents digestion time, and factors such as temperature are improved crystal seed, preparation small crystal grain NaY molecular sieve (KR8601-488B).
3 add dispersion medium.As add methyl alcohol, ethanol, dimethyl sulfoxide (DMSO), and left and rightly revolve sugar etc. can to make crystal grain diameter as dispersion medium be 0.01～0.1 micron X, Y-type small crystal grain molecular sieve (USP3,516,786; EP0,041,338);
4 by improving processing condition, becomes glue as low temperature, stirs for a long time at a high speed, and modes such as micro-wave energy heating make small-grain Y-type, X-type, and ZSM-5 equimolecular sieve (GB1,223,592; USP4,587,115; USP4,778,666; CN1238305; CN1238306).
(CN1033503C) such as horse allosaurus adopts the transparent liquid phase directed agents of transmittance＞75% to prepare the method for small crystal grain NaY molecular sieve.Its preparation process is: prepare the conventional directed agents of transmittance＜30% at first according to a conventional method, sodium silicate solution is joined in the conventional directed agents of transmittance＜30% then, make a kind of mole and consist of (12～180) Na
2O: Al
2O
3: (17～210) SiO
2: (160～3100) H
2The transparent directed agents solution of O transmittance＞75%, it is synthetic then water glass, transparent guide agent, alum liquor and low alkali aluminium acid sodium solution to be carried out the NaY hydro-thermal according to the preparation method of conventional NaY molecular sieve, and wherein the add-on of transparent guide agent is 0.5～25% (with the total Al of system
2O
3The mole number meter), stirred 0.5～2 hour, be warming up to 95～100 ℃, crystallization 5～35 hours, filter, drying makes the small crystal grain NaY molecular sieve product that mean grain size is about 200 nanometers.
Albers etc. (USP3755538) have reported, add a certain amount of B in directed agents, V, and P, Mo, Co, Ge and Ga element the crystallization time of NaY is shortened, and grain fineness number are reduced to 100～300 nanometers.
Many documents had also once been reported and be added into a certain amount of organic substance in synthetic systems, and the grain fineness number of the molecular sieve that is finally synthesized is reduced.Bodart etc. (J.Chim.Phys., 1986,83:777) reported that the Y zeolite that synthesizes has the grain-size of 800 nanometers and 500 nanometers respectively before and after the interpolation tetramethyl ammonium chloride.Maher (USP3516786) is when synthetic, before synthetic system intensification crystallization steps, the organic solvent that adding on a small quantity can be miscible with water in synthetic system, as: dimethyl sulfone, N, dinethylformamide, tetrahydrofuran (THF), methyl alcohol, ethanol, acetone etc., final zeolite crystal is of a size of 10～100 nanometers.But organic solvent is easy to volatilization under the condition of hydrothermal crystallizing, and in order to reduce the organic solvent volatilization that heats up and bring, Ambs etc. (USP4372931) have used glucose, and final grain-size is 35～69 nanometers.Xu Xing medium (CN1113814C) adds the synthetic crystal grain grain of organic dispersion mediums such as glycerol, ethylene glycol, Virahol through the small crystal grain NaY molecular sieve in 300～600 nanometers in directed agents.
Chao Zisheng etc. in patent CN1238305A, CN1238306A, CN1354133A, reported respectively in reaction gel, add rare earth ion, with aluminium form stable comple organic complexing agent, form the synthetic average grain size of method of oil, tensio-active agent and cosurfactant of water-in-oil (W/O) less than the Y zeolite of 300 nanometers with silica-alumina gel.
Yang Xiaoming etc. will not contain directed agents in patent CN1081425A silica-alumina gel was 80～180 ℃ of pre-crystallization 1～10 hour, be cooled to room temperature and add directed agents again, making crystal grain in 5～25 hours 90～100 ℃ of continuation crystallization then is that 100～500 nanometers, silica alumina ratio are about 5.0 small crystal grain NaY molecular sieve.They also in patent CN1160676A with the silicon of conventional directed agents whole silicon source as synthetic material, be mixed with the NaY zeolite product that crystal grain is 100～500 nanometers, silica alumina ratio about 5.0 with the acidifying aluminum salt solution,
The common feature that adopts above several method synthetic small crystal grain NaY molecular sieve is that the silica alumina ratio of product is lower, is fit to the Y zeolite of synthetic X type molecular sieve and silica alumina ratio＜5.8.
Summary of the invention
The purpose of this invention is to provide a kind of with low cost, technology is simple, direct synthetic high silicon aluminium ratio small crystal NaY molecular sieve.
A kind of high silicon aluminium ratio small crystal NaY molecular sieve provided by the present invention, the framework si-al ratio that it is characterized in that the NaY molecular sieve is SiO
2/ Al
2O
3Mol ratio is between 6.0～6.5, and average crystal grain is between 400～600nm.
See that from disclosed document report SiO is not also arranged
2/ Al
2O
3Mol ratio is between 6.0～6.5, and the high silicon aluminium ratio small crystal NaY molecular sieve of average crystal grain between 400～600nm, and this kind molecular sieve is compared conventional Y zeolite and had better structural stability and catalytic activity.
Molecular sieve of the present invention preferably uses direct synthesis technique to obtain, and promptly need not carry out chemistry or physical method carries out dealuminzation to the synthetic molecular sieve that obtains, or dealumination complement silicon is that secondary synthesizes and improves silica alumina ratio.In direct synthesis technique, do not use template in preferred synthesizing.
Preferred molecular sieve of the present invention is to use following direct synthesis technique: first preparation directed agents, the refabrication reaction mixture is after crystallization, filtration, washing, drying and obtain high silicon aluminium ratio small crystal NaY molecular sieve.
Directed agents can be according to (6～30) Na with silicon source, aluminium source, alkali lye and water
2O: Al
2O
3: (6～30) SiO
2: (100～460) H
2The mixed in molar ratio of O after stirring, is descended to stir ageings 0.5～48 hour and is made at 15～60 ℃ mixture.
Reaction mixture can be by (0.5～6) Na
2O: Al
2O
3: (8～30) SiO
2: (100～460) H
2Total molar ratio of O adds entry, silicon source, aluminium source, directed agents under 15～80 ℃, wherein the add-on of directed agents accounts for 1%～50% of reaction mixture weight percent, and the acidity-basicity ph value of control reaction mixture makes 11.0～13.5.
Crystallization preferably adopts two step crystallization, and promptly reaction mixture is through two step crystallization, and the first step is carried out dynamic crystallization: temperature is controlled at 20～80 ℃, and crystallization time is 0.5～24 hour; Second step was carried out static crystallization then: temperature is controlled at 90～140 ℃, and crystallization time is 5～100 hours.
A kind of method for preparing high silicon aluminium ratio small crystal NaY molecular sieve provided by the invention is:
(1) preparation directed agents: silicon source, aluminium source, alkali lye and water are fed intake according to certain proportioning, and ratio range is (6～30) Na
2O: Al
2O
3: (6～30) SiO
2: (100～460) H
2O after stirring, stirs ageing with mixture down at 15～60 ℃ and made directed agents in 0.5～48 hour.
(2) preparation feedback mixture: by (0.5～6) Na
2O: Al
2O
3: (8～30) SiO
2: (100～460) H
2Total molar ratio of O, under 15～80 ℃ of quick stirring condition, add entry, silicon source, aluminium source, directed agents, wherein the add-on in the directed agents accounts for 1%～50% of reaction mixture weight percent, and control reaction mixture acidity-basicity ph value is 11.0～13.5.
(3) synthesizing high-silicon aluminum ratio small crystal grain NaY molecular sieve: with the reaction mixture of step (2) gained crystallization in two steps, the first step is carried out dynamic crystallization: temperature is controlled at 20～80 ℃, and crystallization time is 0.5～24 hour; Second step was carried out static crystallization then: temperature is controlled at 90～140 ℃, and crystallization time is 5～100 hours, after crystallization is finished, more after filtration, washing, drying, makes product.
According to method provided by the present invention, in reaction mixture, do not add any template or additive, only add 1～50% the directed agents account for the reaction mixture weight percent, cost is low.
Method provided by the present invention prepares the directed agents mixture with silicon source, aluminium source, water, alkali lye by proportioning, and its mole ratio range is (6～30) Na
2O: Al
2O
3: (6～30) SiO
2: (100～460) H
2O, wherein the silicon source is a water glass, and the aluminium source is a sodium metaaluminate, and alkali lye is sodium hydroxide solution, after stirring, carries out ageing.
Method provided by the present invention is characterized in that said preparation directed agents is to stir ageing 0.5～48 hour down at 15～60 ℃ in the step (1), preferably stirs ageing down at 15～40 ℃ and makes directed agents in 2～24 hours.The method for preparing directed agents provided by the present invention is different from the directed agents of the synthetic NaY molecular sieve of conventional method, also be different from the method for preparing directed agents among the patent CN1033503C, conventional method is that the ageing under the immobilized condition of directed agents mixture is obtained directed agents when synthesizing the NaY molecular sieve, and preparation directed agents of the present invention is at 15～60 ℃, preferably stirs ageing down at 15～40 ℃ and makes directed agents.
Method provided by the present invention when it is characterized in that in the step (2) said preparation feedback mixture, adds entry, silicon source, aluminium source, directed agents under 40～80 ℃ of quick stirring condition.
Method provided by the present invention, when it is characterized in that the preparation feedback mixture, the adding mode of water, silicon source, aluminium source, directed agents is not emphasized sequencing.Can add entry earlier, stir fast and add silicon source and aluminium source down simultaneously, back adding directed agents stirs, also can under stirring fast, feed intake by the sequencing according to water, aluminium source, silicon source, directed agents, perhaps the sequencing according to water, silicon source, aluminium source, directed agents feeds intake under stirring fast, and perhaps the sequencing according to silicon source, water, directed agents, aluminium source feeds intake under stirring fast.
Method provided by the present invention, it is characterized in that the add-on in the directed agents accounts for 1%～50% of reaction mixture weight percent, and by control directed agents amount come the acidity-basicity ph value of conditioned reaction mixture 11.0～13.5, optimum between 11.5～13.0, do not need to add in addition the potential of hydrogen that gel is regulated in acid.When conventional method prepares the reaction mixture of NaY molecular sieve, add more directed agents often, generally with Al in the system
2O
3The mole number meter adds 1～50% directed agents, adds certain density acid then and comes the acidity-basicity ph value of conditioned reaction mixture about 13.0.The basicity when synthetic, the method for adding directed agents prepare small crystal grain NaY molecular sieve such as USP3 by improving to also have some, and the NaY zeolite crystal diameter of 755,538 described preparations is 0.06 micron, and silica alumina ratio is 5.1.
Method provided by the present invention, its feature are also that with final reaction mixture crystallization in two steps the first step is carried out the dynamic crystallization and the second step static crystallization.The first step dynamic crystallization be meant to reaction mixture carry out physically dynamically, as with agitator to the stirring of reaction mixture or to the vibration of reaction mixture etc.; The second step static crystallization is meant and stops the vibration of reaction mixture or stop the stirring of agitator to reaction mixture, reaction mixture is carried out static crystallization.
Method provided by the present invention, its feature are that also the temperature of the first step dynamic crystallization is controlled at 20～80 ℃, and optimum is at 40～80 ℃, and crystallization time is 0.5～24 hour, and optimum is 1～12 hour; The second step static crystallization: temperature is controlled at 90～140 ℃, and optimum is at 90～120 ℃, and crystallization time is 5～100 hours, and optimum is 10～96 hours, more after filtration, washing, drying, makes the high silicon aluminium ratio small crystal NaY molecular sieve product.
Reaction mixture refers to and comprises water, silicon source, aluminium source and directed agents and potential of hydrogen suitable mixture among the present invention.Wherein water is deionized water or distilled water; The silicon source is one or more mixtures in water glass, silicon sol, silica gel, the white carbon black; The aluminium source is one or more mixtures in sodium metaaluminate, Tai-Ace S 150, aluminum chloride, aluminum nitrate, aluminium hydroxide, the pseudo-boehmite.
Method provided by the present invention is characterized in that crystallization time is short, only needs 5～124 hours, optimum 10～80 hours.Though and patent USP5549881, USP511659, USP4965059, USP4931267, USP4714601, EP0887310, CN96108159, CN97196809 etc. in gel, add organic formwork agent can synthesizing Si-Al than more than 6.0, but need long crystallization time generally to need more than 7 days, the cost of synthesis of molecular sieve improves like this, is unfavorable for industrial application.
Method provided by the present invention is characterized in that additionally adding template or additive, raw materials used inexpensive, be easy to get simple for processly, help reducing the manufacturing cost of NaY.
High silicon aluminium ratio small crystal NaY molecular sieve of the present invention makes molecular sieve compare conventional Y zeolite and has better structural stability and catalytic activity owing to have higher silica alumina ratio and big or small suitable grain-size.
Description of drawings
The XRD figure of Fig. 1 embodiment 1
The SEM figure of Fig. 2 embodiment 1
The size distribution of Fig. 3 embodiment 1
The XRD figure of Fig. 4 Comparative Examples 1
The SEM figure of Fig. 5 Comparative Examples 1
The size distribution of Fig. 6 Comparative Examples 1
Embodiment
For the present invention is described better, further specify the present invention below in conjunction with embodiment and Comparative Examples, but scope of the present invention is not limited only to these embodiment.
In each embodiment and Comparative Examples, the mensuration of acidity-basicity ph value adopts the pHB-4 type pH meter that Shanghai Precision Scientific Apparatus Co., Ltd produces in the reaction mixture, the relative crystallinity of the NaY molecular sieve that synthesizes and the mensuration of silica alumina ratio are with SIMADU XRD6000 type X-ray diffractometer, experiment condition is: the CuKa radiation, pipe is pressed 40kv, tube current 40mA.Its measuring method is measured according to SH/T 0340-92 standard method and (is seen " standard of chemical industry compilation ", China Standard Press, published in 2000), the mensuration of silica alumina ratio is (to see " standard of chemical industry compilation " by SH/T 0339-92 standard method, China Standard Press published in 2000) measure and according to following formula:
Calculate the lattice constant a of NaY molecular sieve.
Then according to the Breck-Flanigen formula:
SiO
2/Al
2O
3＝2(25.858-a)/(a-24.191)
Calculate NaY molecular sieve silica alumina ratio; The specific surface of molecular sieve low temperature N
2Determination of adsorption method (GB/T5816-1995), instrument model are ASAP2020M; The globule size of molecular sieve is measured nano particle size and the Zeta potential analyser that adopts Britain Ma Erwen Instr Ltd. to produce, and model is Zetasizer Nano ZS; The mensuration of the lattice avalanche temperature of molecular sieve is to adopt differential thermal analyzer, and model is Universal V2.5H TA.
Get 10.53g sodium hydrate solid (Beijing Chemical Plant produce, purity is 99%) and be dissolved in the 30.95g water, be cooled to room temperature after, (Tianjin, Tianjin fine chemistry industry institute of section produces, Al to add sodium metaaluminate 2.22g
2O
3Content is 45wt%, Na
2O content is 41wt%) make high alkali deflection aluminium acid sodium solution.(Red Star water glass plant in Beijing produces, SiO to add 36.73g water glass then in high alkali deflection aluminium acid sodium solution
2Content is 28.83wt%, Na
2O content is 8.84wt%), mix the back and made directed agents in 4 hours 40 ℃ of stirring ageings.
14.21g water is positioned in the beaker, and fluid temperature is 60 ℃ in the control beaker, stirs the Al that adds 12.79g50wt% down simultaneously fast
2(SO
4)
3(Nan Zhao China prosperous chemical industry company limited produces, and purity is 99%) solution and 31.91g water glass.After stirring, add above-mentioned directed agents 1.90g, the pH value of gel is 12.5, after stirring, in its stainless steel cauldron of packing into, stirred crystallization 6 hours at 60 ℃, be warming up to 100 ℃ of static crystallizations then 60 hours, and filtered then, wash, dry NaY zeolite product.It is 6.3 that XRD records its silica alumina ratio, and relative crystallinity is 90% (Fig. 1), and average grain size is 505 nanometers (Fig. 2,3), and the BET specific surface area is 742m
2/ g.
NaY zeolite product to gained carries out modification and catalytically active assessment.
The NaY zeolite product of getting gained according to a conventional method with (NH
4)
2SO
4Solution carries out ion-exchange, HY is made in roasting.With the HY sample 750 ℃ of 100% steam-treated 2 hours.The relative crystallinity of XRD determining HY and the crystallization reservation degree after the hydrothermal treatment consists, the results are shown in Table 3.
The NaY zeolite product of getting gained passes through and (NH according to a conventional method
4)
2SO
4USY is made in solion exchange, 500 ℃ 100% steam-treated down.The relative crystallinity of XRD determining USY, the results are shown in Table 3.
After USY molecular sieve after the modification and a certain amount of water mixed, press the prescription of catalyzer again: molecular sieve (in base) 35wt%, matrix Suzhou kaolin (butt) 50wt%, aluminium colloidal sol (in aluminum oxide) 15wt%, the kaolin, the aluminium collosol adhesive that add metering, after stirring with high speed agitator, put into 120 ℃ of baking ovens dry 4 hours, move in the retort furnace 540 ℃ of roastings 4 hours then, pulverize and get 40-60 order particle and handle at 800 ℃ of 100% steam aging and obtained catalyst sample in 4 hours.
The 5.00g catalyst sample is placed in the micro fixed-bed reactor, under 500 ℃ of temperature of reaction, grand celebration heavy oil (subtracting slag by the 30wt% grand celebration mixes with the 70wt% wax oil) is carried out cracking reaction.The reaction evaluating data are listed in table 3.
Embodiment 2
The preparation of each raw material sources and directed agents is with embodiment 1.
With the beaker constant temperature that 13.47g water is housed is 50 ℃, stirs the Al that adds 12.66g 50wt% down simultaneously fast
2(SO
4)
3Solution and 31.55g water glass after stirring, add above-mentioned directed agents 4.40g, and the pH value of gel is 12.8.The interior material of beaker remains at 50 ℃ in the said process.After stirring, in its stainless steel cauldron of packing into,, be warming up to 100 ℃ of static crystallizations then 36 hours, filter then, wash, dry NaY zeolite product 60 ℃ of vibration crystallization 4 hours.
The silica alumina ratio that XRD records the NaY zeolite product is 6.2, and relative crystallinity is 98%, and average grain size is 488 nanometers, and the BET specific surface area is 750m
2/ g.
Embodiment 3
The preparation of each raw material sources and directed agents is with embodiment 1.
With the beaker constant temperature that 14.21g water is housed is 60 ℃, stirs the Al that adds 12.79g 50wt% down simultaneously fast
2(SO
4)
3Solution and 31.91g water glass after stirring, add above-mentioned directed agents 4.31g, and the pH value of gel is 12.8.The interior material of beaker remains at 60 ℃ in the said process.After stirring, in its stainless steel cauldron of packing into, stirred crystallization 4 hours, be warming up to 100 ℃ of static crystallizations then 36 hours, filter then, wash, dry NaY zeolite product at 60 ℃.
The silica alumina ratio that XRD records the NaY zeolite product is 6.3, and relative crystallinity is 98%, and average grain size is 510 nanometers, and the BET specific surface area is 743m
2/ g.
Embodiment 4
Each raw material sources is with embodiment 1.
Get the 16.91g sodium hydrate solid and be dissolved in the 46.46g water, be cooled to room temperature after, add sodium metaaluminate 2.22g and make high alkali deflection aluminium acid sodium solution.In high alkali deflection aluminium acid sodium solution, add 16.32g water glass then, mix the back and made opaque emulsus gel sample directed agents in 4 hours 40 ℃ of dynamic ageings.
To 60 ℃ of the beaker constant temperature of 142.1g water be housed, stir the Al that adds 127.9g 50wt% down simultaneously fast
2(SO
4)
3Solution and 319.1g water glass after stirring, add above-mentioned directed agents 16.6g, and the pH value of gel is 12.6.The interior material of beaker remains at 60 ℃ in the said process.After stirring, in its stainless steel cauldron of packing into, stirred crystallization 6 hours, be warming up to 100 ℃ of static crystallizations then 48 hours, filter then, wash, dry NaY zeolite product at 60 ℃.Recording its silica alumina ratio is 6.1, and relative crystallinity is 90%, and average grain size is 505 nanometers, and the BET specific surface area is 742m
2/ g.
The preparation of each raw material sources and directed agents is with embodiment 1.
To 60 ℃ of the beaker constant temperature of 13.47g water be housed, stir the AlCl that adds 12.41g 30wt% down simultaneously fast
3(Tian Jinshisu village chemical reagent factory produces, content 97%) solution adds 31.56g water glass then, after stirring, adds above-mentioned directed agents 2.16g, and the pH value of gel is 12.4.The interior material of beaker remains at 60 ℃ in the said process.After stirring, in its stainless steel cauldron of packing into, stirred crystallization 6 hours, be warming up to 100 ℃ of static crystallizations then 72 hours, filter then, wash, dry NaY zeolite product at 60 ℃.Recording its silica alumina ratio is 6.5, and relative crystallinity is 86%, and average grain size is 600 nanometers, and the BET specific surface area is 733m
2/ g.
Embodiment 6
The preparation of each raw material sources and directed agents is with embodiment 1.
17.48g water is positioned in the beaker, and fluid temperature is 60 ℃ in the control beaker, stirs the Al that adds 12.79g50wt% down simultaneously fast
2(SO
4)
3Solution and 30.24g water glass.After stirring, add above-mentioned directed agents 1.54g, the pH value of gel is 12.2, after stirring, in its stainless steel cauldron of packing into, 60 ℃ of dynamic crystallizations 6 hours, be warming up to 100 ℃ of static crystallizations then 76 hours, and filtered then, wash, dry NaY zeolite product.It is 6.8 that XRD records its silica alumina ratio, and relative crystallinity is 91%, and average grain size is 515 nanometers, and the BET specific surface area is 752m
2/ g.
Comparative Examples 1
Adopt ordinary method to prepare the NaY molecular sieve, each raw material sources is with embodiment 1.
Get the 153g sodium hydrate solid and be dissolved in the 279g deionized water, be cooled to room temperature after, add the 22.5g sodium metaaluminate and make high alkali deflection aluminium acid sodium solution.In 525g water glass, add high alkali deflection aluminium acid sodium solution then, mix the back and made directed agents in still aging 24 hours in room temperature.
Add 720g water, 222.5g low alkali aluminium acid sodium solution and 242g directed agents successively under in 1547g water glass, stirring, after mixing, pack in the stainless steel cauldron, 100 ℃ of static crystallization 24 hours, filter then, wash, dry NaY zeolite product.It is 5.1 that XRD records its silica alumina ratio, and relative crystallinity is 92% (Fig. 3), and average grain size is 1100 nanometers (Fig. 4,5), and the BET specific surface area is 738m
2/ g.
The NaY zeolite product of this " Comparative Examples 1 " gained is carried out modification by the same procedure described in " embodiment 1 " to be handled and makes HY and USY.And then make catalyzer and carry out catalytically active assessment by identical method, data results sees Table 3.
Comparative Examples 2
The method that repeats CN1160676A prepares the fine-grain NaY molecular sieve.
(Wenzhou catalyst plant is produced, Na at 1431 premium on currency glass
2O79g/l, SiO
2260g/l, proportion d=1.255g/ml) middle 776 rising sodium aluminate solutions (production of Wenzhou catalyst plant, the Na of adding
2O324g/l, Al
2O
354g/l, proportion d=1.310g/ml), 140 liters of sodium hydroxide solutions (produce, Na by Wenzhou catalyst plant
2O329g/l, proportion d=1.355g/ml) and 30 premium on currency, after stirring, obtained directed agents down in still aging 18 hours at 18 ℃.
(Wenzhou catalyst plant is produced, Al to add 313 liters of alum liquors in 108 premium on currency
2O
3106g/l, proportion d=1.258g/ml) and the sulfuric acid (technical pure) of 357Kg98%, after mixing, this mixture is joined in the above-mentioned directed agents, stir after 1 hour, be warming up to 102 ℃ of static crystallization 30 hours, obtain the NaY molecular sieve with washing after filtration.Recording its silica alumina ratio is 5.1, and relative crystallinity is 85%, and average grain size is 200 nanometers, and the BET specific surface area is 790m
2/ g.
Comparative Examples 3
The method that repeats JP61091013 prepares high silicon NaY molecular sieve.
In the beaker of 100mL, add 14.7mL low alkali aluminium acid sodium solution (Lanzhou petrochemical industry catalyst plant product, Al
2O
3Content is 15.3%, Na
2O content is 19.4%), 2.79mL sodium hydroxide solution (Lanzhou petrochemical industry catalyst plant product, Na
2O content is 37.45%) and 8.21mL distilled water, after mixing, slowly add the 50mL silicon sol with suction pipe therein, stirring obtains gel, changed in the reactor in 25 ℃ water-bath ageing over to 24 hours, heat static crystallization 6 days down at 100 ℃ again, obtain the NaY molecular sieve as crystal seed with washing after filtration.
Get the above-mentioned NaY molecular sieve crystal seed 5.7g that makes, sodium hydroxide solution 4.27mL and 8.86mL distilled water, after mixing, slowly add the 100mL silicon sol with suction pipe therein, stirring obtains gel, change in the reactor in 25 ℃ water-bath ageing over to 24 hours, and 100 ℃ of static crystallization of heating 17 days down, obtained the NaY molecular sieve with washing after filtration again.Recording its silica alumina ratio is 5.88, and relative crystallinity is 85%, and average grain size is 1100 nanometers, and the BET specific surface area is 714m
2/ g.
The crystal face data of eight main peaks of table 1 embodiment 1 gained NaY
Annotate: hk1: the crystal indices; 2 θ: diffraction angle; D: crystal face distance; I: diffraction peak intensity
The crystal face data of eight main peaks of table 2 Comparative Examples 1 gained NaY
From table 1, table 2 data as can be known: the 2 θ values at eight main crystal faces of embodiment 1 gained NaY molecular sieve peak are all greater than the 2 θ values at eight main crystal faces of Comparative Examples 1 gained NaY molecular sieve peak, from the calculation formula of lattice constant and silica alumina ratio:
SiO
2/Al
2O
3＝2(25.858-a)/(a-24.191)
Lattice constant and θ value are inversely proportional to as can be known, and silica alumina ratio is inversely proportional to lattice constant, and then silica alumina ratio is directly proportional with the θ value, and the big more silica alumina ratio of θ value is high more.Can infer the silica alumina ratio height of the silica alumina ratio of embodiment 1 synthetic NaY molecular sieve thus than Comparative Examples 1 synthetic NaY molecular sieve.
Table 3
From table 3 data as can be known the catalytic activity of thermostability, hydrothermal stability and the molecular sieve catalyst of the NaY molecular sieve of embodiment 1 gained all be better than the structural stability of NaY molecular sieve of Comparative Examples 1 gained and the catalytic activity of molecular sieve catalyst.
Claims (6)
1, a kind of high silicon aluminium ratio small crystal NaY molecular sieve, the framework si-al ratio that it is characterized in that the NaY molecular sieve is SiO
2/ Al
2O
3Mol ratio is between 6.0～7.0, and average crystal grain is between 300～800nm.
2, a kind of high silicon aluminium ratio small crystal NaY molecular sieve, the framework si-al ratio that it is characterized in that the NaY molecular sieve is SiO
2/ Al
2O
3Mol ratio is between 6.0～6.8, and average crystal grain is between 400～600nm.
3, high silicon aluminium ratio small crystal NaY molecular sieve according to claim 1 is characterized in that molecular sieve is first preparation directed agents, and the refabrication reaction mixture is after crystallization, filtration, washing, drying and obtain high silicon aluminium ratio small crystal NaY molecular sieve.
4, high silicon aluminium ratio small crystal NaY molecular sieve according to claim 3 is characterized in that directed agents is meant silicon source, aluminium source, alkali lye and water according to (6～30) Na
2O: Al
2O
3: (6～30) SiO
2: (100～460) H
2The mixed in molar ratio of O after stirring, is descended to stir ageings 0.5～48 hour and is made at 15～60 ℃ mixture.
5, high silicon aluminium ratio small crystal NaY molecular sieve according to claim 3 is characterized in that reaction mixture is meant by (0.5～6) Na
2O: Al
2O
3: (8～30) SiO
2: (100～460) H
2Total molar ratio of O adds entry, silicon source, aluminium source, directed agents under 15～80 ℃, wherein the add-on of directed agents accounts for 1%～50% of reaction mixture weight percent, and the pH value of control reaction mixture makes 11.0～13.5.
6, high silicon aluminium ratio small crystal NaY molecular sieve according to claim 3 is characterized in that the indication crystallization is a reaction mixture through two step crystallization, and the first step is carried out dynamic crystallization: temperature is controlled at 20～80 ℃, and crystallization time is 0.5～24 hour; Second step was carried out static crystallization then: temperature is controlled at 90～140 ℃, and crystallization time is 5～100 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101254929B (en) * | 2008-04-07 | 2012-07-11 | 华东理工大学 | Method for preparing high silica alumina ratio NaY molecular sieve |
| CN101722023B (en) * | 2008-10-28 | 2012-05-30 | 中国石油化工股份有限公司 | NaY-type molecular sieves and preparation method thereof |
| CN102049283B (en) * | 2009-10-27 | 2013-04-10 | 中国石油化工股份有限公司 | Hydro-cracking catalyst and preparation method thereof |
| CN102049308B (en) * | 2009-10-27 | 2013-04-10 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier and preparation method thereof |
| CN102049280B (en) * | 2009-10-27 | 2013-08-28 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing small crystal grain Y-shaped molecular sieve and preparation method thereof |
| CN102049306B (en) * | 2009-10-27 | 2013-08-28 | 中国石油化工股份有限公司 | Small crystal particle Y-shaped molecular sieve-containing hydrocracking catalyst carrier and preparation method thereof |
| CN102049307B (en) * | 2009-10-27 | 2013-05-01 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier and preparation method thereof |
| CN102049282B (en) * | 2009-10-27 | 2013-04-10 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN103449470B (en) * | 2012-06-01 | 2015-05-20 | 中国石油天然气股份有限公司 | Highly-stable small-grain NaY molecular sieve |
| CN104118885B (en) * | 2013-04-23 | 2016-05-11 | 中国石油天然气股份有限公司 | A kind of synthetic method of high silica alumina ratio NaY zeolite |
| CN104588074B (en) * | 2013-11-03 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of preparation method of catalytic hydro-dearomatization catalyst |
| CN104743572B (en) * | 2013-12-27 | 2018-02-16 | 陕西煤化工技术工程中心有限公司 | A kind of method of the ultra-fine NaY molecular sieve of synthesizing high-silicon aluminum ratio |
| CN105080589B (en) * | 2014-05-12 | 2017-11-03 | 中国石油化工股份有限公司 | A kind of catalyst containing Y type molecular sieve and preparation method |
| CN105084386B (en) * | 2014-05-12 | 2017-11-03 | 中国石油化工股份有限公司 | A kind of surface Silicon-rich small crystal grain Y-shaped molecular sieve and preparation method thereof |
| CN105621448B (en) * | 2014-11-03 | 2017-06-16 | 中国石油化工股份有限公司 | A kind of preparation method of fine grain NaY type molecular sieve |
| CN106946267B (en) * | 2016-01-07 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of EU-1 molecular sieve and its synthetic method |
| CN114655965B (en) * | 2020-12-23 | 2023-10-10 | 中国石油化工股份有限公司 | Method for preparing small-grain NaY |
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