CN106669772B - A kind of compound and preparation method thereof - Google Patents
A kind of compound and preparation method thereof Download PDFInfo
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- CN106669772B CN106669772B CN201510751469.3A CN201510751469A CN106669772B CN 106669772 B CN106669772 B CN 106669772B CN 201510751469 A CN201510751469 A CN 201510751469A CN 106669772 B CN106669772 B CN 106669772B
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- molecular sieve
- aluminium
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000002808 molecular sieve Substances 0.000 claims abstract description 61
- 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 61
- 238000000034 method Methods 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001868 water Inorganic materials 0.000 claims abstract description 19
- 159000000013 aluminium salts Chemical class 0.000 claims abstract description 16
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims abstract description 16
- 239000000725 suspension Substances 0.000 claims abstract description 16
- 239000012452 mother liquor Substances 0.000 claims abstract description 13
- 239000002159 nanocrystal Substances 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 239000004411 aluminium Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000012266 salt solution Substances 0.000 claims abstract description 4
- 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 20
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 12
- 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 10
- 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
- 238000009826 distribution Methods 0.000 claims description 10
- 229960001484 edetic acid Drugs 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
- 238000003756 stirring Methods 0.000 claims description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- -1 silicate ion Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000013081 microcrystal Substances 0.000 claims description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims 1
- 229940125904 compound 1 Drugs 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 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 6
- 235000013339 cereals Nutrition 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 2
- 230000000052 comparative effect Effects 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
- 230000000694 effects Effects 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001399 aluminium compounds Chemical class 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
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate 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
- 238000005516 engineering process Methods 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
- 239000007789 gas 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
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003209 petroleum derivative 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
- 235000009566 rice Nutrition 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
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 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—
Abstract
The present invention discloses a kind of compound and preparation method thereof.The preparation method comprises the following processes: NaY mother liquor of the separation containing nanocrystal first, water is added after washing and suspension is made in aluminium salt, mass content in aluminum salt solution containing aluminium in terms of aluminium oxide is 5%~15%, molecular sieve and the aluminium salt weight ratio in terms of aluminium oxide are 0.7:1 ~ 1.5:1 in suspension, and Y molecular sieve and alumina compound are made after then being evaporated, being roasted.The NaY molecular sieve and alumina compound, the NaY molecular sieve of nano-scale particle of this method preparation can uniformly be combined with each other with aluminium oxide.
Description
Technical field
The present invention relates to a kind of compound and preparation method thereof, a kind of nano NaY molecular sieve and oxidation are related in particular to
Aluminium compound and preparation method thereof.
Background technique
During petroleum product are refined with processing, petroleum component and the various alkane refined by petroleum component, alkene
With the further cracking of cyclic hydrocarbon, isomery occupies consequence with this class process is alkylated, and NaY molecular sieve is made
It plays an important role in such processing for the catalyst of chemical reaction.Eighties of last century mid-term NaY molecular sieve is urged as cracking
Agent enters industrial applications, in subsequent many decades, with advances in technology with the accumulation of experiment experience, NaY molecular sieve
The application range of catalyst has had very big expansion, is extended to gas always from original oil refining field and separates, at water
A variety of directions such as reason and bio-engineering research, play an important role in many fields.
Molecular sieve is prepared in document report, and there are many methods, but widest mode is in industrial conditions for application at present
Directed agents hydrothermal synthesis method, this method directly uses relatively inexpensive waterglass or kaolin as silicon and aluminum source, by making in advance
Introduce nucleus in standby directed agents, add tie element according to the proportion that calculates, guide crystal growth, by control react into
Condition in journey prepares the NaY molecular sieve of different grain size and property.For catalyst NaY molecular sieve, there are many characteristic index
Decide its performance, such as the crystallite dimension of different scale, the number in acid activated centre and accessible degree, cellular structure
Length and range, these characteristics, which have, determines its catalytic efficiency and catalytic performance, has and determines its running life, with its thermostabilization
Property and reaction stability, integrate the service performance for belonging to molecular sieve.
Scientists concentrate on the research interest of molecular sieve in the characteristic of nano-scale NaY in recent years, relatively traditional
The NaY molecular sieve crystal of micron order (particle diameter distribution is at 2~5 microns), nanocrystal possess great specific surface, especially bigger
External surface area, more activated centres can be made to be exposed to outer.More accessible Active sites and shorter duct are tied
Structure is convenient for the expanding of reactant, and reactant diffusion velocity is fast, is not easy to deposit, therefore can reduce side reaction, reduces carbon distribution, favorably
In extending catalyst life, the NaY molecular sieve of nanoscale catalytic performance more better than traditional micron-level molecular sieve can be expected
(J.Phys.Chem.B 1998,102:1696-1702).It is proposed at present there are many patent formula and prepares nano-class molecular sieve
Method, patent CN1133585C devise a kind of method for synthesizing 30~70nm NaY molecular sieve by hydro-thermal mode, patent
USP4778666 is devised through the microwave-assisted method for preparing nano molecular sieve, patent EP0041338A, and USP4372931 makes
Synthesize the X-type molecular sieve of 30~60nm with the mode for adding monosaccharide or polysaccharide in the mixture, patent EP0435625A2 is used
High shear agitation has synthesized the NaY molecular sieve of 100nm or so.
Nanoscale Y molecular sieve exposes obvious disadvantage in preparation and practical application in the prior art, due to nanocrystalline
Body has great surface area, therefore has very high surface energy, is easy to happen reunion in use process and causes specific surface, intergranular
The heavy losses in hole etc., and then affect the catalytic performance of nanoscale Y molecular sieve.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides the compound and its system of a kind of nano NaY molecular sieve and aluminium oxide
Preparation Method.The NaY molecular sieve and alumina compound of this method preparation, the NaY molecular sieve of nano-scale particle can be with aluminium oxide
Uniformly it is combined with each other.
A kind of preparation method of compound, comprises the following processes: NaY mother liquor of the separation containing nanocrystal first, washing
Water and aluminium salt being added afterwards, suspension is made, the mass content in terms of aluminium oxide containing aluminium is 5%~15% in aluminum salt solution, preferably 5%~
10%, molecular sieve and the aluminium salt weight ratio in terms of aluminium oxide are 0.7:1 ~ 1.5:1 in suspension, and preferably 1.0:1 ~ 1.3:1 is optimal
1.1:1 ~ 1.2:1 is selected, Y molecular sieve and alumina compound are made after then being evaporated, being roasted.
In the method for the present invention, the NaY mother liquor containing nanocrystal is made using hydro-thermal method, but is not limited to water
Thermal method.It includes the preparation of directed agents, gel preparation and crystallization process that the NaY mother liquor containing nanocrystal, which is made, in the hydro-thermal method.
The preparation process of the directed agents is as follows: by waterglass, sodium hydroxide, aluminium salt and water are according to 15~20(Na2O):
Al2O3: 15~20(SiO2): 250~350(H2O molar ratio) is mixed, and directed agents stoste is obtained, then by stoste in room
Lower stand of temperature has the micro crystal of guiding role spare to its generation.
The gel preparation course is as follows: by waterglass, sodium hydroxide, aluminium oxide and water are according to 2.5~4.5(Na2O):
Al2O3: 6~12(SiO2): 180~250H2O, preferably 3.5~4.0(Na2O): Al2O3: 8~10(SiO2): 180~200H2O's
Molar ratio is stirred, and then adds the directed agents (on the basis of the material being not added before directed agents) of weight ratio 5~15%, stirring
After generate gel.
The crystallization process is that gel is carried out crystallization under 90~130 °C, and crystallization time is 8~40h, is obtained containing receiving
The NaY mother liquor of rice crystal grain.
In the method for the present invention, using NaY mother liquor of the centrifuge separation containing nanocrystal, washing removes silicate ion and mistake
The alkali of amount.
In the method for the present invention, citric acid, ethylenediamine tetra-acetic acid (EDTA), poly- second two are preferably added into suspended liquid system
One or more of alcohol, polyvinyl alcohol, additional amount be by its mass content in suspension be in terms of 3~10%, preferably 4~
6%.It is that aluminium salt is added after first the nanometer Y molecular sieve after above-mentioned substance, water and washing is mixed that detailed process, which is added, described
Mixing preferably carries out under the action of ultrasonic wave.The substance of the addition can be uniformly dispersed in molecular sieve surface and micro-
Kong Zhong protects the micropore canals of molecular sieve, avoids in aluminium salt evaporation process aluminium oxide in the aggregation of molecular sieve surface.
In the method for the present invention, evaporating temperature is 70~90 degrees Celsius, and the time is 3~5 hours, and maturing temperature 500~650 is taken the photograph
Family name's degree, time are 2~4 hours.
In the method for the present invention, when in addition ethylenediamine tetra-acetic acid (EDTA) in suspended liquid system, polyethylene glycol, polyvinyl alcohol
One or more when, preferably temperature is improved to 120~150 degrees Celsius after evaporation and is handled, processing the time be 4~6
Hour.Above-mentioned treatment process can make substance be added that foaming, solidification occur, and be conducive to be made fluffy mutual evenly dispersed
Y molecular sieve and alumina compound.
A kind of NaY molecular sieve and alumina compound using above method preparation, compound content meter by weight,
NaY and the ratio of aluminium oxide are 0.7:1 ~ 1.5:1, preferably 1.0:1 ~ 1.3:1, most preferably 1.1:1 ~ 1.2:1；NaY molecular sieve
Grain size is 80~200nm, preferably 100~150nm, most preferably 100 ~ 120nm, and the hole in the section 1~5nm of compound holds distribution
For 0.29~0.33cm3The section hole /g, 30~80nm holds 0.13~0.16cm of distribution3/ g, preferably 0.14 ~ 0.16cm3/g.It is compound
Object specific surface area is 410~700m2/ g, preferably 600~700 m2/ g, most preferably 680~700 m2/ g, external surface area 160 ~
310m2/ g, preferably 220 ~ 310m2/ g, most preferably 280 ~ 310m2/ g, B acid content are 0.251~0.344mmol/g, L acid content
For 0.553~0.679mmol/g.
In the method for the present invention, aluminium salt evaporate conversion process in nano NaY molecular sieve crystal act on, can be avoided filtering and
The aggregation of nano NaY molecular sieve in roasting process.Y molecular sieve and alumina compound Y molecular sieve after being fired is with nanoscale
Together with alumina composite, the specific surface area of the compound especially external surface area obviously increases crystal grain, in pore size distribution
The Kong Rong in the section 30~80nm is obviously improved, since the aperture can be with the dynamics half of the target heavy oil macromolecular of catalytic cracking
Diameter matches, and is conducive to the diffusion of heavy oil macromolecular, and better synergistic effect can be played in catalytic reaction process.
Specific embodiment
Further illustrate essence and effect of the invention below by case study on implementation and comparative example, but following embodiment not structure
At limitation of the present invention.Constituent content is weight percent content unless otherwise specified in following embodiment and comparative example.
Embodiment 1
Weigh appropriate sodium metaaluminate, sodium hydroxide is dissolved in water, be sufficiently stirred dissolution after place be cooled to room temperature, strongly
It is added with stirring waterglass (silica quality content 28%, sodium oxide molybdena mass content 8.5%) stirring 20min, is stored at room temperature 24
Hour obtained directed agents, the molar ratio of each substance of directed agents are 20(Na2O): Al2O3: 20(SiO2): 250(H2O).It weighs appropriate
In deionized water, waterglass (silica quality content 28%, oxygen is added in sodium metaaluminate, sodium hydroxide dissolution after completely dissolution
Change sodium mass content 8.5%), the molar ratio of each substance is 4.5(Na2O after mixing): Al2O3: 12(SiO2): 250H2O, then plus
Enter directed agents, additional amount is the 15% of quality, continues stirring until plastic, is put into the liner reaction kettle of polytetrafluoroethylene (PTFE), is heated to
130 degree of reactions, 4 hours mother liquors of the acquisition containing nano NaY molecular sieve.To the mother liquor centrifugation containing nano NaY molecular sieve, washing 3
Water is added after secondary and suspension is made in aluminium salt, the mass content (in terms of aluminium oxide) of aluminium salt is 5% in suspension, molecular sieve and oxygen
The ratio for changing aluminium is 1.5:1, is evaporated 5 hours through 70 degrees Celsius, after 650 degrees Celsius roast 2 hours, obtains product, is labeled as
AlY-1, property are as follows: containing 60%NaY molecular sieve；The grain size of NaY molecular sieve molecular sieve is 100~150nm；Compound
Kong Rong in the aperture 1~5nm section is distributed as 0.06cm3The aperture section hole /g, 30~80nm, which holds, is distributed as 0.06cm3/g；It is compound
The specific surface area of object is 232m2/ g, wherein external surface area is 176m2/ gB acid content is 0.21mmol/g, and L acid content is
0.38mmol/g。
Embodiment 2
Weigh appropriate sodium metaaluminate, sodium hydroxide is dissolved in water, be sufficiently stirred dissolution after place be cooled to room temperature, strongly
It is added with stirring waterglass (silica quality content 28%, sodium oxide molybdena mass content 8.5%) stirring 20min, is stored at room temperature 24
Hour obtained directed agents, the molar ratio of each substance of directed agents are 15(Na2O): Al2O3: 15(SiO2): 350(H2O).It weighs appropriate
In deionized water, waterglass (silica quality content 28%, oxygen is added in sodium metaaluminate, sodium hydroxide dissolution after completely dissolution
Change sodium mass content 8.5%), the molar ratio of each substance is 2.5(Na after mixing2O): Al2O3: 6(SiO2): 120H2Then O is added
Directed agents, additional amount are the 5% of mass ratio, continue stirring until plastic, are put into the liner reaction kettle of polytetrafluoroethylene (PTFE), are heated to
100 degree of reactions, 40 hours mother liquors of the acquisition containing nano NaY molecular sieve.To the mother liquor centrifugation containing nano NaY molecular sieve, washing
Water and aluminium salt are added after 3 times, suspension are made, the mass content (in terms of aluminium oxide) of aluminium salt is 15% in suspension, molecular sieve with
The ratio of aluminium oxide is 0.7:1, is evaporated 3 hours through 90 degrees Celsius, after 550 degrees Celsius of roasting 2h, obtains product, is labeled as AlY-
2, property is as follows: containing 40%NaY molecular sieve；The grain size of NaY molecular sieve molecular sieve is 150~200nm；Compound has
Following pore size distribution: the hole in the aperture 1~5nm section holds 0.06cm3The section hole /g, 30~80nm holds 0.07cm3/g；Compound
Specific surface area is 320m2/ g, wherein external surface area is 257m2/ g, B acid content are 0.24mmol/g, and L acid content is 0.46mmol/
g。
Embodiment 3
With embodiment 1, the difference is that contain ethylenediamine tetra-acetic acid during obtained suspension is suspended, mass content 10%,
It is handled for 120 degrees Celsius after evaporation, the processing time is 6h.Product is obtained, AlY-3 is labeled as, property is as follows: containing 60%NaY
Molecular sieve；The grain size of NaY molecular sieve molecular sieve is 100~150nm；Compound has the following hole 1~5nm of pore size distribution
Hold 0.32cm3/ g, 30~80nm section 0.15cm3/g；The specific surface area of compound is 687m2/ g, wherein external surface area be
289m2/ gB acid content is 0.35mmol/g, and L acid content is 0.62mmol/g.
Embodiment 4
With embodiment 2, the difference is that containing polyethylene glycol, mass content 3%, evaporation during obtained suspension is suspended
It is handled for 150 degrees Celsius afterwards, the processing time is 4h, obtains product, is labeled as AlY-4, and property is as follows: containing 20%NaY molecule
Sieve；The grain size of NaY molecular sieve molecular sieve is 150~200nm；Compound has following pore size distribution: the section 1~5nm hole
Hold 0.32cm3/ g, 30~80nm section 0.13cm3/g；The specific surface area of compound is 631m2/ g, wherein external surface area be
302m2/ gB acid content is 0.31mmol/g, and L acid content is 0.56mmol/g.
By the comparison of embodiment, it can be seen that be added ethylenediamine tetra-acetic acid (EDTA), one in polyethylene glycol, polyvinyl alcohol
Kind or it is several after, the Kong Rong in the section 1~5nm and the section 30~80nm rises appreciably, and whole specific surface area have it is bright
Aobvious to increase, wherein mainly from the growth of micropore, external surface area also has to be increased by a small margin for the contribution of specific surface area, illustrates foaming agent
Effect has been played, more micropores are not only remained, but also the mesoporous influence from particles agglomerate, while alleviating crystal
Aggregation tendency remains more external surface areas.
Claims (13)
1. a kind of preparation method of compound, it is characterised in that: comprise the following processes: NaY of the separation containing nanocrystal first
Mother liquor, is added water after washing and suspension is made in aluminium salt, ethylenediamine tetra-acetic acid (EDTA) is added in suspension, polyethylene glycol gathers
One or more of vinyl alcohol；Mass content in aluminum salt solution containing aluminium in terms of aluminium oxide is 5%~15%, molecule in suspension
Sieve is 0.7:1 ~ 1.5:1 with the aluminium salt weight ratio in terms of aluminium oxide, handles 4~6 in 120~150 DEG C after then being evaporated, being evaporated
Y molecular sieve and alumina compound is made after hour, roasting.
2. according to the method described in claim 1, it is characterized by: the mass content in aluminum salt solution containing aluminium in terms of aluminium oxide is
5%~10%, molecular sieve and the aluminium salt weight ratio in terms of aluminium oxide are 1.0:1 ~ 1.3:1 in suspension.
3. according to the method described in claim 1, it is characterized by: the NaY mother liquor containing nanocrystal uses hydro-thermal
Method is made, and it includes the preparation of directed agents, gel preparation and crystallization mistake that the NaY mother liquor containing nanocrystal, which is made, in the hydro-thermal method
Journey.
4. according to the method described in claim 3, it is characterized by: the preparation process of the directed agents is as follows: by waterglass, hydrogen
Sodium oxide molybdena, aluminium salt and water are according to 15~20(Na2O): Al2O3: 15~20(SiO2): 250~350(H2O molar ratio mixing) is stirred
It mixes, obtains directed agents stoste, then standing stoste at room temperature to generate to it has the micro crystal of guiding role spare.
5. according to the method described in claim 3, it is characterized by: the gel preparation course is as follows: by waterglass, hydroxide
Sodium, aluminium oxide and water are according to 2.5~4.5(Na2O): Al2O3: 6~12(SiO2): 180~250H2The molar ratio of O is stirred,
Then the directed agents for adding weight ratio 5~15%, generate gel after stirring.
6. according to the method described in claim 5, it is characterized by: the gel preparation course is as follows: by waterglass, hydroxide
Sodium, aluminium oxide and water are according to 3.5~4.0(Na2O): Al2O3: 8~10(SiO2): 180~200H2The molar ratio of O is stirred.
7. according to the method described in claim 3, it is characterized by: the crystallization process be by gel at 90~130 DEG C into
Row crystallization, crystallization time are 8~40h, obtain the NaY mother liquor containing nanocrystal.
8. according to the method described in claim 1, it is characterized by: being washed using NaY mother liquor of the centrifuge separation containing nanocrystal
Wash away silicate ion and excessive alkali.
9. according to the method described in claim 1, it is characterized by: citric acid is added into suspended liquid system, ethylenediamine tetrem
Sour (EDTA), one or more of polyethylene glycol, polyvinyl alcohol, additional amount is by its mass content in suspension be in terms of
3~10%.
10. according to the method described in claim 1, it is characterized by: evaporating temperature be 70~90 DEG C, the time be 3~5 hours,
500~650 DEG C of maturing temperature, the time is 2~4 hours.
11. a kind of compound prepared using claims 1 to 10 either method, it is characterised in that: the compound is by weight
The ratio of content meter, NaY and aluminium oxide is 0.7:1 ~ 1.5:1；The grain size of NaY molecular sieve is 80~200nm, compound 1
The Kong Rong in the section~5nm is distributed as 0.29~0.33cm3The section hole /g, 30~80nm holds 0.13~0.16cm of distribution3/ g, it is compound
Object specific surface area is 410~700m2/ g, 160 ~ 310m of external surface area2/ g, B acid content are 0.251~0.344mmol/g, and L acid contains
Amount is 0.553~0.679mmol/g.
12. compound according to claim 11, it is characterised in that: compound content meter by weight, NaY and oxidation
The ratio of aluminium is 1.0:1 ~ 1.3:1, and the grain size of NaY molecular sieve is 100~150nm, and the section 30~80nm hole holds distribution
0.14~0.16cm3/ g, compound specific surface area are 600~700 m2/ g, 220 ~ 310m of external surface area2/g。
13. compound according to claim 12, it is characterised in that: compound content meter by weight, NaY and oxidation
The ratio of aluminium is 1.1:1 ~ 1.2:1；The grain size of NaY molecular sieve is 100 ~ 120nm, and compound 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 |
Non-Patent Citations (1)
| Title |
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| 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;于菲菲;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20090615;正文第27-29、58-70页 |
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