CN114057211A - Preparation method of aluminum oxide material - Google Patents
Preparation method of aluminum oxide material Download PDFInfo
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- CN114057211A CN114057211A CN202010728985.5A CN202010728985A CN114057211A CN 114057211 A CN114057211 A CN 114057211A CN 202010728985 A CN202010728985 A CN 202010728985A CN 114057211 A CN114057211 A CN 114057211A
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- 239000000463 material Substances 0.000 title claims abstract description 23
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 178
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 42
- 239000007864 aqueous solution Substances 0.000 claims abstract description 41
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 35
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000032683 aging Effects 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- 230000002378 acidificating effect Effects 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000009826 distribution Methods 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 43
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 10
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 8
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 2
- 159000000013 aluminium salts Chemical class 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000000295 fuel oil Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- 125000004817 pentamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000011164 primary particle Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 39
- 238000003756 stirring Methods 0.000 description 33
- 239000002253 acid Substances 0.000 description 20
- 239000003513 alkali Substances 0.000 description 19
- 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 18
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 18
- 229910052708 sodium Inorganic materials 0.000 description 18
- 239000011734 sodium Substances 0.000 description 18
- 239000013078 crystal Substances 0.000 description 13
- 230000001276 controlling effect Effects 0.000 description 11
- 239000008213 purified water Substances 0.000 description 11
- 239000012429 reaction media Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 230000005653 Brownian motion process Effects 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005537 brownian motion Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
Abstract
The invention discloses a preparation method of an aluminum oxide material, which comprises the following steps: (1) adding a certain amount of organic solvent and metal salt into a reaction container, adding an acidic aluminum salt aqueous solution I and a basic aluminum salt aqueous solution I in a concurrent flow manner under the conditions of low temperature and high pressure, carrying out neutralization gelling reaction, and separating sol from the organic solvent after the reaction is finished; (2) adding a certain amount of bottom water into a reaction container, then adding the sol obtained in the step (1), mixing, and adding an acidic aluminum salt aqueous solution II and a basic aluminum salt aqueous solution II in a concurrent flow manner at a certain temperature and under a certain pressure to perform neutralization gelling reaction; (3) and after the gelling reaction is finished, carrying out aging reaction on the reaction system at high temperature and high pressure, and filtering, drying and roasting the aged material to obtain the aluminum oxide material. The invention prepares the alumina material with concentrated particle size distribution, high crystallinity and larger specific surface and pore volume by controlling the size and the crystallinity of primary particles, and can be used in the fields of catalysis, adsorption and the like.
Description
Technical Field
The invention belongs to the field of inorganic material preparation, and particularly relates to a preparation method of an aluminum oxide material.
Background
Precipitation refers to the process of chemical reaction in the liquid phase to form insoluble substances and form a new solid phase to settle out of the liquid phase. From the classic theory of precipitation, the process of precipitate formation is divided into: 1) and (3) crystal nucleus generation: the molecules in the local region are clustered due to the continuous collisional motion of the molecules or ions, and the clustering is not only due to the collisions between the moving particles in the solution. And adhere to each other again by weak acting force (van der waals force), and also generate chemical bonds through crystals, and the aggregate is solidified; 2) and (3) crystal nucleus growth: the colloid is uniform, the particles are fine, and the nucleation and the crystal growth are very powerful. The cluster molecular particles contact each other and are combined to grow up. Since the aggregation rate is greater than the orientation rate, it is less orderly arranged at the faster aggregation rate to form amorphous particles, which gradually change into orderly arranged crystals by dehydration condensation during aging of the precipitate. The coprecipitation method is a typical method for preparing aluminum hydroxide. The method is characterized in that water is used as a medium, raw materials are prepared into aluminum salt, then certain solution concentration, solution flow rate, temperature and reaction time are controlled, and acid/alkali is used for neutralization. But the coprecipitated product is in particular Al (OH)3
The surface hydrophilic hydroxyl group (and water molecules are combined in the surface hydrophilic hydroxyl group), the high temperature easily causes the violent molecular Brownian motion, the particles are easy to cluster, the molecular polarity is small, and the solubility is very micro, so the aggregation rate is far greater than the orientation rate, amorphous gelatinous precipitate is easy to generate, the crystallinity is low, the crystal form is incomplete, and the pore structure is not ideal.
CN103789390A discloses a preparation method of pseudo-boehmite, which comprises the following steps: (1) carrying out gelling reaction on the acidic aluminum salt solution and the alkaline compound, and then aging; carrying out gelling reaction and aging under the condition of ultrasonic radiation, wherein ultrasonic waves with different frequencies are adopted in the gelling reaction process and the aging process, and the ultrasonic waves with the frequency of 10-160 kHz are adopted in the gelling reaction process; the ultrasonic frequency adopted in the aging process is 1-50 KHz higher than that in the gelling reaction process; (2) filtering and washing the aged material; (3) and (3) drying the material obtained in the step (2) to obtain the pseudo-boehmite.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of an aluminum oxide material. The alumina material with concentrated particle size distribution, high crystallinity, large specific surface area and large pore volume is prepared by controlling the size and crystallinity of the primary particles, and can be used in the fields of catalysis, adsorption and the like.
The preparation method of the aluminum oxide material comprises the following steps:
(1) adding a certain amount of organic solvent and metal salt into a reaction container, adding an acidic aluminum salt aqueous solution I and a basic aluminum salt aqueous solution I in a concurrent flow manner under the conditions of low temperature and high pressure, carrying out neutralization gelling reaction, and separating sol from the organic solvent after the reaction is finished; (2) adding a certain amount of bottom water into a reaction container, then adding the sol obtained in the step (1), mixing, and adding an acidic aluminum salt aqueous solution II and a basic aluminum salt aqueous solution II in a concurrent flow manner at a certain temperature and under a certain pressure to perform neutralization gelling reaction; (3) and after the gelling reaction is finished, carrying out aging reaction on the reaction system at high temperature and high pressure, and filtering, drying and roasting the aged material to obtain the aluminum oxide material.
In the method of the invention, the reaction vessel is a pressure-resistant vessel, and a high-pressure reaction kettle can be generally selected.
In the method, the organic solvent in the step (1) is one or more of alkane, alkene, organic alcohol or organic acid which is not miscible with water or slightly soluble in water; wherein the alkane is of the formula CnH2n+2(n.gtoreq.5) one or more alkanes, preferably one or more of pentane, hexane or dodecane; wherein the olefin is of the formula CnH2n(n.gtoreq.5) one or more olefins; preferably penteneAnd/or hexene; the organic alcohol has a molecular formula of CnH2n+2Monohydric alcohol of O (n is more than or equal to 6) and molecular formula of CnH2n+2-x(OH)x(x.gtoreq.3) one or more of polyols, preferably one or more of n-hexanol, n-heptanol, glycerol; the organic acid is one or more of aliphatic and/or aromatic carboxylic acid, such as benzoic acid and the like.
In the method, the adding amount of the organic solvent in the step (1) is 1/5-1/2 of the volume of the reaction vessel.
In the method, the metal salt in the step (1) is one or more of AgCl, ZnS, CuS or HgS; the addition amount of the metal salt is the Al in the acidic aluminum salt and the basic aluminum salt in the step (1)2O30.1 to 5%, preferably 0.5 to 2% by mass of (A).
In the method, the low-temperature and high-pressure conditions in the step (1) are as follows: the temperature is-15 ℃, preferably 0-15 ℃, and the pressure is 1-10 MPa, preferably 5-10 MPa; the pH value of the neutralization gelling reaction in the step (1) is 2-6, preferably 2-5, and the reaction time is 10-180 minutes, preferably 10-60 minutes. The reaction is preferably carried out under the condition of stirring, and the stirring speed is 100-500 rad/min, preferably 150-500 rad/min.
In the method, the acidic aluminum salt aqueous solution I in the step (1) is AlCl3、Al2(SO4)3Or Al (NO)3One or more of aqueous solutions, preferably Al2(SO4)3And/or AlCl3Aqueous solution, acidic aluminium salt aqueous solution with concentration of Al2O310-100 g/100mL, and the flow rate is 10-80 mL/min; the alkaline aluminum salt aqueous solution is selected from NaAlO2Or KAlO2One or two of the aqueous solutions, preferably NaAlO2Aqueous solution, alkaline aluminum salt aqueous solution with concentration of Al2O310-100 g/100mL, and 10-80 mL/min.
In the method of the invention, the particle size distribution of the sol obtained by separation in the step (1) is as follows: the proportion of the grain diameter less than 50nm is 0.5-1%, the proportion of the grain diameter between 50nm and 100nm is 2-5%, and the proportion of the grain diameter more than 100nm is 94-97%; the degree of crystallization is not less than 95%.
In the method, the amount of the bottom water added in the step (2) is 1/5-1/2 of the volume of the reaction vessel.
In the method, the reaction temperature in the step (2) is 100-300 ℃, preferably 150-250 ℃, the reaction pressure is 5-15 MPa, preferably 10-15 MPa, and the reaction pressure in the step (2) is 1-5 MPa higher than that in the step (1). The step (2) is carried out under the condition of stirring, and the stirring speed is 100-500 rad/min, preferably 200-500 rad/min.
In the method, the acidic aluminum salt aqueous solution II in the step (2) is AlCl3、Al2(SO4)3Or Al (NO)3One or more of the above aqueous solutions, preferably Al2(SO4)3And/or AlCl3The concentration of the aqueous solution II of acidic aluminum salt is Al2O310-100 g/100mL, and the flow rate is 10-80 mL/min; the alkaline aluminum salt aqueous solution II is selected from NaAlO2Or KAlO2One or two of the aqueous solutions, preferably NaAlO2Aqueous solution, alkaline aluminum salt aqueous solution with concentration of Al2O310-100 g/100mL, and 10-80 mL/min. The pH value of the neutralization gelling reaction in the step (2) is 7-11, preferably 7-10, and the reaction pH value in the step (2) is 2-5 higher than that in the step (1); the neutralization and gelling reaction time is 60-120 minutes.
In the method of the invention, the aging reaction conditions in the step (3) are as follows: the temperature is 300-500 ℃, the aging pressure is 15-20 MPa, and the aging time is 60-360 minutes. The aging temperature in the step (3) is 100-250 ℃ higher than the reaction temperature in the step (2); the aging is carried out under the condition of stirring, and the stirring speed is preferably 500-800 r/min.
In the method, the drying temperature in the step (3) is 100-450 ℃, preferably 150-400 ℃, the drying time is 1-10 hours, and the drying mode can be flash drying, cyclone drying, oven drying, spray drying and the like; the roasting temperature is 300-800 ℃, preferably 350-550 ℃, and the roasting time is 2-5 hours, preferably 2-4 hours.
The invention also provides an alumina material, which has the following properties: the pore volume is 0.95-1.2 mL/g-1(ii) a The specific surface area is 290-350 m2·g-1(ii) a The pore diameter is not less than 80nm, preferably 80-100 nm; a degree of crystallization of not less than 90%, preferably 95% to 99%; the particle size distribution is concentrated and is as follows: the proportion of the grain diameter less than 50 mu m is 0.5-1%, the proportion of the grain diameter between 50 and 100 mu m is 2-5%, and the proportion of the grain diameter more than 100 mu m is 94-97%.
The aluminum oxide material can be used in the fields of catalysis, adsorption and the like, and is particularly suitable for preparing a heavy oil hydrotreating catalyst.
Compared with the prior art, the invention has the following advantages:
1. because of the coating of hydrophilic hydroxyl on the surface of the aluminum hydroxide hydrosol, the aluminum hydroxide hydrosol is easy to polymerize into giant molecules through hydroxyl bridges and precipitate to form gel. In the method, an organic solvent which is not miscible with water or slightly soluble in water is used as a reaction medium, and neutralization reaction is carried out by controlling pressure and temperature, so that on one hand, the aluminum hydroxide hydrosol generated by neutralization forms hydrophobic sol due to the existence of the organic solvent which is not miscible with water around, and mutual adhesion and aggregation of particles are avoided; on the other hand, under the pressure and temperature conditions in the step (1), the aggregation of sol-gel molecules or ions due to collision is reduced;
2. in the method, in the gel forming process, polar molecules or ions with small molecules, large polarity and larger orientation speed are used as seed crystals to ensure that gel particles are directionally arranged into ordered crystal precipitates or colloidal particles with crystal structures; then a small amount of amorphous aluminum hydroxide is dissolved under the condition of lower pH value, namely acid condition, and the generated ordered arrangement pseudo-boehmite is retained;
3. in the method, a large number of particles with complete crystal forms are aggregated to form pseudo-boehmite and precipitate under the conditions of high temperature, high pressure and high pH value of the sol particles with complete crystal forms obtained in the step (1), and meanwhile, the generation of alumina trihydrate is avoided; the precipitated pseudoboehmite particles with complete crystal forms are subjected to aging reaction under the conditions of high pressure and high temperature, so that the aluminum oxide material with high crystallization purity, large pores, concentrated pore size distribution and concentrated particle size distribution is finally formed.
Detailed Description
In the method, the specific surface area and the pore volume are measured by adopting a low-temperature liquid nitrogen adsorption method; the particle size distribution is measured by a laser particle size distribution instrument; the crystallinity was determined by X-ray diffraction (XRD).
The method for producing alumina of the present invention is described in more detail below by way of specific examples. The examples are merely illustrative of specific embodiments of the process of the present invention and do not limit the scope of the invention.
Example 1
Adding 2L of n-hexanol serving as a reaction medium into a 10L high-pressure reaction kettle, adding 1.6g of AgCl, adjusting the pressure of the high-pressure reaction kettle to 5MPa, adjusting the reaction temperature to 10 ℃, and adjusting the stirring speed to 200 rad/min. After the mixture is uniformly stirred, an acid liquor feed port and an alkali liquor feed port at the upper end of the high-pressure reaction kettle are opened, the flow rates of an aluminum sulfate solution with the concentration of 20g/100mL and a sodium metaaluminate solution with the concentration of 10g/100mL are respectively controlled to be 20mL/min and 15mL/min, the pH value of the reaction is adjusted to be 2.5, after the neutralization reaction is carried out for 15min, the organic solvent and the sol in the high-pressure reaction kettle are separated, and the property of the sol A is shown in table 1.
Adding the sol into the high-pressure reaction kettle, adding 2.5L of purified water into the high-pressure reaction kettle, adjusting the pressure of the high-pressure reaction kettle to 10MPa, the reaction temperature to 180 ℃, and the stirring speed to 300 rad/min. Opening an acid liquor feed port and an alkali liquor feed port at the upper end of the high-pressure reaction kettle, controlling the flow rates of the aluminum sulfate solution with the concentration of 20g/100mL and the sodium metaaluminate solution with the concentration of 10g/100mL to be 15mL/min and 20mL/min respectively, adjusting the pH value of the reaction to be 7.5, and carrying out neutralization reaction for 60 min.
After the neutralization reaction is finished, the pressure of a high-pressure reaction kettle is adjusted to be 15MPa, the reaction temperature is 280 ℃, the stirring speed is 500rad/min, after aging is carried out for 120min, filtration is carried out, drying is carried out for 4h at 150 ℃, and roasting is carried out for 3h at 400 ℃ to obtain the required alumina A, wherein the properties of the alumina A are shown in Table 2.
Example 2
Adding 2.5L of cyclohexane serving as a reaction medium into a 10L high-pressure reaction kettle, adding 9g of AgCl, adjusting the pressure of the high-pressure reaction kettle to be 4MPa, adjusting the reaction temperature to be 0 ℃, and stirring at the speed of 300 rad/min. After the mixture is uniformly stirred, an acid liquor feed port and an alkali liquor feed port at the upper end of the high-pressure reaction kettle are opened, the flow rates of an aluminum sulfate solution with the concentration of 30g/100mL and a sodium metaaluminate solution with the concentration of 25g/100mL are respectively controlled to be 30mL/min and 25mL/min, the pH value of the reaction is adjusted to be 5.0, after the neutralization reaction is carried out for 30min, the organic solvent and the sol in the high-pressure reaction kettle are separated, and the property of the sol B is shown in table 1.
Adding the sol into the high-pressure reaction kettle, adding 2.5L of purified water into the high-pressure reaction kettle, adjusting the pressure of the high-pressure reaction kettle to 12MPa, the reaction temperature to 150 ℃, and the stirring speed to 500 rad/min. Opening an acid liquor feed port and an alkali liquor feed port at the upper end of the high-pressure reaction kettle, controlling the flow rates of the aluminum sulfate solution with the concentration of 30g/100mL and the sodium metaaluminate solution with the concentration of 25g/100mL to be 20mL/min and 30mL/min respectively, adjusting the pH value of the reaction to be 10.0, and carrying out a neutralization reaction for 120 min.
After the neutralization reaction is finished, the pressure of the high-pressure reaction kettle is adjusted to be 20MPa, the reaction temperature is 250 ℃, the stirring speed is 500rad/min, after aging is 120min, the required alumina B is obtained by filtering, drying is carried out for 5h at 180 ℃, and roasting is carried out for 4h at 350 ℃, and the properties of the alumina B are shown in Table 2.
Example 3
5L of benzoic acid is added into a 10L high-pressure reaction kettle to be used as a reaction medium, 13g of AgCl is added, the pressure of the high-pressure reaction kettle is adjusted to be 8MPa, the reaction temperature is 15 ℃, and the stirring speed is 250 rad/min. After the mixture is uniformly stirred, an acid liquor feed port and an alkali liquor feed port at the upper end of the high-pressure reaction kettle are opened, the flow rates of an aluminum sulfate solution with the concentration of 40g/100mL and a sodium metaaluminate solution with the concentration of 35g/100mL are respectively controlled to be 20mL/min and 10mL/min, the pH value of the reaction is adjusted to be 4.5, after the neutralization reaction is carried out for 60min, the organic solvent and the sol in the high-pressure reaction kettle are separated, and the property of the sol C is shown in table 1.
Adding the sol into the high-pressure reaction kettle, adding 2.5L of purified water into the high-pressure reaction kettle, adjusting the pressure of the high-pressure reaction kettle to 12MPa, the reaction temperature to 200 ℃, and the stirring speed to 400 rad/min. Opening an acid liquor feed port and an alkali liquor feed port at the upper end of the high-pressure reaction kettle, controlling the flow rates of an aluminum sulfate solution with the concentration of 25g/100mL and a sodium metaaluminate solution with the concentration of 30g/100mL to be 10mL/min and 25mL/min respectively, adjusting the pH value of the reaction to be 9.5, and carrying out a neutralization reaction for 100 min.
After the neutralization reaction is finished, the pressure of the high-pressure reaction kettle is adjusted to be 15MPa, the reaction temperature is 300 ℃, the stirring speed is 400rad/min, after aging is 240min, the required alumina C is obtained by filtering, drying at 200 ℃ for 3h and roasting at 500 ℃ for 4h, and the properties of the alumina C are shown in Table 2.
Example 4
4L of styrene is added into a 10L high-pressure reaction kettle as a reaction medium, 6.18g of AgCl is added, the pressure of the high-pressure reaction kettle is adjusted to be 9MPa, the reaction temperature is adjusted to be 5 ℃, and the stirring speed is adjusted to be 300 rad/min. After the mixture is uniformly stirred, an acid liquor feed port and an alkali liquor feed port at the upper end of the high-pressure reaction kettle are opened, the flow rates of an aluminum sulfate solution with the concentration of 50g/100mL and a sodium metaaluminate solution with the concentration of 25g/100mL are respectively controlled to be 20mL/min and 15mL/min, the pH value of the reaction is adjusted to be 3.5, after the neutralization reaction is carried out for 45min, the organic solvent and the sol in the high-pressure reaction kettle are separated, and the property of the sol D is shown in table 1.
Adding the sol into the high-pressure reaction kettle, adding 2.5L of purified water into the high-pressure reaction kettle, adjusting the pressure of the high-pressure reaction kettle to 15MPa, the reaction temperature to 190 ℃, and the stirring speed to 450 rad/min. Opening an acid liquor feed port and an alkali liquor feed port at the upper end of the high-pressure reaction kettle, controlling the flow rates of the aluminum sulfate solution with the concentration of 30g/100mL and the sodium metaaluminate solution with the concentration of 45g/100mL to be 25mL/min and 40mL/min respectively, adjusting the pH value of the reaction to be 8.5, and carrying out neutralization reaction for 80 min.
After the neutralization reaction is finished, the pressure of the high-pressure reaction kettle is adjusted to be 20MPa, the reaction temperature is 400 ℃, the stirring speed is 500rad/min, after aging is carried out for 360min, the required alumina D is obtained by filtering, drying is carried out for 2h at 180 ℃, and roasting is carried out for 3h at 400 ℃, and the properties of the alumina D are shown in Table 2.
Comparative example 1
4L of styrene is added into a 10L high-pressure reaction kettle as a reaction medium, the pressure of the high-pressure reaction kettle is adjusted to be 5MPa, the reaction temperature is adjusted to be 5 ℃, and the stirring speed is adjusted to be 300 rad/min. After the mixture is uniformly stirred, an acid liquor feed port and an alkali liquor feed port at the upper end of the high-pressure reaction kettle are opened, the flow rates of an aluminum sulfate solution with the concentration of 50g/100mL and a sodium metaaluminate solution with the concentration of 25g/100mL are respectively controlled to be 20mL/min and 15mL/min, the pH value of the reaction is adjusted to be 3.5, after the neutralization reaction is carried out for 45min, the organic solvent and the sol in the high-pressure reaction kettle are separated, and the property of the sol E is shown in table 1.
Adding the sol into the high-pressure reaction kettle, adding 2.5L of purified water into the high-pressure reaction kettle, adjusting the pressure of the high-pressure reaction kettle to 15MPa, the reaction temperature to 190 ℃, and the stirring speed to 450 rad/min. Opening an acid liquor feed port and an alkali liquor feed port at the upper end of the high-pressure reaction kettle, controlling the flow rates of the aluminum sulfate solution with the concentration of 30g/100mL and the sodium metaaluminate solution with the concentration of 45g/100mL to be 25mL/min and 40mL/min respectively, adjusting the pH value of the reaction to be 8.5, and carrying out neutralization reaction for 80 min.
After the neutralization reaction is finished, the pressure of the high-pressure reaction kettle is adjusted to be 20MPa, the reaction temperature is 400 ℃, the stirring speed is 500rad/min, after aging is carried out for 360min, the required alumina E is obtained by filtering, drying is carried out for 2h at 180 ℃, and roasting is carried out for 3h at 400 ℃, and the properties of the alumina E are shown in Table 2.
Comparative example 2
4L of purified water is added into a 10L high-pressure reaction kettle as a reaction medium, the pressure of the high-pressure reaction kettle is adjusted to be 4MPa, the reaction temperature is adjusted to be 5 ℃, and the stirring speed is adjusted to be 300 rad/min. After the mixture is uniformly stirred, an acid liquor feed port and an alkali liquor feed port at the upper end of the high-pressure reaction kettle are opened, the flow rates of an aluminum sulfate solution with the concentration of 50g/100mL and a sodium metaaluminate solution with the concentration of 25g/100mL are respectively controlled to be 20mL/min and 15mL/min, the reaction pH value is adjusted to be 3.5, after neutralization reaction is carried out for 45min, sol is separated, and the properties of the sol F are shown in table 1.
Adding the sol into the high-pressure reaction kettle, adding 2.5L of purified water into the high-pressure reaction kettle, adjusting the pressure of the high-pressure reaction kettle to 12MPa, the reaction temperature to 190 ℃, and the stirring speed to 450 rad/min. Opening an acid liquor feed port and an alkali liquor feed port at the upper end of the high-pressure reaction kettle, controlling the flow rates of the aluminum sulfate solution with the concentration of 30g/100mL and the sodium metaaluminate solution with the concentration of 45g/100mL to be 25mL/min and 40mL/min respectively, adjusting the pH value of the reaction to be 8.5, and carrying out neutralization reaction for 80 min.
After the neutralization reaction is finished, the pressure of the high-pressure reaction kettle is adjusted to be 20MPa, the reaction temperature is 400 ℃, the stirring speed is 500rad/min, after aging is carried out for 360min, the required alumina F is obtained by filtering, drying is carried out for 2h at 180 ℃, and roasting is carried out for 3h at 400 ℃, and the properties of the alumina F are shown in Table 2.
Comparative example 3
4L of purified water is added into a 10L high-pressure reaction kettle as a reaction medium, the pressure of the high-pressure reaction kettle is adjusted to be 5MPa, the reaction temperature is 100 ℃, and the stirring speed is 300 rad/min. After the mixture is uniformly stirred, an acid liquor feed port and an alkali liquor feed port at the upper end of the high-pressure reaction kettle are opened, the flow rates of an aluminum sulfate solution with the concentration of 50G/100mL and a sodium metaaluminate solution with the concentration of 25G/100mL are respectively controlled to be 20mL/min and 15mL/min, the pH value of the reaction is adjusted to be 3.5, after the neutralization reaction is carried out for 45min, the sol is separated, and the properties of the sol G are shown in table 1.
Adding the sol into the high-pressure reaction kettle, adding 2.5L of purified water into the high-pressure reaction kettle, adjusting the pressure of the high-pressure reaction kettle to 15MPa, the reaction temperature to 190 ℃, and the stirring speed to 450 rad/min. Opening an acid liquor feed port and an alkali liquor feed port at the upper end of the high-pressure reaction kettle, controlling the flow rates of the aluminum sulfate solution with the concentration of 30g/100mL and the sodium metaaluminate solution with the concentration of 45g/100mL to be 25mL/min and 40mL/min respectively, adjusting the pH value of the reaction to be 8.5, and carrying out neutralization reaction for 80 min.
After the neutralization reaction is finished, the pressure of the high-pressure reaction kettle is adjusted to be 20MPa, the reaction temperature is 400 ℃, the stirring speed is 500rad/min, after aging is carried out for 360min, the required alumina G is obtained by filtering, drying is carried out for 2h at 180 ℃, and roasting is carried out for 3h at 400 ℃, and the properties of the alumina G are shown in Table 2.
Comparative example 4
4L of styrene is added into a 10L high-pressure reaction kettle to be used as a reaction medium, 6.18g of AgCl is added, the pressure and the normal pressure of the high-pressure reaction kettle are regulated, the reaction temperature is 120 ℃, and the stirring speed is 300 rad/min. After the mixture is uniformly stirred, an acid liquor feed port and an alkali liquor feed port at the upper end of the high-pressure reaction kettle are opened, the flow rates of an aluminum sulfate solution with the concentration of 50g/100mL and a sodium metaaluminate solution with the concentration of 25g/100mL are respectively controlled to be 20mL/min and 15mL/min, the pH value of the reaction is adjusted to be 3.5, after the neutralization reaction is carried out for 45min, the organic solvent and the sol in the high-pressure reaction kettle are separated, and the property of the sol H is shown in table 1.
Adding the sol into the high-pressure reaction kettle, adding 2.5L of purified water into the high-pressure reaction kettle, adjusting the pressure of the high-pressure reaction kettle to 12MPa, the reaction temperature to 190 ℃, and the stirring speed to 450 rad/min. Opening an acid liquor feed port and an alkali liquor feed port at the upper end of the high-pressure reaction kettle, controlling the flow rates of the aluminum sulfate solution with the concentration of 30g/100mL and the sodium metaaluminate solution with the concentration of 45g/100mL to be 25mL/min and 40mL/min respectively, adjusting the pH value of the reaction to be 8.5, and carrying out neutralization reaction for 80 min.
After the neutralization reaction is finished, the pressure of the high-pressure reaction kettle is adjusted to be 20MPa, the reaction temperature is 400 ℃, the stirring speed is 500rad/min, after aging is carried out for 360min, the required alumina H is obtained by filtering, drying is carried out for 2H at 180 ℃, and roasting is carried out for 3H at 400 ℃, and the properties of the alumina H are shown in Table 2.
Comparative example 5
4L of styrene is added into a 10L high-pressure reaction kettle to be used as a reaction medium, 6.18g of AgCl is added, the pressure of the high-pressure reaction kettle is adjusted to be 10MPa, the reaction temperature is adjusted to be 5 ℃, and the stirring speed is adjusted to be 300 rad/min. After the mixture is uniformly stirred, an acid liquor feed port and an alkali liquor feed port at the upper end of the high-pressure reaction kettle are opened, the flow rates of an aluminum sulfate solution with the concentration of 50g/100mL and a sodium metaaluminate solution with the concentration of 25g/100mL are respectively controlled to be 20mL/min and 15mL/min, the pH value of the reaction is adjusted to be 3.5, after the neutralization reaction is carried out for 45min, the organic solvent and the sol in the high-pressure reaction kettle are separated, and the property of the sol I is shown in table 1.
Adding the sol into the high-pressure reaction kettle, adding 2.5L of purified water into the high-pressure reaction kettle, adjusting the pressure of the high-pressure reaction kettle to 15MPa, the reaction temperature to 190 ℃, and the stirring speed to 450 rad/min. Opening an acid liquor feed port and an alkali liquor feed port at the upper end of the high-pressure reaction kettle, controlling the flow rates of the aluminum sulfate solution with the concentration of 30g/100mL and the sodium metaaluminate solution with the concentration of 45g/100mL to be 25mL/min and 40mL/min respectively, adjusting the pH value of the reaction to be 8.5, and carrying out neutralization reaction for 80 min.
After the neutralization reaction is finished, the pressure and the normal pressure of the high-pressure reaction kettle are adjusted, the reaction temperature is 70 ℃, the stirring speed is 500rad/min, after aging is carried out for 360min, the required alumina I is obtained by filtering, drying is carried out for 2h at 180 ℃, and roasting is carried out for 3h at 400 ℃, and the properties of the alumina I are shown in Table 2.
TABLE 1 Sol Properties in examples and comparative examples
TABLE 2 properties of alumina in examples and comparative examples
As can be seen from tables 1 and 2, the method of the present invention uses a sol with high crystallinity and concentrated particle size distribution as a crystal, and the prepared alumina has larger pore diameter and pore volume, higher specific surface area, larger crystallinity and concentrated particle size distribution.
Claims (21)
1. The preparation method of the aluminum oxide material is characterized by comprising the following steps of: (1) adding a certain amount of organic solvent and metal salt into a reaction container, adding an acidic aluminum salt aqueous solution I and a basic aluminum salt aqueous solution I in a concurrent flow manner under the conditions of low temperature and high pressure, carrying out neutralization gelling reaction, and separating sol from the organic solvent after the reaction is finished; (2) adding a certain amount of bottom water into a reaction container, then adding the sol obtained in the step (1), mixing, and adding an acidic aluminum salt aqueous solution II and a basic aluminum salt aqueous solution II in a concurrent flow manner at a certain temperature and under a certain pressure to perform neutralization gelling reaction; (3) and after the gelling reaction is finished, carrying out aging reaction on the reaction system at high temperature and high pressure, and filtering, drying and roasting the aged material to obtain the aluminum oxide material.
2. The method of claim 1, wherein: the organic solvent in the step (1) is one or more of alkane, alkene, organic alcohol or organic acid which is not miscible with water or slightly soluble in water.
3. The method of claim 2, wherein: the alkane has a molecular formula of CnH2n+2(n.gtoreq.5) one or more alkanes, preferably one or more pentane, hexane or dodecane; olefin having the formula CnH2n(n.gtoreq.5) one or more of olefins, preferably pentenes and/or hexenes; the organic alcohol has a molecular formula of CnH2n+2Monohydric alcohol of O (n is more than or equal to 6) and molecular formula of CnH2n+2-x(OH)x(x.gtoreq.3) polyolsPreferably one or more of n-hexanol, n-heptanol, glycerol; the organic acid is one or more of aliphatic and/or aromatic carboxylic acid.
4. The method of claim 1, wherein: in the step (1), the adding amount of the organic solvent is 1/5-1/2 of the volume of the reaction vessel.
5. The method of claim 1, wherein: the metal salt in the step (1) is one or more of AgCl, ZnS, CuS or HgS.
6. The method of claim 1, wherein: the addition amount of the metal salt is the Al in the acidic aluminum salt and the basic aluminum salt in the step (1)2O30.1 to 5%, preferably 0.5 to 2% by mass of (A).
7. The method of claim 1, wherein: the low-temperature and high-pressure conditions of the step (1) are as follows: the temperature is-15 to 15 ℃, preferably 0 to 15 ℃, and the pressure is 1 to 10MPa, preferably 5 to 10 MPa.
8. The method of claim 1, wherein: the pH value of the neutralization gelling reaction in the step (1) is 2-6, and the reaction time is 10-180 minutes.
9. The method of claim 1, wherein: the acidic aluminum salt aqueous solution I in the step (1) is AlCl3、Al2(SO4)3Or Al (NO)3One or more of aqueous solutions, preferably Al2(SO4)3And/or AlCl3Aqueous solution, acidic aluminium salt aqueous solution with concentration of Al2O310-100 g/100mL, and 10-80 mL/min.
10. The method of claim 1, wherein: the alkaline aluminum salt in the step (1) is water-solubleThe liquid is NaAlO2Or KAlO2One or two of the aqueous solutions, preferably NaAlO2Aqueous solution, alkaline aluminum salt aqueous solution with concentration of Al2O310-100 g/100mL, and 10-80 mL/min.
11. The method of claim 1, wherein: the particle size distribution of the sol obtained by separation in the step (1) is as follows: the proportion of the grain diameter less than 50nm is 0.5-1%, the proportion of the grain diameter between 50nm and 100nm is 2-5%, and the proportion of the grain diameter more than 100nm is 94-97%; the degree of crystallization is not less than 95%.
12. The method of claim 1, wherein: the amount of the bottom water added in the step (2) is 1/5-1/2 of the volume of the reaction vessel.
13. The method of claim 1, wherein: the reaction temperature in the step (2) is 100-300 ℃, preferably 150-250 ℃, and the reaction pressure is 5-15 MPa, preferably 10-15 MPa.
14. The method of claim 1, wherein: the reaction pressure in the step (2) is 1-5 MPa higher than that in the step (1).
15. The method of claim 1, wherein: the acidic aluminum salt aqueous solution II in the step (2) is AlCl3、Al2(SO4)3Or Al (NO)3One or more of the above aqueous solutions, preferably Al2(SO4)3And/or AlCl3The concentration of the aqueous solution II of acidic aluminum salt is Al2O310-100 g/100mL, and the flow rate is 10-80 mL/min; the alkaline aluminum salt aqueous solution II is selected from NaAlO2Or KAlO2One or two of the aqueous solutions, preferably NaAlO2Aqueous solution, alkaline aluminum salt aqueous solution with concentration of Al2O310-100 g/100mL, and 10-80 mL/min.
16. The method of claim 1, wherein: the pH value of the neutralization gelling reaction in the step (2) is 7-11; the reaction pH value of the step (2) is 2-5 higher than that of the step (1); the neutralization and gelling reaction time is 60-120 minutes.
17. The method of claim 1, wherein: the aging reaction conditions in the step (3): the temperature is 300-500 ℃, the aging pressure is 15-20 MPa, and the aging time is 60-360 minutes.
18. The method of claim 1, wherein: the aging temperature in the step (3) is 100-250 ℃ higher than the reaction temperature in the step (2).
19. The method of claim 1, wherein: the drying temperature in the step (3) is 100-450 ℃, and the drying time is 1-10 hours; the roasting temperature is 300-800 ℃, and the roasting time is 2-5 hours.
20. An alumina material characterized by: the material has the following properties: the pore volume is 0.95-1.2 mL/g-1(ii) a The specific surface area is 290-350 m2·g-1(ii) a The pore diameter is not less than 80nm, preferably 80-100 nm; a degree of crystallization of not less than 90%, preferably 95% to 99%; the particle size distribution is as follows: the proportion of the grain diameter less than 50 mu m is 0.5-1%, the proportion of the grain diameter between 50 and 100 mu m is 2-5%, and the proportion of the grain diameter more than 100 mu m is 94-97%.
21. Use of the alumina material of claim 20 in the preparation of a heavy oil hydroprocessing catalyst.
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