CN106669772A - Compound and preparation method thereof - Google Patents
Compound and preparation method thereof Download PDFInfo
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- CN106669772A CN106669772A CN201510751469.3A CN201510751469A CN106669772A CN 106669772 A CN106669772 A CN 106669772A CN 201510751469 A CN201510751469 A CN 201510751469A CN 106669772 A CN106669772 A CN 106669772A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 150000001875 compounds Chemical class 0.000 title claims abstract description 9
- 239000002808 molecular sieve Substances 0.000 claims abstract description 63
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910001868 water Inorganic materials 0.000 claims abstract description 18
- 239000002159 nanocrystal Substances 0.000 claims abstract description 13
- 238000001704 evaporation Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- -1 aluminum oxide compound Chemical class 0.000 claims abstract description 4
- 239000012266 salt solution Substances 0.000 claims abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 78
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000011148 porous material Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 14
- 159000000013 aluminium salts Chemical class 0.000 claims description 14
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 14
- 239000010413 mother solution Substances 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 13
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 229910052681 coesite Inorganic materials 0.000 claims description 10
- 229910052593 corundum Inorganic materials 0.000 claims description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims description 10
- 235000019353 potassium silicate Nutrition 0.000 claims description 10
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052682 stishovite Inorganic materials 0.000 claims description 10
- 229910052905 tridymite Inorganic materials 0.000 claims description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 239000011550 stock solution Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000013081 microcrystal Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 3
- 239000008187 granular material Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 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 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 229910001948 sodium oxide Inorganic materials 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229950000845 politef Drugs 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 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 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- B01J35/19—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- B01J35/617—
-
- B01J35/633—
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a compound and a preparation method thereof. The preparation method comprises the following steps: separating NaY mother liquid containing nanocrystals, washing, and adding water and aluminum salt to prepare turbid liquid, wherein the mass content of aluminum of an aluminum salt solution based on aluminum oxide is 5 to 15 percent, and the weight ratio of a molecular sieve to the aluminum salt based on the aluminum oxide in the turbid liquid is 0.7:1 to 1.5:1; evaporating and roasting to obtain a Y molecular sieve and aluminum oxide compound. According to the NaY molecular sieve and aluminum oxide compound prepared by the method, the nano-scale granule NaY molecular sieve can be compounded with the aluminum oxide uniformly.
Description
Technical field
The present invention relates to a kind of complex and preparation method thereof, relates in particular to a kind of nano NaY molecular sieve and alumina compound and preparation method thereof.
Background technology
During oil product are refined with processing, petroleum component and the various alkane refined by petroleum component, the further cracking of alkene and cyclic hydrocarbon, this class process occupies consequence to isomery with alkylation, and NaY molecular sieve plays an important role in such processing as the catalyst of chemical reaction.Eighties of last century mid-term NaY molecular sieve enters industrial applications as catalyst for cracking, in subsequent many decades, with the progress and the accumulation of experiment experience of technology, the range of application of NaY molecular sieve catalyst has had very big expansion, gas is extended to always from original oil refining field to separate, various directions such as water process and bio-engineering research, play an important role in many fields.
Molecular sieve is prepared in document report various methods, but in industrial conditions widest mode is directed agents hydrothermal synthesis method for application at present, the method directly uses relatively inexpensive waterglass or Kaolin as silicon and aluminum source, by introducing nucleus in the prior directed agents for preparing, according to the proportioning addition tie element for calculating, guiding crystal growth, by the condition in control reaction process the NaY molecular sieve of different grain size and property is prepared.For catalyst NaY molecular sieve, there is numerous characteristics index to decide its performance, the crystallite dimension of such as different scale, the number in acid active center and accessible degree, the length and scope of pore passage structure, these characteristics have its catalytic efficiency of decision and catalytic performance, there is its running life of decision, with its heat stability and reaction stability, the performance for belonging to molecular sieve is integrated.
In recent years scientists are concentrated in the characteristic of nano-scale NaY to the research interest of molecular sieve, relatively conventional micron order（Particle diameter distribution is at 2～5 microns）NaY molecular sieve crystal, nanocrystal possesses great specific surface, especially bigger external surface area, and more active center can be made to expose outside.More accessible Active sites are easy to the expanding of reactant with shorter pore passage structure, reactant diffusion velocity is fast, it is difficult deposition, therefore side reaction can be reduced, reduce carbon distribution, be conducive to extending catalyst life, the NaY molecular sieve catalytic performance more more preferable than traditional micron-level molecular sieve of nanoscale can be expected（J.Phys.Chem.B 1998,102：1696-1702）.There are many patent formulas to propose the method for preparing nano-class molecular sieve at present, patent CN1133585C devises a kind of method for synthesizing 30～70nm NaY molecular sieves by hydro-thermal mode, patent USP4778666 devises the method for preparing nano molecular sieve by microwave-assisted, patent EP0041338A, USP4372931 synthesizes the X-type molecular sieve of 30～60nm using the mode for adding monosaccharide or polysaccharide in the mixture, and patent EP0435625A2 has synthesized the NaY molecular sieve of 100nm or so using high shear agitation.
Nanoscale Y molecular sieve exposes obvious shortcoming in preparation and practical application in prior art, because nanocrystal has great surface area, therefore there is very high surface energy, it is susceptible to reunite during use and causes the heavy losses of specific surface, intracrystalline pore etc., and then have impact on the catalytic performance of nanoscale Y molecular sieve.
The content of the invention
For the deficiencies in the prior art, the present invention provides complex of a kind of nano NaY molecular sieve and aluminium oxide and preparation method thereof.NaY molecular sieve and alumina compound prepared by the method, the NaY molecular sieve of nano-scale particle can uniformly be combined with each other with aluminium oxide.
A kind of preparation method of complex, including following process：Separate the NaY mother solutions containing nanocrystal first, add water and aluminium salt that suspension is obtained after washing, the mass content counted with aluminium oxide containing aluminum in aluminum salt solution as 5%～15%, preferably 5%～10%, molecular sieve and the aluminium salt weight ratio counted with aluminium oxide are as 0.7 in suspension：1~1.5：1, preferably 1.0:1~1.3:1, most preferably 1.1：1~1.2：1, Y molecular sieve and alumina compound are then obtained Jing after evaporation, roasting.
In the inventive method, the described NaY mother solutions containing nanocrystal are obtained using hydro-thermal method, but are not limited to hydro-thermal method.The hydro-thermal method is obtained the NaY mother solutions containing nanocrystal includes that the preparation of directed agents, gel are prepared and crystallization process.
The preparation process of the directed agents is as follows：By waterglass, sodium hydroxide, aluminium salt is with water according to 15～20（Na2O）：Al2O3：15～20（SiO2）：250～350（H2O）Mixed in molar ratio stirring, obtain directed agents stock solution, subsequently stock solution is stood at room temperature treat its generate with guide effect micro crystal it is standby.
The gel preparation course is as follows：By waterglass, sodium hydroxide, aluminium oxide is with water according to 2.5～4.5（Na2O）：Al2O3：6～12（SiO2）：180～250H2O, preferably 3.5～4.0（Na2O）：Al2O3：8～10（SiO2）：180～200H2The mol ratio stirring mixing of O, then adds directed agents of the weight than 5～15%（On the basis of the material being not added with before directed agents）, gel is generated after stirring.
The crystallization process is that gel is carried out into crystallization under 90～130 °C, and crystallization time is 8～40h, obtains the NaY mother solutions containing nanocrystal.
In the inventive method, the NaY mother solutions of nanocrystal are contained using centrifugation, washing removes the alkali of silicate ion and excess.
In the inventive method, preferably citric acid, ethylenediaminetetraacetic acid are added in suspended liquid system（EDTA）, one or more in Polyethylene Glycol, polyvinyl alcohol, addition is mass content with it in suspension to count 3～10%, preferably 4～6%.Detailed process is added to be first after the nanometer Y molecular sieve mixing after above-mentioned substance, water and washing aluminium salt, the mixing will to be added to carry out preferably in the presence of ultrasound wave.The material of the addition can be uniformly dispersed in molecular sieve surface and micropore, protect the micropore canals of molecular sieve, it is to avoid aggregation of the aluminium oxide in molecular sieve surface in aluminium salt evaporation process.
In the inventive method, evaporating temperature is 70～90 degrees Celsius, and the time is 3～5 hours, 500～650 degrees Celsius of sintering temperature, and the time is 2～4 hours.
In the inventive method, when adding ethylenediaminetetraacetic acid in suspended liquid system（EDTA）, during one or more in Polyethylene Glycol, polyvinyl alcohol, preferably temperature being improved to 120～150 degrees Celsius after evaporation and processed, process time is 4～6 hours.Above-mentioned processing procedure can make added material that foaming, solidification occur, and be conducive to that fluffy mutual homodisperse Y molecular sieve and alumina compound is obtained.
NaY molecular sieve and alumina compound prepared by a kind of employing said method, complex content meter by weight, NaY is 0.7 with the ratio of aluminium oxide：1~1.5：1, preferably 1.0:1~1.3:1, most preferably 1.1：1~1.2：1；The grain size of NaY molecular sieve is 80～200nm, most preferably preferably 100～150nm, 100 ~ 120nm, and 1～5nm of complex interval pore volume is distributed as 0.29～0.33cm3/ g, 30～80nm interval pore volume is distributed 0.13～0.16cm3/ g, preferably 0.14 ~ 0.16cm3/g.Complex specific surface area is 410～700m2/ g, preferably 600～700 m2/ g, most preferably 680～700 m2/ g, 160 ~ 310m of external surface area2/ g, preferably 220 ~ 310m2/ g, most preferably 280 ~ 310m2/ g, B-acid content is 0.251～0.344mmol/g, and L acid content is 0.553～0.679mmol/g.
In the inventive method, with the effect of nano NaY molecular sieve crystal in aluminium salt evaporation conversion process, the aggregation of nano NaY molecular sieve in filtration and roasting process can be avoided.Y molecular sieve after fired and alumina compound Y molecular sieve are with nanometer-size die with together with alumina composite, the specific surface area of the complex is particularly external surface area substantially to be increased, 30～80nm interval pore volume is obviously improved in pore size distribution, because the aperture can match with the kinetics radius of the target heavy oil macromole of catalytic cracking, be conducive to the diffusion of heavy oil macromole, more preferable synergism can be played in catalytic reaction process.
Specific embodiment
The essence and effect of the present invention are further illustrated below by case study on implementation and comparative example, but following examples are not construed as limiting the invention.If no special instructions constituent content is weight percent content in following examples and comparative example.
Embodiment 1
Weigh appropriate sodium metaaluminate, sodium hydroxide to be dissolved in water, be sufficiently stirred for placing to be cooled under room temperature, strong agitation after dissolving adding waterglass（Silicon dioxide quality content 28%, sodium oxide mass content 8.5%）Stirring 20min, is stored at room temperature 24 hours prepared directed agents, and the mol ratio of each material of directed agents is 20（Na2O）：Al2O3：20（SiO2）：250（H2O）.Weigh appropriate sodium metaaluminate, sodium hydroxide to dissolve in deionized water, fully add waterglass after dissolving（Silicon dioxide quality content 28%, sodium oxide mass content 8.5%）, the mol ratio of each material is 4.5 after mixing（Na2O）：Al2O3：12（SiO2）：250H2O, is subsequently adding directed agents, and addition is the 15% of quality, continues stirring until plastic, in being put into the liner reactor of politef, is heated to 130 degree of reactions and obtains the mother solution containing nano NaY molecular sieve in 4 hours.Mother solution containing nano NaY molecular sieve is centrifuged, washing adds afterwards for 3 times water and aluminium salt that suspension, the mass content of aluminium salt in suspension is obtained（In terms of aluminium oxide）For 5%, the ratio of molecular sieve and aluminium oxide is 1.5：1, Jing 70 degree Celsius evaporates 5 hours, after 650 degrees Celsius of roastings 2 hours, obtains product, is labeled as AlY-1, and property is as follows：Containing 60%NaY molecular sieves；The grain size of NaY molecular sieve molecular sieve is 100～150nm；The complex pore volume interval in 1～5nm apertures is distributed as 0.06cm3/ g, 30～80nm aperture interval pore volume is distributed as 0.06cm3/g；The specific surface area of complex is 232m2/ g, wherein external surface area are 176m2/ gB acid contents are 0.21mmol/g, and L acid content is 0.38mmol/g.
Embodiment 2
Weigh appropriate sodium metaaluminate, sodium hydroxide to be dissolved in water, be sufficiently stirred for placing to be cooled under room temperature, strong agitation after dissolving adding waterglass（Silicon dioxide quality content 28%, sodium oxide mass content 8.5%）Stirring 20min, is stored at room temperature 24 hours prepared directed agents, and the mol ratio of each material of directed agents is 15（Na2O）：Al2O3：15（SiO2）：350（H2O）.Weigh appropriate sodium metaaluminate, sodium hydroxide to dissolve in deionized water, fully add waterglass after dissolving（Silicon dioxide quality content 28%, sodium oxide mass content 8.5%）, the mol ratio of each material is 2.5 after mixing（Na2O）：Al2O3：6（SiO2）：120H2O, is subsequently adding directed agents, and addition is the 5% of mass ratio, continues stirring until plastic, in being put into the liner reactor of politef, is heated to 100 degree of reactions and obtains the mother solution containing nano NaY molecular sieve in 40 hours.Mother solution containing nano NaY molecular sieve is centrifuged, washing adds afterwards for 3 times water and aluminium salt that suspension, the mass content of aluminium salt in suspension is obtained（In terms of aluminium oxide）For 15%, the ratio of molecular sieve and aluminium oxide is 0.7：1, Jing 90 degree Celsius evaporates 3 hours, after 550 degrees Celsius of roasting 2h, obtains product, is labeled as AlY-2, and property is as follows：Containing 40%NaY molecular sieves；The grain size of NaY molecular sieve molecular sieve is 150～200nm；Complex has following pore size distribution：The interval pore volume 0.06cm in 1～5nm apertures3/ g, 30～80nm interval pore volume 0.07cm3/g；The specific surface area of complex is 320m2/ g, wherein external surface area are 257m2/ g, B-acid content is 0.24mmol/g, and L acid content is 0.46mmol/g.
Embodiment 3
With embodiment 1, difference be obtained suspension it is suspended in contain ethylenediaminetetraacetic acid, mass content is 10%, and 120 degrees Celsius are processed after evaporation, and process time is 6h.Product is obtained, AlY-3 is labeled as, property is as follows：Containing 60%NaY molecular sieves；The grain size of NaY molecular sieve molecular sieve is 100～150nm；Complex has following pore size distribution 1～5nm pore volume 0.32cm3/ g, 30～80nm interval 0.15cm3/g；The specific surface area of complex is 687m2/ g, wherein external surface area are 289m2/ gB acid contents are 0.35mmol/g, and L acid content is 0.62mmol/g.
Embodiment 4
With embodiment 2, difference be obtained suspension it is suspended in contain Polyethylene Glycol, mass content is 3%, and 150 degrees Celsius are processed after evaporation, and process time is 4h, obtain product, be labeled as AlY-4, property is as follows：Containing 20%NaY molecular sieves；The grain size of NaY molecular sieve molecular sieve is 150～200nm；Complex has following pore size distribution：1～5nm intervals pore volume 0.32cm3/ g, 30～80nm interval 0.13cm3/g；The specific surface area of complex is 631m2/ g, wherein external surface area are 302m2/ gB acid contents are 0.31mmol/g, and L acid content is 0.56mmol/g.
By the contrast of embodiment, it can be seen that add ethylenediaminetetraacetic acid（EDTA）After one or more in Polyethylene Glycol, polyvinyl alcohol, the pore volume that 1～5nm is interval and 30～80nm is interval rises appreciably, and overall specific surface area rises appreciably, wherein growth of the contribution of specific surface area essentially from micropore, external surface area also has and increases by a small margin, illustrate that foaming agent has played effect, not only remain more micropores, also cause the mesoporous impact from particles agglomerate, the aggregation tendency of crystal is alleviated simultaneously, remains more external surface areas.
Claims (14)
1. a kind of preparation method of complex, it is characterised in that：Including following process：The NaY mother solutions containing nanocrystal being separated first, adding water and aluminium salt that suspension is obtained after washing, as 5%～15%, molecular sieve and the aluminium salt weight ratio counted with aluminium oxide are as 0.7 in suspension for the mass content counted with aluminium oxide containing aluminum in aluminum salt solution：1~1.5：1, Y molecular sieve and alumina compound are then obtained Jing after evaporation, roasting.
2. method according to claim 1, it is characterised in that：, as 5%～10%, molecular sieve and the aluminium salt weight ratio counted with aluminium oxide are as 1.0 in suspension for the mass content counted with aluminium oxide containing aluminum in aluminum salt solution:1~1.3:1.
3. method according to claim 1, it is characterised in that：The described NaY mother solutions containing nanocrystal are obtained using hydro-thermal method, and the hydro-thermal method is obtained the NaY mother solutions containing nanocrystal includes that the preparation of directed agents, gel are prepared and crystallization process.
4. method according to claim 3, it is characterised in that：The preparation process of the directed agents is as follows：By waterglass, sodium hydroxide, aluminium salt is with water according to 15～20（Na2O）：Al2O3：15～20（SiO2）：250～350（H2O）Mixed in molar ratio stirring, obtain directed agents stock solution, subsequently stock solution is stood at room temperature treat its generate with guide effect micro crystal it is standby.
5. method according to claim 3, it is characterised in that：The gel preparation course is as follows：By waterglass, sodium hydroxide, aluminium oxide is with water according to 2.5～4.5（Na2O）：Al2O3：6～12（SiO2）：180～250H2The mol ratio stirring mixing of O, then adds directed agents of the weight than 5～15%, and gel is generated after stirring.
6. method according to claim 5, it is characterised in that：The gel preparation course is as follows：By waterglass, sodium hydroxide, aluminium oxide is with water according to 3.5～4.0（Na2O）：Al2O3：8～10（SiO2）：180～200H2The mol ratio stirring mixing of O.
7. method according to claim 3, it is characterised in that：The crystallization process is that gel is carried out into crystallization under 90～130 °C, and crystallization time is 8～40h, obtains the NaY mother solutions containing nanocrystal.
8. method according to claim 1, it is characterised in that：The NaY mother solutions of nanocrystal are contained using centrifugation, washing removes the alkali of silicate ion and excess.
9. method according to claim 1, it is characterised in that：Citric acid, ethylenediaminetetraacetic acid are added in suspended liquid system（EDTA）, one or more in Polyethylene Glycol, polyvinyl alcohol, addition is mass content with it in suspension to count 3～10%.
10. method according to claim 1, it is characterised in that：Evaporating temperature is 70～90 degrees Celsius, and the time is 3～5 hours, 500～650 degrees Celsius of sintering temperature, and the time is 2～4 hours.
11. methods according to claim 1, it is characterised in that：In the inventive method, when adding ethylenediaminetetraacetic acid in suspended liquid system（EDTA）, during one or more in Polyethylene Glycol, polyvinyl alcohol, preferably temperature being improved to 120～150 degrees Celsius after evaporation and processed, process time is 4～6 hours.
Complex prepared by a kind of 12. employing claim 1 to 11 either method, it is characterised in that：Complex content meter by weight, NaY is 0.7 with the ratio of aluminium oxide：1~1.5：1；The grain size of NaY molecular sieve is 80～200nm, and 1～5nm of complex interval pore volume is distributed as 0.29～0.33cm3/ g, 30～80nm interval pore volume is distributed 0.13～0.16cm3/ g, complex specific surface area is 410～700m2/ g, 160 ~ 310m of external surface area2/ g, B-acid content is 0.251～0.344mmol/g, and L acid content is 0.553～0.679mmol/g.
13. complex according to claim 12, it is characterised in that：Complex content meter by weight, NaY is 1.0 with the ratio of aluminium oxide:1~1.3:1, the grain size of NaY molecular sieve is 100～150nm, and 30～80nm intervals pore volume is distributed 0.14 ~ 0.16cm3/ g, complex specific surface area is 600～700 m2/ g, 220 ~ 310m of external surface area2/g。
14. complex according to claim 13, it is characterised in that：Complex content meter by weight, NaY is 1.1 with the ratio of aluminium oxide：1~1.2：1；The grain size of NaY molecular sieve is 100 ~ 120nm, and complex specific surface area is 680～700 m2/ g, 280 ~ 310m of external surface area2/g。
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| CN101759198A (en) * | 2008-12-24 | 2010-06-30 | 中国石油化工股份有限公司 | Small crystal particle Y-shaped molecular sieve and preparation method thereof |
| CN103100433A (en) * | 2011-11-11 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method of composite carrier material |
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| CN101759198A (en) * | 2008-12-24 | 2010-06-30 | 中国石油化工股份有限公司 | Small crystal particle Y-shaped molecular sieve and preparation method thereof |
| CN103100433A (en) * | 2011-11-11 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method of composite carrier material |
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| Title |
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| 于菲菲: "用于柴油加氢改质催化剂载体的超微Y/Al2O3复合材料的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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