CN106582597A - Silicon-modified alumina, as well as preparation method and application thereof - Google Patents
Silicon-modified alumina, as well as preparation method and application thereof Download PDFInfo
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 273
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 72
- 239000011148 porous material Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- 230000004048 modification Effects 0.000 claims description 59
- 238000012986 modification Methods 0.000 claims description 59
- 239000002253 acid Substances 0.000 claims description 49
- 229910001593 boehmite Inorganic materials 0.000 claims description 39
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 17
- 239000011707 mineral Substances 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 238000001935 peptisation Methods 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 5
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 238000004523 catalytic cracking Methods 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 239000010703 silicon Substances 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 abstract 3
- 239000007848 Bronsted acid Substances 0.000 abstract 2
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 150000007522 mineralic acids Chemical class 0.000 abstract 1
- 239000002002 slurry Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- -1 polysiloxanes Polymers 0.000 description 9
- 239000003643 water by type Substances 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910018512 Al—OH Inorganic materials 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical class [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910002800 Si–O–Al Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J21/12—Silica and 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention provides silicon-modified alumina, as well as a preparation method and application thereof. Alumina modified by silicon sol comprises the following steps of (1) acidifying and peptizing pseudo-boehmite slurry with inorganic acid to obtain pseudo-boehmite sol; (2) adding silica sol into the pseudo-boehmite sol to obtain a first mixture; (3) regulating the pH value of the first mixture in a range that the pH is 1 to 11 according to different requirements for the content of surface bronsted acid and pore volume improvement degree of alumina, and conducting a reaction for a period of time under a heating condition to obtain a second mixture; (4) crystallizing the second mixture to obtain a third mixture; and (5) filtering, washing, drying and roasting the third mixture to obtain the silicon-modified alumina. Flexible conversion between emphasizing pore volume improvement and bronsted acid content improvement can be realized by regulating the pH value of the first mixture, so that the method has a wide application prospect.
Description
Technical field
The invention belongs to catalyst technical field, and in particular to a kind of Si modification aluminium oxide and its preparation method and application.
Background technology
In catalytic cracking field, the increasingly in poor quality of raw material is put forward higher requirement to catalyst, especially to making
For the aluminium oxide that substrate and binding agent are used, do not require nothing more than its surface to have it is a certain amount of(B) sour position is reducing
The coking of catalyst, while also requiring which will have larger specific surface area and pore volume to improve mass transfer, the heat transfer energy of catalyst
Power.
Researchers mainly make alumina surface produce B-acid position using the method for addition modifying agent at present, and surface acidity changes
Property agent is most commonly used that silicon-containing compound, including inorganic silicon source：Ludox, waterglass, silicic acid, and organic silicon source (TEOS,
TMOS) etc..The generation of B-acid position on Si modification aluminium oxide is primarily due to the formation of silicone hydroxyl, the silicone hydroxyl on amorphous silica-alumina
Generally there are three kinds of forms：Individually the hydroxyl on silanol base shows the B-acid position of weaker acid；If strong on silanol base and aluminium oxide
L acid is the undersaturated Al in room3+There is the B-acid position that reciprocal action can then produce a kind of middle strong acidity；Another is then without fixed
The bridge hydroxyl group formed in type sial, although the amount of this kind of hydroxyl is minimum but which is acid most strong.
And for the expanding method of aluminium oxide, mainly include two kinds of Physical and chemical method.Physical method typically by
Physical means, i.e., add expanding agent (block copolymer, Polyethylene Glycol and starch etc.), during the plastic of aluminium oxide by roasting
Burn off removes expanding agent so as to reach the purpose of reaming.Chemical method typically adds auxiliary agent in the preparation process of aluminium oxide, such as
The regulation and control with realization to the pore structure of aluminium oxide such as Ludox, sodium silicate.
CN 1590413A disclose a kind of preparation method of Si modification alumina supporting material, by molten with polysiloxanes
Liquid process crystalline aluminum oxide after, drying, roasting and be obtained modified aluminas.In carrier prepared by the method, silicon oxide is covered in
The top layer of aluminium oxide, and being connected with chemical bond with aluminium oxide, can effectively utilizes alumina surface acidity, make load active component
Afterwards, catalyst activity increases.
CN 1951554A disclose a kind of preparation method of silicone modified aluminum hydroxide solid elastomer.In the invention Si modification hydrogen-oxygen
Change in the preparation process of aluminum dry glue, acid aluminium salt solution is neutralized after plastic reaction with alkaline compound solution, is added organic
Silicon carries out aging synthesis.Roasting is converted into the γ-Al of Si modification to silicone modified aluminum hydroxide solid elastomer under optimum conditions2O3, which has
Higher specific surface area, larger pore volume and aperture.
CN 1714927A disclose a kind of preparation method of silica-alumina.The preparation side of the silica-alumina
Method includes preparing a kind of salic water dirty solution, introduces a kind of solution of silicon-containing compound, aging and drying afterwards, wherein
The solution of described silicon-containing compound is a kind of mother solution of synthesis of molecular sieve.The ratio table of silica-alumina prepared by the method
Area and pore volume increase.
It can be seen that, although many for the method for the pore volume and surface acidity that improve aluminium oxide in prior art, at present
Also do not have a kind of to realize stressing to improve pore volume and stressing to improve the modified aluminas that flexible conversion is carried out between B-acid content
Technique.
The content of the invention
To overcome the problems referred to above, it is an object of the invention to provide a kind of preparation method of Si modification aluminium oxide.
It is a further object of the present invention to provide a kind of use Si modification aluminium oxide obtained in said method.
It is yet another object of the invention to provide more than one state Si modification aluminium oxide being catalyzed as obtained in substrate or carrier
Agent.
To reach above-mentioned purpose, the invention provides a kind of preparation method of Si modification aluminium oxide, wherein, the method includes
Following steps：
(1) acidifying peptization is carried out to boehmite serosity using mineral acid, obtains boehmite colloidal sol；
(2) Ludox is added in the boehmite colloidal sol, obtain the first mixture；
(3) improve the different of degree according to the surface B-acid content and pore volume to aluminium oxide to require, in the range of pH=1-11
The pH value of the first mixture is adjusted, then reaction for a period of time, obtains the second mixture in a heated condition；To first
The rule that the pH value of mixture is adjusted is：The raising degree of the lower surface B-acid content to aluminium oxide of pH value is bigger, pH value
The raising degree of the higher pore volume to aluminium oxide is bigger；
(4) Crystallizing treatment is carried out to second mixture, obtains the 3rd mixture；
(5) the 3rd mixture obtains Si modification aluminium oxide through filter washing, drying, roasting.
Under the preparation system of said method, it has been found that when the pH value of the first mixture is lower, the table to aluminium oxide
It is larger that face B-acid content improves degree；And when the pH value of the first mixture is higher, it is larger to the pore volume raising degree of aluminium oxide.
Therefore, the present invention provides the method being modified to aluminium oxide, by the pH value for adjusting the first mixture, you can to realize in side
Improving pore volume again and stressing to improve carry out between B-acid content flexible conversion, therefore, the method is with a wide range of applications.
In the above-mentioned method being modified to aluminium oxide, it is preferable that the consumption of the mineral acid in step (1) meets
Following condition：H in mineral acid+With the Al in boehmite serosity3+Mol ratio be 0.03-0.1:1, or make the thin water aluminum of plan
The pH of stone colloidal sol is 2.5-5.0.Mineral acid can be hydrochloric acid, nitric acid or sulphuric acid etc., be made into the aqueous solution that concentration is 1-6mol/L
When using preferable.
In the above-mentioned method being modified to aluminium oxide, it is preferable that carry out being acidified the concrete steps of peptization in step (1)
Including：The Deca mineral acid in boehmite serosity, continues to react 5-60min after completion of dropping at 30-90 DEG C.
In the above-mentioned method being modified to aluminium oxide, it is preferable that the consumption of the Ludox in step (2) meets
Following condition：The Al in Si and boehmite colloidal sol in Ludox3+Mol ratio be 0.1-0.3:1.
In the above-mentioned method being modified to aluminium oxide, it is preferable that the pH value of the first mixture is carried out in step (3)
During regulation, the reagent for using is mineral acid or inorganic base；The mineral acid includes one or more in hydrochloric acid, nitric acid and sulphuric acid
Combination；The inorganic base includes the combination of one or more in potassium hydroxide, sodium hydroxide and ammonia.Mineral acid and inorganic
Alkali is typically made into the solution that concentration is 1-6mol/L and uses preferably.
In the above-mentioned method being modified to aluminium oxide, it is preferable that after having adjusted pH in step (3), reacting by heating
Condition is to react 20-24h at 30-90 DEG C.The reaction is to form more Al-OH and Si- in specific pH value range
OH, during need stirring.In addition, after pH has been adjusted, being preferably added a certain amount of deionized water with the flowing of regulation system
Property.
In the above-mentioned method being modified to aluminium oxide, we are also found surprisingly that：When by the pH value of the first mixture
When being adjusted to pH=1-2, there is a stage for suddenly being lifted in the surface B-acid content of aluminium oxide；When by the pH of the first mixture
Value is adjusted to pH=10-11, and the pore volume of aluminium oxide there is also a stage for suddenly being lifted.Specifically, in the present invention
In preferred implementation, when the pH value of the first mixture is 1-2, not only the pore volume and specific surface area of aluminium oxide is improved,
The degree that more importantly B/L is lifted becomes big (B/L reaches 0.92) suddenly；In another preferred embodiment, the first mixture
PH value be 10-11 when, not only the B-acid content of aluminium oxide is improved, it is often more important that pore volume lifted degree become suddenly
(pore volume has reached 1.00cm greatly3/ g, and specific surface area has also reached 336m2/g).For this purpose, according to the discovery, only can pass through
The pH of the first mixture is set as into desired value, you can obtain Si modification aluminium oxide of the surface rich in B-acid or big pore volume Si modification
Aluminium oxide.
In the above-mentioned method being modified to aluminium oxide, it is preferable that the condition of the Crystallizing treatment in step (4)
For：Crystallization 12-24h at 100-120 DEG C.Carrying out Crystallizing treatment under this condition (includes self-generated pressure or certain outer press ring
Border), Al-OH and Si-OH can be made to be condensed to form Si-O-Al structures, so as to increase the B-acid position of alumina surface.
In the above-mentioned method being modified to aluminium oxide, it is preferable that the condition of the roasting of step (5) is：450-
Roasting 4-6h at 650 DEG C.
In a kind of preferred implementation that the present invention is provided, the preparation method of Si modification aluminium oxide is comprised the following steps：
(1) acidifying peptization is carried out to boehmite serosity using mineral acid, obtains boehmite colloidal sol；Mineral acid
Consumption meets following condition：H in mineral acid+With the Al in boehmite serosity3+Mol ratio be 0.03-0.1:1, or make
The pH of boehmite colloidal sol is 2.5-5.0；
(2) Ludox is added in the boehmite colloidal sol, obtain the first mixture；The consumption of Ludox meet with
Lower condition：The Al in Si and boehmite colloidal sol in Ludox3+Mol ratio be 0.1-0.3:1；
(3) improve the different of degree according to the surface B-acid content and pore volume to aluminium oxide to require, in the range of pH=1-11
The pH value of the first mixture is adjusted, then reaction for a period of time, obtains the second mixture in a heated condition；To first
The rule that the pH value of mixture is adjusted is：The raising degree of the lower surface B-acid content to aluminium oxide of pH value is bigger, pH value
The raising degree of the higher pore volume to aluminium oxide is bigger；
(4) Crystallizing treatment is carried out to second mixture, obtains the 3rd mixture；The condition of crystallization is：In 100-120
Crystallization 12-24h at DEG C；
(5) the 3rd mixture obtains Si modification aluminium oxide through filter washing, drying, roasting；The condition of roasting is：
Roasting 4-6h at 450-650 DEG C.
Present invention also offers Si modification aluminium oxide obtained in said method；Preferably, the Si modification aluminium oxide is table
Si modification aluminium oxide (when the pH value of first mixture be adjusted to pH=1-2) of the face rich in B-acid or big pore volume Si modification aluminium oxide
(when the pH value of the first mixture is adjusted to pH=10-11)；The B/L of Si modification aluminium oxide of the surface rich in B-acid is 40-
95%, the pore volume of the big pore volume Si modification aluminium oxide is 0.8-1.2cm3/g。
It can be seen that, the method provided using the present invention can be obtained the excellent Si modification aluminium oxide of overall performance, and can be flexible
Adjustment is to alumina modified emphasis.
Present invention also offers above-mentioned Si modification aluminium oxide is used as catalyst obtained in substrate or carrier；Preferably, it is described
Catalyst includes catalytic cracking catalyst or hydrogenation catalyst.For example, split using above-mentioned Si modification aluminium oxide as the catalysis of substrate
Change catalyst, or, using above-mentioned Si modification aluminium oxide as the hydrogenation catalyst of carrier.
Description of the drawings
Fig. 1 is the XRD figure of silica sol modified aluminium oxide in embodiment 1, embodiment 2 and embodiment 3；
Fig. 2 is the nitrogen Adsorption and desorption isotherms figure of silica sol modified aluminium oxide in embodiment 1, embodiment 2 and embodiment 3；
Fig. 3 is the graph of pore diameter distribution of silica sol modified aluminium oxide in embodiment 1, embodiment 2 and embodiment 3；
Fig. 4 is the pyridine adsorption FT-IR spectrogram of silica sol modified aluminium oxide in embodiment 1, embodiment 2 and embodiment 3.
Specific embodiment
In order to be more clearly understood to the technical characteristic of the present invention, purpose and beneficial effect, now to skill of the invention
Art scheme carry out it is described further below, but it is not intended that to the present invention can practical range restriction.
Embodiment 1
A kind of preparation method of Si modification aluminium oxide is present embodiments provided, also, it is rich that surface has been obtained using the method
Si modification aluminium oxide containing B-acid, concrete preparation process include：
(1) 22g boehmites are added in 50mL deionized waters and are beaten 5-10min, boehmite serosity is obtained；
To in boehmite serosity, the hydrochloric acid solution of the 6mol/L of Deca 5mL makes which be acidified peptization, and 1h is persistently stirred after completion of dropping,
Obtain boehmite colloidal sol；
(2) first to Deca 12g Ludox in above-mentioned boehmite colloidal sol, obtain the first mixture；
(3) pH value of the first mixture is adjusted to 1-2 with the hydrochloric acid solution of 6mol/L, then be added thereto to 50mL deionizations
Water, continues reaction 20h, obtains the second mixture under 30 DEG C of water-baths；
(4) by the second mixture at 120 DEG C crystallization 18h, obtain the 3rd mixture；
(5) by the 3rd mixture filtering and washing to neutrality, 12h, then the roasting 4h at 550 DEG C are then dried at 100 DEG C
Obtain Si modification alumina product (be designated as sample A) of the surface rich in B-acid.
Embodiment 2
A kind of preparation method of Si modification aluminium oxide is present embodiments provided, also, has been obtained to pore volume using the method
There is the Si modification aluminium oxide of improvement with surface B-acid content, concrete preparation process includes：
(1) 22g boehmites are added in 50mL deionized waters and are beaten 5-10min, boehmite serosity is obtained；
To in boehmite serosity, the hydrochloric acid solution of the 6mol/L of Deca 5mL makes which be acidified peptization, and 1h is persistently stirred after completion of dropping,
Obtain boehmite colloidal sol；
(2) first to Deca 12g Ludox in above-mentioned boehmite colloidal sol, obtain the first mixture；
(3) pH value of the first mixture is adjusted to 5-6 with ammonia spirit, then be added thereto to 50mL deionized waters, 30 DEG C
Continue reaction 20h under water-bath, obtain the second mixture；
(4) by the second mixture at 120 DEG C crystallization 18h, obtain the 3rd mixture；
(5) by the 3rd mixture filtering and washing to neutrality, 12h, then the roasting 4h at 550 DEG C are then dried at 100 DEG C
Obtain Si modification alumina product (being designated as sample B).
Embodiment 3
A kind of preparation method of Si modification aluminium oxide is present embodiments provided, also, big pore volume has been obtained using the method
Si modification aluminium oxide, concrete preparation process include：
(1) 22g boehmites are added in 50mL deionized waters and are beaten 5-10min, boehmite serosity is obtained；
To in boehmite serosity, the hydrochloric acid solution of the 6mol/L of Deca 5mL makes which be acidified peptization, and 1h is persistently stirred after completion of dropping,
Obtain boehmite colloidal sol；
(2) first to Deca 12g Ludox in above-mentioned boehmite colloidal sol, obtain the first mixture；
(3) pH value of the first mixture is adjusted to 10-11 with ammonia spirit, then be added thereto to 50mL deionized waters, 30
Continue reaction 20h under DEG C water-bath, obtain the second mixture；
(4) by the second mixture at 120 DEG C crystallization 18h, obtain the 3rd mixture；
(5) by the 3rd mixture filtering and washing to neutrality, 12h, then the roasting 4h at 550 DEG C are then dried at 100 DEG C
Obtain big pore volume Si modification alumina product (being designated as sample C).
Embodiment 4
A kind of preparation method of Si modification aluminium oxide is present embodiments provided, also, big pore volume has been obtained using the method
Si modification aluminium oxide, concrete preparation process include：
(1) 22g boehmites are added in 50mL deionized waters and are beaten 5-10min, boehmite serosity is obtained；
To in boehmite serosity, the hydrochloric acid solution of the 6mol/L of Deca 5mL makes which be acidified peptization, and 1h is persistently stirred after completion of dropping,
Obtain boehmite colloidal sol；
(2) first to Deca 12g Ludox in above-mentioned boehmite colloidal sol, obtain the first mixture；
(3) pH value of the first mixture is adjusted to 10-11 with ammonia spirit, then be added thereto to 50mL deionized waters, 30
Continue reaction 20h under DEG C water-bath, obtain the second mixture；
(4) by the second mixture at 120 DEG C crystallization 18h, obtain the 3rd mixture；
(5) by the 3rd mixture filtering and washing to neutrality, 12h, then the roasting 4h at 450 DEG C are then dried at 100 DEG C
Obtain big pore volume Si modification alumina product (being designated as sample D).
Embodiment 5
A kind of preparation method of Si modification aluminium oxide is present embodiments provided, also, big pore volume has been obtained using the method
Si modification aluminium oxide, concrete preparation process include：
(1) 22g boehmites are added in 50mL deionized waters and are beaten 5-10min, boehmite serosity is obtained；
To in boehmite serosity, the hydrochloric acid solution of the 6mol/L of Deca 5mL makes which be acidified peptization, and 1h is persistently stirred after completion of dropping,
Obtain boehmite colloidal sol；
(2) first to Deca 12g Ludox in above-mentioned boehmite colloidal sol, obtain the first mixture；
(3) pH value of the first mixture is adjusted to 10-11 with ammonia spirit, then be added thereto to 50mL deionized waters, 30
Continue reaction 20h under DEG C water-bath, obtain the second mixture；
(4) by the second mixture at 120 DEG C crystallization 18h, obtain the 3rd mixture；
(5) by the 3rd mixture filtering and washing to neutrality, 12h, then the roasting 4h at 650 DEG C are then dried at 100 DEG C
Obtain big pore volume Si modification alumina product (being designated as sample E).
Test case 1
This test case provides the test experiments of product in embodiment 1-5.
Wherein, Fig. 1 is the XRD figure of silica sol modified aluminium oxide in embodiment 1-3；Fig. 2 changes for Ludox in embodiment 1-3
The nitrogen Adsorption and desorption isotherms figure of property aluminium oxide；Fig. 3 is the graph of pore diameter distribution of silica sol modified aluminium oxide in embodiment 1-3；Fig. 4
For the pyridine adsorption FT-IR spectrogram of silica sol modified aluminium oxide in embodiment 1-3.
In embodiment 1-5, the performance parameter of silica sol modified aluminium oxide is shown in Table 1.
The performance parameter of meso-porous alumina sample of the table 1 rich in B-acid
By table 1, Fig. 1-Fig. 4, the method provided using the present invention can prepare the Si modification oxygen of excellent performance
Change aluminum product, and Si modification alumina sample of the obtained surface rich in B-acid, the ratio of its B/L acid amount can reach 0.92, institute
Obtained big pore volume Si modification alumina sample, its pore volume are up to 1.00cm3/ g, aperture reach 11.9nm.
Claims (10)
1. a kind of preparation method of Si modification aluminium oxide, wherein, the method is comprised the following steps：
(1) acidifying peptization is carried out to boehmite serosity using mineral acid, obtains boehmite colloidal sol；
(2) Ludox is added in the boehmite colloidal sol, obtain the first mixture；
(3) require according to improving the different of degree to the surface B-acid content of aluminium oxide and pore volume, to the in the range of the pH=1-11
The pH value of one mixture is adjusted, and then reaction for a period of time, obtains the second mixture in a heated condition；Mix to first
The rule that the pH value of thing is adjusted is：The raising degree of the lower surface B-acid content to aluminium oxide of pH value is bigger, and pH value is higher
It is bigger to the raising degree of the pore volume of aluminium oxide；
(4) Crystallizing treatment is carried out to second mixture, obtains the 3rd mixture；
(5) the 3rd mixture obtains Si modification aluminium oxide through filter washing, drying, roasting.
2. the preparation method of Si modification aluminium oxide according to claim 1, wherein, the mineral acid in step (1)
Consumption meets following condition：H in mineral acid+With the Al in boehmite serosity3+Mol ratio be 0.03-0.1:1, or make
The pH of boehmite colloidal sol is 2.5-5.0.
3. the preparation method of Si modification aluminium oxide according to claim 1, wherein, carry out being acidified peptization in step (1)
Concrete steps include：The Deca mineral acid in boehmite serosity, continues to react 5- after completion of dropping at 30-90 DEG C
60min。
4. the preparation method of Si modification aluminium oxide according to claim 1, wherein, the Ludox in step (2)
Consumption meets following condition：The Al in Si and boehmite colloidal sol in Ludox3+Mol ratio be 0.1-0.3:1.
5. the preparation method of Si modification aluminium oxide according to claim 1, wherein, to the first mixture in step (3)
When pH value is adjusted, the reagent for using is mineral acid or inorganic base；
The mineral acid includes the combination of one or more in hydrochloric acid, nitric acid and sulphuric acid；
The inorganic base includes the combination of one or more in potassium hydroxide, sodium hydroxide and ammonia.
6. the preparation method of Si modification aluminium oxide according to claim 1, wherein, in step (3), when laying particular emphasis on raising
During the surface B-acid content of aluminium oxide, the pH value of the first mixture is adjusted to into pH=1-2；
When the pore volume for improving aluminium oxide is laid particular emphasis on, the pH value of the first mixture is adjusted to into pH=10-11.
7. the preparation method of Si modification aluminium oxide according to claim 1, wherein, the Crystallizing treatment in step (4)
Condition be：Crystallization 12-24h at 100-120 DEG C.
8. the preparation method of Si modification aluminium oxide according to claim 1, wherein, the condition of the roasting of step (5)
For：Roasting 4-6h at 450-650 DEG C.
9. Si modification aluminium oxide obtained in the method by described in claim 1-8 any one；
Preferably, the Si modification aluminium oxide is Si modification aluminium oxide of the surface rich in B-acid or big pore volume Si modification aluminium oxide；Institute
The B/L for stating Si modification aluminium oxide of the surface rich in B-acid is 40-95%, and the pore volume of the big pore volume Si modification aluminium oxide is 0.8-
1.2cm3/g。
10. using catalyst obtained in the Si modification aluminium oxide as substrate or carrier described in claim 9；Preferably, it is described to urge
Agent includes catalytic cracking catalyst or hydrogenation catalyst.
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