CN117699834A - Mesoporous pseudo-boehmite with surface rich in hydroxyl groups and preparation method thereof - Google Patents
Mesoporous pseudo-boehmite with surface rich in hydroxyl groups and preparation method thereof Download PDFInfo
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- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 title claims abstract description 92
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 230000032683 aging Effects 0.000 claims abstract description 82
- 239000011148 porous material Substances 0.000 claims abstract description 29
- 238000001935 peptisation Methods 0.000 claims abstract description 10
- 239000002002 slurry Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 24
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 19
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 230000000284 resting effect Effects 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 238000004364 calculation method Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 3
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 20
- 239000011734 sodium Substances 0.000 abstract description 13
- 238000005406 washing Methods 0.000 abstract description 13
- 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 abstract description 12
- 229910052708 sodium Inorganic materials 0.000 abstract description 12
- 239000001569 carbon dioxide Substances 0.000 abstract description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 10
- 238000001035 drying Methods 0.000 abstract description 6
- 239000012065 filter cake Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 238000004523 catalytic cracking Methods 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- -1 aluminum oxide compound Chemical class 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000020477 pH reduction Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000190022 Pilea cadierei Species 0.000 description 1
- 235000009470 Theobroma cacao Nutrition 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 244000240602 cacao Species 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003921 oil 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
- 238000005504 petroleum refining Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Catalysts (AREA)
Abstract
A mesoporous pseudo-boehmite with rich hydroxyl groups on the surface and a preparation method thereof, wherein the pseudo-boehmite has a critical pore diameter of more than 4.5nm and not more than 12nm and I 3000～3800 6.0cm ‑1 ·mg ‑1 ～8.5cm ‑1 ·mg ‑1 . The preparation method comprises the following steps: and (3) reacting the sodium metaaluminate solution with carbon dioxide gas, carrying out staged aging under the hydrothermal condition of existence of a hydroxyl regulator, washing and drying. The pseudo-boehmite prepared by the invention has high crystallinity, large grain size, large pore diameter, abundant surface hydroxyl groups and good peptization performance.
Description
Technical field:
the invention relates to a mesoporous pseudo-boehmite with a surface rich in hydroxyl groups and a preparation method thereof.
Background
The chemical formula of the pseudo-boehmite is AlOOH.nH 2 O(0<n<1) Is an aluminum oxide compound with water content greater than boehmite and grain size smaller than boehmite. It is a crystalline phase which is easy to generate in the process of synthesizing aluminum hydroxide, the crystallization is incomplete, and the typical crystal form is very thin wrinkled lamellar crystal.
The preparation method of pseudo-boehmite mainly comprises an aluminum alkoxide hydrolysis method, a precipitation method and the like, and the precipitation method is divided into an acid method and an alkali method. The aluminum alkoxide hydrolysis method takes aluminum metal and higher alcohols (n-amyl alcohol, n-hexyl alcohol and isopropyl alcohol) as raw materials, aluminum alkoxide is formed by reacting the aluminum metal with the alcohols in the presence of a catalyst, and then the aluminum alkoxide is hydrolyzed to obtain pseudo-boehmite. But the method has high production cost and complex production process. The alkali precipitation method is a method for preparing pseudo-boehmite by utilizing alkali to neutralize and precipitate acidic aluminum salt, and the common aluminum salt comprises Al 2 (SO 4 ) 3 ，Al(NO 3 ) 3 ,AlCl 3 And the like, the common alkali precipitants are NaOH and NH 3 ·H 2 O、NaAlO 2 、Na 2 CO 3 Etc. The acid precipitation method is a method for preparing pseudo-boehmite by neutralizing and precipitating alkaline aluminate, which is typically sodium aluminate, with acid which may be strong acid (HNO) 3 、H 2 SO 4 Etc.) may be a weak acid (NH 4 HCO 3 、NaHCO 3 Etc.) and CO 2 Etc. Wherein NaAlO 2 -CO 2 The method is also called carbonization method, the carbonization method can be used for producing alumina by sintering method, and intermediate product NaAlO is utilized 2 Solution and aluminium plant exhaust gas CO 2 As a reaction raw material, the process is simple, byproducts, waste liquid and the like in the production process can be returned to the production flow of the alumina for recycling, and the method is the method with the lowest cost for industrially producing the pseudo-boehmite at present.
Pseudo-boehmite in petroleum refining andthe catalyst is widely applied to petrochemical industry, and is commonly used as a binder of a catalytic cracking catalyst and a hydrogenation catalyst carrier (gamma-Al 2 O 3 ) Is a precursor of (a). Pseudoboehmite is an important raw material in semi-synthetic catalytic cracking catalysts. The pseudo-boehmite has good bonding property after acidification, and can also form a specific mesoporous structure after the catalyst is prepared and formed.
The pseudo-boehmite prepared by the conventional carbonization method has low crystallinity, can have a pore diameter of only 3.8nm, and can only provide a mesoporous structure of 3.8nm when being prepared into a catalytic cracking catalyst. The catalytic cracking raw material has larger molecular size and is obviously hindered from diffusing in a pore canal of 3.8 nm. This impediment limits efficient diffusion and conversion of heavy oil feedstock molecules, which is detrimental to reducing coke yield and improving product distribution. At present, the application of pseudo-boehmite prepared by a carbonization method in a catalytic cracking catalyst can provide larger pore size distribution, but the pseudo-boehmite with larger pore size has poor wear resistance, and a pore structure with larger pore size can not be directly formed after acidification.
The invention comprises the following steps:
one of the technical problems to be solved by the invention is to provide the mesoporous pseudo-boehmite with good bonding performance, which is rich in surface hydroxyl groups. The second technical problem to be solved by the invention is to provide a preparation method of the pseudo-boehmite.
The invention provides a pseudo-boehmite, the pore diameter of the pseudo-boehmite is more than 4.5nm and not more than 12nm, I 3000～3800 6.0cm -1 ·mg -1 ～8.5cm -1 ·mg -1 ，I 3000～3800 Is expressed in the wavelength of 3000cm of infrared light -1 ～3800cm -1 Infrared absorption intensity of hydroxyl groups on pseudo-boehmite surface within the range I 3000～3800 The calculation method of (C) is that the sample is at 3000cm -1 ～3800cm -1 The ratio of the area of the absorption peak to the mass of the sample in the range.
Preferably, the pseudo-boehmite provided by the invention has the grain size D (130) Is greater than 4nm to 10nm, preferably 5nm to 8.5nm, for example 5.1 to 8.5nm or 5.5 to 8.5nm or6-8.2 nm. Preferably, the invention provides the D of the pseudo-boehmite (130) /D (020) The value of =1.0 to 1.5 is, for example, 1.1 to 1.4 or 1.2 to 1.35, preferably 1.1 to 1.3. The pseudo-boehmite can keep larger pore diameter after acidification.
Wherein D is (130) Represents the grain size, D, of a crystal face represented by a (130) peak (corresponding to 2θ=38.3°) in an XRD spectrum of pseudo-boehmite grains (020) The crystal grain size of the crystal face represented by the (020) peak (corresponding to 2θ=14.1°) in the XRD spectrum of pseudo-boehmite crystal grain is represented.
The pseudo-boehmite provided by the invention can have a pore diameter of more than 4.5nm and less than 12nm, preferably 4.8 nm-11 nm, such as 5-10nm or 5.5-9 nm or 6-8.5nm or 7-9nm. The aperture refers to the diameter of the hole.
The crystallinity of the pseudo-boehmite provided by the invention is 85% -110%, preferably 88% -108%, for example 90% -105%.
The pore volume of the pseudo-boehmite provided by the invention is 0.30cm 3 /g～0.58cm 3 Per g, preferably 0.31cm 3 /g～0.52cm 3 For example, 0.33 to 0.5cm 3 /g。
The pseudo-boehmite provided by the invention is I 3000～3800 6.0cm -1 ·mg -1 ～8.5/cm -1 ·mg -1 For example, 6.2 to 8.3cm -1 ·mg -1 。
The peptization index of the pseudo-boehmite provided by the invention is 90% -100%, preferably 93% -99%.
The invention provides a preparation method of pseudo-boehmite, which comprises the following steps:
(1) By bringing sodium aluminate solution with CO 2 Reacting to generate first slurry;
(2) Aging the first slurry under a certain condition, and adding a hydroxyl regulator in the aging process, wherein the hydroxyl regulator is urea and/or ammonia water to obtain aged slurry, namely second slurry, and the aging temperature is more than 100 ℃ and not more than 185 ℃;
(3) The slurry after aging is filtered, washed and dried.
The preparation method of pseudo-boehmite according to the invention, wherein in the step (1), the concentration of the sodium aluminate solution is Al 2 O 3 Preferably 5 to 60g/L. The sodium aluminate solution may be commercially available or prepared according to existing methods, and in one embodiment, the sodium aluminate solution is prepared by a method comprising: reacting aluminium hydroxide with alkali liquor at 90-120 deg.C for 1-4 h, diluting to Al 2 O 3 The concentration is 5-60 g/L. The lye is for example sodium hydroxide solution. The caustic ratio of the sodium metaaluminate solution is, for example, 1.0 to 3.2.
According to the method for preparing pseudo-boehmite of the invention, in the step (1), sodium aluminate solution and CO are mixed 2 Contact reaction, CO-containing can be introduced into the sodium metaaluminate solution 2 Is reacted with a gas containing CO 2 CO in gas 2 The volume concentration of (2) is 20 to 100%, for example 40 to 100%.
According to the preparation method of pseudo-boehmite, sodium aluminate solution and CO 2 The pH value of the reaction end point is 8.5-10.5.
According to the method for preparing pseudo-boehmite of the present invention, in the step (1), the reaction initiation temperature is preferably 10 to 35℃and the temperature at the reaction end is preferably 15 to 55 ℃.
According to the method for preparing pseudo-boehmite, the step (1) comprises the steps of mixing sodium aluminate solution with CO 2 Contact reaction of sodium aluminate solution with CO 2 The reaction time of the reaction is preferably 20 to 70 minutes.
In one embodiment, in step (1), the sodium aluminate solution is mixed with CO 2 The reaction conditions include 10-35 deg.c initial temperature, 15-55 deg.c final temperature and 20-70 min reaction time. Sodium aluminate solution and CO 2 The pH value of the reaction end point is 8.5-10.5. Preferably, the sodium aluminate solution is mixed with CO 2 Reacting sodium aluminate solution with CO-containing 2 Is a gas contact reaction of the above-mentioned catalyst, said catalyst contains CO 2 CO in the gas of (a) 2 The volume concentration of (2) is 20-100%.
Preferably, in step (2), the aging is performed under the following conditions: aging at rest, and stirringAging under stirring; the pseudo-boehmite obtained by the method has a grain size D (130) ＝4nm～10nm，D (130) /D (020) 1.0 to 1.5. May have a higher cocoa aperture.
In step (2), the first slurry is aged under conditions, in one embodiment at a temperature of 100 to 185 ℃, preferably 120 to 160 ℃ or 135 to 160 ℃. The first slurry may be heated to 100 to 185 c, preferably 120 to 160 c or 135 to 160 c, and then aged at that temperature. Preferably, the first slurry is raised from the reaction endpoint temperature to the aging temperature for no more than 60 minutes. Preferably, the temperature from the start of ageing to the end of ageing is carried out at a constant temperature, by which is meant that the temperature of the resting ageing and the stirring ageing is controlled to be constant, for example, the resting ageing and the stirring ageing preferably differ by not more than 2 ℃.
In the step (2), the aging pressure is preferably 0.2 to 1MPa.
In the step (2), the stirring speed is controlled to be 50-400 r/min. The stirring can be carried out by adopting the existing stirring method, and the aging slurry is driven by a stirring paddle to rotate in the aging kettle.
In the step (2), the aging time of the aging is preferably 2 to 10 hours.
In the step (2), the mixture is firstly aged at a certain temperature in a static state and then is aged under stirring. The static aging is performed without stirring during aging, so that the slurry is in a static state, for example, the slurry can be subjected to static aging. Preferably, the first slurry is first left to stand and age at the aging temperature for 1 to 4 hours, for example 2 to 3 hours, and then stirred and aged at the aging temperature for 1 to 6 hours. The stirring speed may be 50 to 400r/min, for example 60 to 400r/min.
In one embodiment, in the step (2), the first slurry is aged under certain conditions, the aging temperature is 100-185 ℃, and the pressure is 0.2-1 MPa, and the reaction is carried out for 2-10 hours at constant temperature for aging; wherein the first slurry is firstly kept stand and aged for 1 to 4 hours, for example, 2 to 3 hours, then the aging temperature and pressure are kept, stirring is applied, the stirring speed is controlled to be 50 to 400r/min, for example, 60 to 400r/min, and the stirring aging time is 1 to 6 hours.
Step (2) adding a hydroxyl modifier, preferably ureaOr ammonia water, the addition amount is 0.5-2 wt% of the alumina content in the pseudo-boehmite. The concentration of the ammonia water (NH 3 Calculated as) is 15 to 25 weight percent.
Preferably, the hydroxyl modifier is stopped with CO in step (1) 2 After the reaction, the mixture was added before aging with stirring. Typically, the hydroxyl modifier is added after a period of resting aging, such as during resting aging or after resting aging has ended and before agitation aging has begun.
And (3) filtering, washing and drying the aged slurry to obtain the macroporous pseudo-boehmite with the surface rich in hydroxyl groups and specific pore size distribution. Through static aging and stirring aging, the crystal with specific crystal characteristics and grain size D (130) Is greater than 4nm to 10nm, such as 4.5-9nm or 5-8nm, D (130) /D (020) =1.0 to 1.5, e.g. 1.1 to 1.3. In one embodiment, the washing condition is that deionized water with the temperature of 70-100 ℃ is used for washing until the pH value of the wet filter cake is 7-7.5. The drying temperature is preferably 60 to 98 ℃, for example 70 to 98 ℃, preferably 70 to 95 ℃, and the drying time is for example 2 to 4 hours.
The pseudo-boehmite provided by the invention has rich surface hydroxyl groups, larger pore diameter, higher crystallinity and good peptization property. The pseudo-boehmite provided by the invention has good bonding property, and can reduce the coke selectivity of hydrocarbon oil conversion when being applied to a catalytic cracking catalyst.
The preparation method of pseudo-boehmite provided by the invention is environment-friendly, low in cost and easy to implement, and fills the blank of the pseudo-boehmite technology suitable for catalytic cracking catalysts produced by a carbonization method. The pseudo-boehmite with better binding property and higher pore size distribution can be obtained, and the pseudo-boehmite has high crystallinity, large grain size, specific crystal structure and good peptization.
The pseudo-boehmite provided by the invention can be used for preparing a catalyst, and after acidification, the obtained catalyst can have larger pore diameter and better strength, for example, the pseudo-boehmite is used for preparing a catalytic cracking catalyst, and can be directly acidified without hole expanding treatment to obtain the catalytic cracking catalyst with larger pore diameter, for example, the pore diameter of more than 5nm and better wear resistance.
Compared with the existing pseudo-boehmite, the pseudo-boehmite can provide more mesoporous structures, has higher pore diameters, better catalyst strength (lower attrition index), lower coke selectivity of the obtained catalytic cracking catalyst and better product distribution, for example, can lead to higher yields of liquefied gas and gasoline.
Detailed Description
The following examples further illustrate the invention but are not intended to limit it.
In the present application, the crystallinity and the grain size D of the sample are measured by X-ray powder diffraction (XRD) and are measured by the standard methods of RIPP145-90 and RIPP146-90 (see, e.g., petrochemical analysis methods (RIPP test methods) Yang Cuiding, published by science publishers, 1990). The crystallinity of the sample was calculated from the (130 crystal plane) peak at 2θ=38.3°. According to the Scherrer formulaThe grain size is calculated, where k=1.075, λ is the anode radiation kα 1 The wavelength of the spectral line, beta, is the half-width of a particular diffraction peak of pseudo-boehmite, and theta is the Bragg diffraction angle of the diffraction peak. D (D) (130) Indicating the grain size of the sample in the direction perpendicular to the (130) plane,/and> β 130 is the half-width of the diffraction peak of the sample (130). D (D) (020) Represents the grain size of the sample in a plane perpendicular to the (020) plane, ->β 020 The half-width of the diffraction peak of the sample (020).
In the present application, the distribution of the cells and the cell volume (cell bodyProduct) is determined by a low-temperature nitrogen static capacity adsorption method, a specific surface area and a pore volume are calculated by using a two-parameter BET formula, pore size distribution is calculated by using a BJH formula, and the pore size corresponding to the highest point of a pore size distribution curve is the fractional pore size of a sample. The sample was 1.33X10 using ASAP 2405N V1.01 automatic adsorber from Micromeritics, USA -2 Vacuum degassing at 300 deg.C under Pa for 4 hr, and mixing with N 2 The adsorption-desorption isotherms of the samples were determined at 77.4K for the adsorption media.
In this application, determination of peptization index: weighing 10 g of pseudo-boehmite, roasting for 3 hours at 600 ℃, placing in a drier for cooling, cooling to room temperature, and weighing to obtain W 0 Gram to give dry basis a 0 ＝W 0 Weighing pseudo-boehmite by weight m 1 ＝6/a 0 Gram, will weigh m 1 Placing the pseudo-boehmite into a 100mL polytetrafluoroethylene cup, adding deionized water to 40 g, uniformly stirring by using a magnetic rotor, adding 20mL of 0.19N dilute nitric acid solution, magnetically stirring for 20 minutes, pouring all the solution into a centrifuge tube, placing into the centrifuge, and centrifugally separating for 20 minutes at a rotation speed of 1900 rpm. Pouring the upper colloid solution, placing in a weighed crucible, drying at 80deg.C, roasting at 600deg.C for 3 hr, cooling in a drier, cooling to room temperature, and weighing to obtain m 2 Gram, peptization index di= (m) 2 /6)*100％。
In the present application, I 3000～3800 The measuring method comprises the following steps: infrared hydroxyl groups of the samples were measured using a Nicolet 6700 fourier transform infrared spectrometer manufactured by Thermo Fisher, usa, under the following conditions: resolution of 4.0cm -1 Scanning range of 400cm -1 ～4000cm -1 . Samples all need to be under high vacuum 1.0X10 -3 Purifying for 2h under Pa and 450 ℃. I 3000～3800 The calculation method of (C) is that the sample has a wavelength of 3000cm in infrared light -1 ～3800cm -1 The ratio of the area of the infrared absorption peak of the hydroxyl group on the surface of pseudo-boehmite to the mass of the sample in the range.
Sodium metaaluminate, caustic ratio 1, analytically pure, produced by Shanghai microphone Biochemical technology Co.
Example 1
Concentration of 20gAl 2 O 3 The sodium metaaluminate solution/L is subjected to gel forming reaction with 40% carbon dioxide gas (wherein the carbon dioxide gas is 40% in volume fraction and the balance is nitrogen gas), and the final PH value is controlled to be 9.5. After transferring the obtained slurry to an aging kettle, standing and aging for 3 hours at 135 ℃ and 0.35MPa, adding 0.8 weight percent (based on the weight of the slurry based on the mass of aluminum oxide) of urea, starting stirring under the conditions of maintaining temperature and pressure, maintaining the stirring speed at 150r/min, and continuously aging for 1 hour. And after the aging is finished, carrying out solid-liquid separation on the obtained slurry, and continuously washing with deionized water at 85 ℃ for half an hour until the pH value of the wet filter cake is 7.1, thereby obtaining the pseudo-boehmite wet filter cake with impurities removed. The wet cake was dried at 80℃for 3 hours and pulverized to give pseudo-boehmite powder S1, the physicochemical properties of which are shown in Table 1.
Example 2
Concentration of 45gAl 2 O 3 Sodium metaaluminate solution/L with a volume fraction of 60% carbon dioxide gas (CO 2 60% by volume and the balance nitrogen) and controlling the end point pH value to 10.3. After transferring the obtained slurry to an aging kettle, standing and aging for 2.5h at 180deg.C under 1.0MPa, adding 1.5% (based on the mass of alumina in the slurry) ammonia water (ammonia water concentration is NH) 3 20 wt.%) then stirring was started, the stirring rate was kept at 450r/min and the mixture was aged for 1 hour at 180℃and 1.0 MPa. And after the aging is finished, carrying out solid-liquid separation on the obtained slurry, and continuously washing with deionized water at 95 ℃ for half an hour until the pH value of the wet filter cake is 7.3, thereby obtaining the pseudo-boehmite wet filter cake with impurities removed. The wet cake was dried at 90℃for 4 hours and crushed to give pseudo-boehmite powder S2, the physicochemical properties of which are shown in Table 1.
Example 3
Concentration of 8gAl 2 O 3 Sodium metaaluminate solution/L with 35% carbon dioxide gas (CO) 2 35% by volume, the balance nitrogen) and controlling the end point pH value to 9.2. After transferring the obtained slurry to an aging tank, 1.8% (based on the mass of alumina) of ammonia water (ammonia water concentration: NH) was added 3 20 wt%) and uniformly stirring, then standing and ageing at 120 deg.C under 0.2MPa for 3.5 hr, then holding temperature and making it implementStirring is started under the conditions of the pressure of 120 ℃ and 0.2MPa, the stirring speed is kept at 120r/min, and the aging is carried out for 2.5 hours. And after the aging is finished, carrying out solid-liquid separation on the obtained slurry, and continuously washing with deionized water at 75 ℃ for half an hour until the pH value of the wet filter cake is 7.2, thereby obtaining the pseudo-boehmite wet filter cake with impurities removed. The wet cake was dried at 75℃for 4 hours and crushed to give pseudo-boehmite powder S3, the physicochemical properties of which are shown in Table 1.
Example 4
Concentration of 15gAl 2 O 3 Sodium metaaluminate solution/L with 50% by volume of carbon dioxide gas (CO 2 50% by volume, the balance nitrogen) and controlling the end point PH to 9.9. After transferring the obtained slurry to an aging kettle, adding 1.8% (based on the mass of the alumina) of urea, standing and aging for 4 hours at 150 ℃ and 0.48MPa, then stirring at the temperature and pressure of 150 ℃ and 0.48MPa, maintaining the stirring speed of 250r/min, and aging for 3 hours. And after the aging is finished, carrying out solid-liquid separation on the obtained slurry, and continuously washing with deionized water at 80 ℃ for half an hour until the pH value of the wet filter cake is 7.2, thereby obtaining the pseudo-boehmite wet filter cake with impurities removed. The wet cake was dried at 85℃for 4 hours and crushed to give pseudo-boehmite powder S4, the physicochemical properties of which are shown in Table 1.
Example 5
Concentration of 55gAl 2 O 3 Sodium metaaluminate solution/L with a volume fraction of 90% carbon dioxide gas (CO 2 90% by volume, the balance nitrogen) and controlling the end point pH value to 10.3. After transferring the obtained slurry to an aging tank, 0.7% (based on the mass of alumina) of ammonia water (ammonia water concentration: NH) was added 3 20 wt.%) at 160 deg.C and 0.62MPa, standing and ageing for 6 hr, then under the condition of maintaining 160 deg.C and 0.62MPa, stirring, maintaining stirring rate at 350r/min and ageing for 4.5 hr. And after the aging is finished, carrying out solid-liquid separation on the obtained slurry, and continuously washing with deionized water at 90 ℃ for half an hour until the pH value of the wet filter cake is 7.2, thereby obtaining the pseudo-boehmite wet filter cake with impurities removed. The wet cake was dried at 95℃for 4 hours and pulverized to give pseudo-boehmite powder S5, the physicochemical properties of which are shown in Table 1.
Comparative example 1
Concentration of 20gAl 2 O 3 And (3) carrying out gelling reaction on the sodium metaaluminate solution/L and carbon dioxide gas with the volume fraction of 40%, and controlling the end point PH value to be 9.5. After transferring the obtained slurry to an aging kettle, standing and aging for 3 hours at 90 ℃, carrying out solid-liquid separation on the obtained slurry after aging, continuously washing with deionized water at 78 ℃ for half an hour to obtain a product filter cake with impurities removed, drying for 3 hours at 90 ℃, and crushing to obtain pseudo-boehmite powder D1, wherein the physicochemical properties are shown in Table 1.
Comparative example 2
Concentration of 20gAl 2 O 3 And (3) carrying out gelling reaction on the sodium metaaluminate solution/L and carbon dioxide gas with the volume fraction of 40%, and controlling the end point PH value to be 9.5. After transferring the obtained slurry to an aging kettle, standing and aging for 3.5 hours at 135 ℃ and 0.35 MPa. And after the aging is finished, carrying out solid-liquid separation on the obtained slurry, and continuously washing with deionized water at 80 ℃ for half an hour to obtain the pseudo-boehmite wet filter cake with impurities removed. The wet cake was dried at 80℃for 3 hours and pulverized to give pseudo-boehmite powder D2, the physicochemical properties of which are shown in Table 1.
Comparative example 3
With Al 2 O 3 45g/L high-purity sodium aluminate solution is taken as raw material, and CO with the concentration of 40 percent is introduced 2 Performing gel forming reaction, controlling the flow rate per hour to be 3.0m 3 Reaction time is controlled to be 40 minutes, and Al is controlled 2 O 3 5g/l remained and the final temperature was controlled at 35 ℃. The slurry after the reaction was subjected to separation washing, and the filter cake was washed with high purity water at 85 ℃ until the filter cake pH was 7.0. Adding high-purity water into the obtained filter cake, stirring, adding urea with the concentration of 8g/L, stirring for 50min, transferring the slurry into high-pressure kettle equipment, controlling the kettle temperature to be 150 ℃, controlling the pressure to be 0.6MPa, standing and aging for 3h. After the aging, the mixture is washed continuously with deionized water at 85 ℃ for half an hour, filtered and dried at 90 ℃. The final product pseudo-boehmite D3 is obtained by crushing, and the physicochemical properties are shown in Table 1.
Comparative example 4
Concentration of 45gAl 2 O 3 Sodium metaaluminate solution/L with a volume fraction of 60% carbon dioxide gas (CO 2 60% by volume and the balance nitrogen) and controlling the end point pH value to 10.3. After transferring the obtained slurry to an aging kettle, maintaining the stirring rate at 180 ℃ and 1.0MPa450r/min, and aging for 3.5h. And after the aging is finished, carrying out solid-liquid separation on the obtained slurry, and continuously washing with deionized water at 95 ℃ for half an hour until the pH value of the wet filter cake is 7.3, thereby obtaining the pseudo-boehmite wet filter cake with impurities removed. The wet cake was dried at 90℃for 4 hours and crushed to give pseudo-boehmite powder D4, the physicochemical properties of which are shown in Table 1.
TABLE 1 pseudo-boehmite properties
* Acidification conditions: acid aluminium ratio (concentration 36 wt% HCl: al) 2 O 3 Mass ratio) of 0.2, the solid content of the acidified mixture being 10% by weight; the roasting temperature is 550 ℃, and the roasting time is 2 hours.
As can be seen from Table 1, the pseudo-boehmite provided by the invention has rich surface hydroxyl groups, larger pore diameter, higher crystallinity, larger grain size, larger D (130)/D (020), better peptization performance, and still larger pore diameter of the baked sample after peptization.
Claims (12)
1. A mesoporous pseudo-boehmite with rich hydroxyl groups on the surface, the pore diameter of the pseudo-boehmite is more than 4.5nm and not more than 12nm, I 3000～3800 6.0cm -1 ·mg -1 ～8.5cm -1 ·mg -1 ，I 3000～3800 Is expressed in the wavelength of 3000cm of infrared light -1 ～3800cm -1 Infrared absorption intensity of hydroxyl groups on pseudo-boehmite surface within the range I 3000～3800 The calculation method of (C) is that the sample is at 3000cm -1 ～3800cm -1 The ratio of the area of the absorption peak to the mass of the sample in the range.
2. Pseudo-boehmite according to claim 1 characterized in that the pseudo-boehmite has a pore size of preferably 4.8 nm-11 nm, for example 5 nm-10 nm.
3. Pseudo-boehmite according to claim 1 or 2 characterized in that the grain size D of the pseudo-boehmite (130) ＝4nm～10nm, preferably 5-8.5 nm; d (D) (130) /D (020) 1.0 to 1.5, the pseudo-boehmite is D (130) /D (020) Preferably 1.1 to 1.3.
4. A pseudo-boehmite according to claim 1, 2 or 3 wherein the crystallinity of the pseudo-boehmite is from 85% to 110%; the crystallinity of the pseudo-boehmite is preferably 88% -108%; the peptization index of the pseudo-boehmite is 90% -100%, and the peptization index is 93% -99%; the pore volume of the pseudo-boehmite is 0.3cm 3 /g～0.58cm 3 For example 0.31cm 3 /g～0.52cm 3 /g。
5. A method for preparing pseudo-boehmite, comprising the following steps:
(1) By bringing sodium aluminate solution with CO 2 Reacting to form a first slurry;
(2) Aging the first slurry under a certain condition, and adding a hydroxyl regulator in the aging process, wherein the hydroxyl regulator is urea and/or ammonia water to obtain aged slurry, and the aging temperature is above 100 ℃ and not more than 185 ℃; preferably, the conditions are ageing: firstly standing and aging, and then aging under stirring;
(3) The slurry after aging is filtered, washed and dried.
6. The method according to claim 5, wherein in step (1), the sodium aluminate solution is mixed with CO 2 The pH value of the reaction end point is 8.5-10.5, and the Al of the sodium aluminate solution 2 O 3 The concentration is 5-60 g/L.
7. The method according to claim 5 or 6, wherein in step (1), the sodium aluminate solution is mixed with CO 2 The reaction conditions include introducing CO into sodium aluminate solution 2 CO-containing at a concentration of 20% to 100% by volume 2 The gas is reacted, the initial temperature of the reaction is 10-35 ℃, and the final temperature of the reaction is preferably 15-55 ℃.
8. The method according to claim 5, 6 or 7, wherein the slurry in step (2) is aged at a temperature of 100 to 185 ℃ and at a pressure of 0.2 to 1Mpa for a time of 2 to 10 hours.
9. A method according to claim 5 or 8, wherein in step (2) the resting ageing time is from 1 to 4 hours, for example from 2 to 3 hours, and the ageing time is from 1 to 6 hours with stirring; the stirring speed of the stirring aging can be 50-400 r/min.
10. A method according to claim 5, 6, 7, 8 or 9, characterized in that the aging temperature is 120-160 ℃, the aging preferably being constant temperature aging.
11. A method according to any of claims 5-10, characterized in that the hydroxyl modifier is added after a period of rest ageing, before stirring ageing, for example during rest ageing or before stirring ageing starts after the end of rest ageing; the hydroxyl modifier comprises 0.5 to 2 weight percent of the first slurry calculated as alumina; wherein the concentration of ammonia in the aqueous ammonia is preferably 15 to 25% by weight.
12. Use of pseudo-boehmite according to any one of claims 1-4 in the preparation of a catalyst.
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| TW112133142A TW202411163A (en) | 2022-08-31 | 2023-08-31 | Mesoporous pseudo-boehmite having hydroxyl-rich surface, catalytic cracking catalyst containing pseudo-boehmite, and preparation and use thereof |
| PCT/CN2023/116100 WO2024046421A1 (en) | 2022-08-31 | 2023-08-31 | Mesoporous pseudo-boehmite having hydroxyl-rich surface, catalytic cracking catalyst containing pseudo-boehmite, and preparation and use thereof |
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