CN114057211B - Preparation method of alumina material - Google Patents
Preparation method of alumina material Download PDFInfo
- Publication number
- CN114057211B CN114057211B CN202010728985.5A CN202010728985A CN114057211B CN 114057211 B CN114057211 B CN 114057211B CN 202010728985 A CN202010728985 A CN 202010728985A CN 114057211 B CN114057211 B CN 114057211B
- Authority
- CN
- China
- Prior art keywords
- reaction
- pressure
- aluminum salt
- aqueous solution
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 156
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 41
- 239000007864 aqueous solution Substances 0.000 claims abstract description 39
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 33
- 230000032683 aging Effects 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- 238000009826 distribution Methods 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 230000002378 acidificating effect Effects 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
- 238000005755 formation reaction Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 44
- 239000002253 acid Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 7
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 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
- 244000205754 Colocasia esculenta Species 0.000 claims description 4
- 235000006481 Colocasia esculenta Nutrition 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 3
- -1 aromatic carboxylic acids Chemical class 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000000295 fuel oil Substances 0.000 claims description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims 1
- 235000011187 glycerol Nutrition 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000011164 primary particle Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 40
- 239000000243 solution Substances 0.000 description 39
- 239000007788 liquid Substances 0.000 description 38
- 230000001105 regulatory effect Effects 0.000 description 22
- 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
- 230000001276 controlling effect Effects 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 12
- 239000008213 purified water Substances 0.000 description 11
- 239000012429 reaction media Substances 0.000 description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 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
- 238000004220 aggregation Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 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
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 3
- 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
- 238000001354 calcination Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 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
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method 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
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 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
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 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
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 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
- 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
- 239000000126 substance Substances 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 alumina 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 an alkaline aluminum salt aqueous solution I in parallel flow under the conditions of low temperature and high pressure, carrying out neutralization and gel formation 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, adding the sol obtained in the step (1), mixing, and adding an acidic aluminum salt aqueous solution II and an alkaline aluminum salt aqueous solution II in parallel flow at a certain temperature and under a certain pressure to perform neutralization and gel forming reaction; (3) After the gelling reaction is finished, the reaction system is subjected to aging reaction at high temperature and high pressure, and the aged material is filtered, dried and roasted to obtain the alumina 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 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 alumina material.
Background
Precipitation refers to chemical reaction in liquid phaseInsoluble materials and forms a new solid phase which settles out of the liquid phase. From classical theoretical analysis of precipitation, the precipitate formation process is divided into: 1) Nucleation: as molecules or ions continue to collide, molecules in localized areas aggregate into clusters, not only due to collisions between moving particles in solution. And the adhesive is adhered to each other by weak acting force (Van der Waals force), chemical bonds are generated by crystals, and the aggregate is solidified; 2) Crystal nucleus growth: the colloid is uniform, the particles are fine, and the method has very strong effect on nucleation and crystal growth. Cluster molecular particles are contacted with each other and combined to grow. Since the aggregation rate is greater than the orientation rate, the ordered arrangement is less well at the faster aggregation rate, thereby generating amorphous particles, and the dehydration polycondensation gradually turns into ordered arrangement crystals as the precipitate ages. The coprecipitation method is a typical method for preparing aluminum hydroxide. The method is to take water as a medium, prepare the raw materials into aluminum salt, and then control certain solution concentration, solution flow rate, temperature and reaction time, and neutralize with acid/alkali. However, the coprecipitated products are in particular Al (OH) 3
The hydrophilic hydroxyl groups on the surface (water molecules are combined in the hydrophilic hydroxyl groups), the strong molecular Brownian motion is easily caused at high temperature, the aggregation among particles is easy to occur, the molecular polarity is small, the solubility is very tiny, so that the aggregation rate is far greater than the orientation rate, amorphous gelatinous precipitation is easily generated, the crystallinity is low, the crystal form is incomplete, and the pore structure is not ideal.
CN103789390a discloses a preparation method of pseudo-boehmite, comprising the following steps: (1) Performing gel forming reaction on the acidic aluminum salt solution and an alkaline compound, and then aging; the glue forming reaction and aging are carried out under the condition of ultrasonic radiation, ultrasonic waves with different frequencies are adopted in the glue forming reaction process and the aging process, and ultrasonic waves with the frequency of 10-160 kHz are adopted in the glue forming reaction process; the aging process adopts ultrasonic frequency which is 1-50 KHz higher than that of the gel forming reaction process; (2) filtering and washing the aged materials; (3) And (3) drying the material obtained in the step (2) to obtain pseudo-boehmite.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of an alumina material. By controlling the size and crystallinity of primary particles, the alumina material with concentrated particle size distribution, high crystallinity and larger specific surface and pore volume is prepared.
The preparation method of the alumina 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 an alkaline aluminum salt aqueous solution I in parallel flow under the conditions of low temperature and high pressure, carrying out neutralization and gel formation 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, adding the sol obtained in the step (1), mixing, and adding an acidic aluminum salt aqueous solution II and an alkaline aluminum salt aqueous solution II in parallel flow at a certain temperature and under a certain pressure to perform neutralization and gel forming reaction; (3) After the gelling reaction is finished, the reaction system is subjected to aging reaction at high temperature and high pressure, and the aged material is filtered, dried and roasted to obtain the alumina material.
In the method of the invention, the reaction vessel is a pressure-resistant vessel, and a high-pressure reaction vessel can be generally selected.
In the method of the invention, the organic solvent in the step (1) is one or more of alkane, alkene, organic alcohol or organic acid which are not mutually soluble or slightly soluble in water; wherein the alkane has the molecular formula of C n H 2n+2 (n.gtoreq.5) one or more alkanes, preferably one or more pentanes, hexanes or dodecanes, etc.; wherein the olefin has the formula C n H 2n (n.gtoreq.5) one or more olefins; preferably pentene and/or hexene; the molecular formula of the organic alcohol is C n H 2n+2 Monohydric alcohol of O (n is more than or equal to 6) and molecular formula C n H 2n+2-x (OH) x One or more of the polyols of (x.gtoreq.3), preferably one or more of n-hexanol, n-heptanol, glycerol; the organic acid is one or more of aliphatic and/or aromatic carboxylic acids, such as benzoic acid, and the like.
In the method of the invention, the addition amount of the organic solvent in the step (1) is 1/5 to 1/2 of the volume of the reaction vessel.
In the method of the invention, the metal salt in the step (1) is one or more of AgCl, znS, cuS, hgS and the like; the metal salt is added in the amount of Al in the acidic aluminum salt and the alkaline aluminum salt in the step (1) 2 O 3 0.1 to 5%, preferably 0.5 to 2% of the mass of the composition.
In the method of the invention, the low temperature and high pressure conditions in 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 10MPa; the pH value of the neutralization and gel forming 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 stirring at a rate of from 100 to 500rad/min, preferably from 150 to 500rad/min.
In the method of the invention, the acid aluminum salt aqueous solution I in the step (1) is AlCl 3 、Al 2 (SO 4 ) 3 Or Al (NO) 3 One or more of the aqueous solutions, preferably Al 2 (SO 4 ) 3 And/or AlCl 3 Aqueous solution, concentration of acidic aluminum salt aqueous solution is Al 2 O 3 The flow rate is 10-80 mL/min and the flow rate is 10-100 g/100 mL; the alkaline aluminum salt aqueous solution is selected from NaAlO 2 Or KAlO 2 One or two of the aqueous solutions, preferably NaAlO 2 Aqueous solution, alkaline aluminum salt aqueous solution concentration of Al 2 O 3 The flow rate is 10-80 mL/min and the flow rate is 10-100 g/100 mL.
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 particle diameter less than 50nm is 0.5% -1%, the proportion of the particle diameter of 50-100 nm is 2% -5%, and the proportion of the particle diameter more than 100nm is 94% -97%; the crystallinity is less than 95%.
In the method of the invention, the bottom water added in the step (2) is 1/5 to 1/2 of the volume of the reaction vessel.
In the process of the present invention, the reaction temperature in the step (2) is 100 to 300 ℃, preferably 150 to 250 ℃, and the reaction pressure is 5 to 15MPa, preferably 10 to 15MPa, and the reaction pressure in the step (2) is 1 to 5MPa higher than the reaction pressure in the step (1). Step (2) is carried out under stirring at a rate of 100 to 500rad/min, preferably 200 to 500rad/min.
In the method of the invention, the acid aluminum salt aqueous solution II in the step (2) is AlCl 3 、Al 2 (SO 4 ) 3 Or Al (NO) 3 One or more of the aqueous solutions, preferably Al 2 (SO 4 ) 3 And/or AlCl 3 The concentration of the aqueous solution, the acidic aluminum salt aqueous solution II is Al 2 O 3 The flow rate is 10-80 mL/min and the flow rate is 10-100 g/100 mL; the alkaline aluminum salt aqueous solution II is selected from NaAlO 2 Or KAlO 2 One or two of the aqueous solutions, preferably NaAlO 2 Aqueous solution, alkaline aluminum salt aqueous solution concentration of Al 2 O 3 The flow rate is 10-80 mL/min and the flow rate is 10-100 g/100 mL. The pH value of the neutralization gel forming reaction in the step (2) is 7-11, preferably 7-10, and the pH value of the reaction in the step (2) is 2-5 higher than that in the step (1); the neutralization and gel forming reaction time is 60-120 minutes.
In the method of the present invention, the aging reaction conditions of step (3): 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 stirring conditions, preferably at a stirring speed of 500 to 800r/min.
In the method, the drying temperature in the step (3) is 100-450 ℃, preferably 150-400 ℃ and the drying time is 1-10 hours, and the drying mode can be flash evaporation drying, cyclone drying, oven drying, spray drying and the like; the calcination temperature is 300-800 ℃, preferably 350-550 ℃, and the calcination time is 2-5 hours, preferably 2-4 hours.
The invention also provides an alumina material which has the following properties: pore volume is 0.95-1.2 mL g -1 The method comprises the steps of carrying out a first treatment on the surface of the The specific surface area is 290-350 m 2 ·g -1 The method comprises the steps of carrying out a first treatment on the surface of the The pore diameter is not less than 80nm, preferably 80-100 nm; crystallinity not less than 90%, preferably 95% -99%; the particle size distribution is concentrated, and the particle size distribution is as follows: the proportion of the particle size less than 50 mu m is 0.5% -1%, the proportion of the particle size of 50-100 mu m is 2% -5%, and the proportion of the particle size more than 100 mu m is 94% -97%.
The alumina material of the invention can be used in the fields of catalysis, adsorption and the like, and is especially suitable for preparing a heavy oil hydrotreating catalyst.
Compared with the prior art, the invention has the following advantages:
1. because of the wrapping of hydrophilic hydroxyl groups on the surface of the aluminum hydroxide hydrosol, the aluminum hydroxide hydrosol is easy to polymerize into giant molecules through hydroxyl bridges to precipitate and form gel. In the method, an organic solvent which is not mutually soluble or slightly soluble with water is used as a reaction medium, and the neutralization reaction is carried out by controlling the pressure and the temperature, so that on one hand, the aluminum hydroxide hydrosol generated by neutralization forms hydrophobic hydrosol due to the existence of the organic solvent which is not mutually soluble with water around, and the mutual adhesion and aggregation among particles are avoided; on the other hand, under the pressure and temperature conditions of the step (1), the aggregation of sol-gel molecules or ions due to collision is reduced;
2. in the gel forming process, polar molecules or ions with small molecules, large polarity and larger orientation rate are used as seed crystals, so that gel particles are oriented and arranged into ordered crystal precipitation or colloidal particles with a crystal structure; then, a small amount of amorphous aluminum hydroxide is dissolved under the condition of lower pH value, namely acidity, so that the generated ordered pseudo-boehmite is reserved;
3. in the method, a large amount of crystal form complete sol particles are aggregated to form pseudo-boehmite to be precipitated under the conditions of high temperature, high pressure and higher pH value, and meanwhile, the generation of alumina trihydrate is avoided; the precipitated pseudo-boehmite particles with complete crystal forms are subjected to aging reaction under the conditions of high pressure and high temperature, so that the alumina material with high crystal purity, large pore size, 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; crystallinity is determined by X-ray diffraction (XRD).
The method for producing alumina of the present invention will be described in more detail by way of specific examples. The examples are merely illustrative of specific embodiments of the method of the invention and do not constitute a limitation on the scope of the invention.
Example 1
2L of n-hexanol was added as a reaction medium to a 10L autoclave, 1.6g of AgCl was added, the autoclave pressure was adjusted to 5MPa, the reaction temperature was 10℃and the stirring rate was 200rad/min. After stirring uniformly, opening an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the high-pressure reaction kettle, controlling 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 to be respectively 20mL/min and 15mL/min, adjusting the pH value of the reaction to be 2.5, and separating an organic solvent from sol in the high-pressure reaction kettle after neutralization reaction for 15min, wherein the property of 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, regulating the pressure of the high-pressure reaction kettle to 10MPa, reacting at 180 ℃ and stirring at the rate of 300rad/min. Opening an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the high-pressure reaction kettle, controlling 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 to be 15mL/min and 20mL/min respectively, adjusting the pH value of the reaction to 7.5, and carrying out neutralization reaction for 60min.
After the neutralization reaction, the pressure of the high-pressure reaction kettle is regulated to 15MPa, the reaction temperature is 280 ℃, the stirring speed is 500rad/min, the aging is carried out for 120min, and the required aluminum oxide A is obtained after filtering, drying at 150 ℃ for 4h and roasting at 400 ℃ for 3h, and the properties are shown in Table 2.
Example 2
To a 10L autoclave was added.2.5L of cyclohexane as a reaction medium, 9g of AgCl was added, the autoclave pressure was adjusted to 4MPa, the reaction temperature was 0℃and the stirring rate was 300rad/min. After stirring uniformly, opening an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the high-pressure reaction kettle, controlling 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 to be 30mL/min and 25mL/min respectively, adjusting the pH value of the reaction to be 5.0, and separating an organic solvent from sol in the high-pressure reaction kettle after neutralization reaction for 30min, wherein the property of 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, regulating the pressure of the high-pressure reaction kettle to 12MPa, reacting at 150 ℃ and stirring at a rate of 500rad/min. Opening an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the high-pressure reaction kettle, controlling 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 to be respectively 20mL/min and 30mL/min, adjusting the pH value of the reaction to be 10.0, and carrying out neutralization reaction for 120min.
After the neutralization reaction, the pressure of the high-pressure reaction kettle is regulated to 20MPa, the reaction temperature is 250 ℃, the stirring speed is 500rad/min, the aging is carried out for 120min, the required aluminum oxide B is obtained after filtering, drying at 180 ℃ for 5h and roasting at 350 ℃ for 4h, and the properties are shown in Table 2.
Example 3
5L of benzoic acid was added as a reaction medium to a 10L autoclave, 13g of AgCl was added, the autoclave pressure was adjusted to 8MPa, the reaction temperature was 15℃and the stirring rate was 250rad/min. After stirring uniformly, opening an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the high-pressure reaction kettle, controlling 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 to be respectively 20mL/min and 10mL/min, adjusting the pH value of the reaction to be 4.5, and separating an organic solvent from sol in the high-pressure reaction kettle after neutralization reaction for 60min, wherein the property of 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, regulating the pressure of the high-pressure reaction kettle to 12MPa, reacting at 200 ℃, and stirring at 400rad/min. Opening an acid liquid feed inlet and an alkali liquid feed inlet 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 9.5, and carrying out neutralization reaction for 100min.
After the neutralization reaction, the pressure of the high-pressure reaction kettle is regulated to 15MPa, the reaction temperature is 300 ℃, the stirring speed is 400rad/min, the aging is carried out for 240min, and the required aluminum oxide C is obtained after filtering, drying at 200 ℃ for 3h and roasting at 500 ℃ for 4h, and the properties are shown in Table 2.
Example 4
4L of styrene as a reaction medium was added to a 10L autoclave, 6.18g of AgCl was added, the autoclave pressure was adjusted to 9MPa, the reaction temperature was 5℃and the stirring rate was 300rad/min. After stirring uniformly, opening an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the high-pressure reaction kettle, controlling 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 to be respectively 20mL/min and 15mL/min, adjusting the pH value of the reaction to 3.5, and separating an organic solvent from sol in the high-pressure reaction kettle after neutralization reaction for 45min, wherein 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, regulating the pressure of the high-pressure reaction kettle to 15MPa, and reacting at 190 ℃ with the stirring rate of 450rad/min. Opening an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the high-pressure reaction kettle, controlling the flow rates of an aluminum sulfate solution with the concentration of 30g/100mL and a 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 8.5, and carrying out neutralization reaction for 80min.
After the neutralization reaction, the pressure of the high-pressure reaction kettle is regulated to 20MPa, the reaction temperature is 400 ℃, the stirring speed is 500rad/min, the aging is carried out for 360min, the mixture is filtered, dried at 180 ℃ for 2h and baked at 400 ℃ for 3h, and the required aluminum oxide D is obtained, and the properties are shown in Table 2.
Comparative example 1
4L of styrene was added as a reaction medium to a 10L autoclave, the autoclave pressure was adjusted to 5MPa, the reaction temperature was 5℃and the stirring rate was 300rad/min. After stirring uniformly, opening an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the high-pressure reaction kettle, controlling 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 to be respectively 20mL/min and 15mL/min, adjusting the pH value of the reaction to 3.5, and separating an organic solvent from sol in the high-pressure reaction kettle after neutralization reaction for 45min, wherein the property of 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, regulating the pressure of the high-pressure reaction kettle to 15MPa, and reacting at 190 ℃ with the stirring rate of 450rad/min. Opening an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the high-pressure reaction kettle, controlling the flow rates of an aluminum sulfate solution with the concentration of 30g/100mL and a 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 8.5, and carrying out neutralization reaction for 80min.
After the neutralization reaction, the pressure of the high-pressure reaction kettle is regulated to 20MPa, the reaction temperature is 400 ℃, the stirring speed is 500rad/min, the aging is carried out for 360min, the mixture is filtered, dried at 180 ℃ for 2h and baked at 400 ℃ for 3h, and the required aluminum oxide E is obtained, and the properties 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 regulated to be 4MPa, the reaction temperature is 5 ℃, and the stirring speed is 300rad/min. After stirring uniformly, an acid liquid feed inlet and an alkali liquid feed inlet 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 controlled to be 20mL/min and 15mL/min respectively, the pH value of the reaction is regulated to 3.5, after neutralization reaction is carried out for 45min, the sol is separated, and the property of the sol F 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, regulating the pressure of the high-pressure reaction kettle to 12MPa, and reacting at 190 ℃ with the stirring rate of 450rad/min. Opening an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the high-pressure reaction kettle, controlling the flow rates of an aluminum sulfate solution with the concentration of 30g/100mL and a 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 8.5, and carrying out neutralization reaction for 80min.
After the neutralization reaction, the pressure of the high-pressure reaction kettle is regulated to 20MPa, the reaction temperature is 400 ℃, the stirring speed is 500rad/min, the aging is carried out for 360min, the mixture is filtered, dried at 180 ℃ for 2h and baked at 400 ℃ for 3h, and the required aluminum oxide F is obtained, and the properties 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 regulated to 5MPa, the reaction temperature is 100 ℃, and the stirring speed is 300rad/min. After stirring uniformly, an acid liquid feed inlet and an alkali liquid feed inlet 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 controlled to be 20mL/min and 15mL/min respectively, the pH value of the reaction is regulated to 3.5, after neutralization reaction is carried out for 45min, the sol is separated, and the property of the sol G 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, regulating the pressure of the high-pressure reaction kettle to 15MPa, and reacting at 190 ℃ with the stirring rate of 450rad/min. Opening an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the high-pressure reaction kettle, controlling the flow rates of an aluminum sulfate solution with the concentration of 30g/100mL and a 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 8.5, and carrying out neutralization reaction for 80min.
After the neutralization reaction, the pressure of the high-pressure reaction kettle is regulated to 20MPa, the reaction temperature is 400 ℃, the stirring speed is 500rad/min, the aging is carried out for 360min, the mixture is filtered, dried at 180 ℃ for 2h and baked at 400 ℃ for 3h, and the required aluminum oxide G is obtained, and the properties are shown in Table 2.
Comparative example 4
4L of styrene as a reaction medium was added to a 10L autoclave, 6.18g of AgCl was added, the autoclave pressure was adjusted to atmospheric pressure, the reaction temperature was 120℃and the stirring rate was 300rad/min. After stirring uniformly, opening an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the high-pressure reaction kettle, controlling 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 to be respectively 20mL/min and 15mL/min, adjusting the pH value of the reaction to 3.5, and separating an organic solvent from sol in the high-pressure reaction kettle after neutralization reaction for 45min, wherein 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, regulating the pressure of the high-pressure reaction kettle to 12MPa, and reacting at 190 ℃ with the stirring rate of 450rad/min. Opening an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the high-pressure reaction kettle, controlling the flow rates of an aluminum sulfate solution with the concentration of 30g/100mL and a 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 8.5, and carrying out neutralization reaction for 80min.
After the neutralization reaction, the pressure of the high-pressure reaction kettle is regulated to 20MPa, the reaction temperature is 400 ℃, the stirring speed is 500rad/min, the aging is carried out for 360min, the mixture is filtered, dried at 180 ℃ for 2H and baked at 400 ℃ for 3H, and the required aluminum oxide H is obtained, and the properties are shown in Table 2.
Comparative example 5
4L of styrene as a reaction medium was added to a 10L autoclave, 6.18g of AgCl was added, the autoclave pressure was adjusted to 10MPa, the reaction temperature was 5℃and the stirring rate was 300rad/min. After stirring uniformly, opening an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the high-pressure reaction kettle, controlling 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 to be respectively 20mL/min and 15mL/min, adjusting the pH value of the reaction to 3.5, and separating an organic solvent from sol in the high-pressure reaction kettle after neutralization reaction for 45min, wherein the property of the sol I is shown in the table 1.
Adding the sol into the high-pressure reaction kettle, adding 2.5L of purified water into the high-pressure reaction kettle, regulating the pressure of the high-pressure reaction kettle to 15MPa, and reacting at 190 ℃ with the stirring rate of 450rad/min. Opening an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the high-pressure reaction kettle, controlling the flow rates of an aluminum sulfate solution with the concentration of 30g/100mL and a 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 8.5, and carrying out neutralization reaction for 80min.
After the neutralization reaction, the pressure of the high-pressure reaction kettle is regulated to normal pressure, the reaction temperature is 70 ℃, the stirring speed is 500rad/min, the aging is carried out for 360min, the mixture is filtered, dried at 180 ℃ for 2h and baked at 400 ℃ for 3h, and the required aluminum oxide I is obtained, and the properties are shown in Table 2.
Table 1 properties of sol 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 sol with high crystallinity and concentrated particle size distribution as crystal, and the prepared alumina has larger pore diameter and pore volume, higher specific surface area, larger crystallinity and concentrated particle size distribution.
Claims (20)
1. The preparation method of the alumina material is characterized by comprising 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 an alkaline aluminum salt aqueous solution I in parallel flow under the conditions of low temperature and high pressure, carrying out neutralization and gel formation 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, adding the sol obtained in the step (1), mixing, and adding an acidic aluminum salt aqueous solution II and an alkaline aluminum salt aqueous solution II in parallel flow at a certain temperature and under a certain pressure to perform neutralization and gel forming reaction; (3) After the gelling reaction is finished, the reaction system is subjected to aging reaction at high temperature and high pressure, and the aged materials are filtered, dried and roasted to obtain an alumina material; the organic solvent in the step (1) is one or more of alkane, alkene, organic alcohol or organic acid which are not mutually soluble or slightly soluble in water; the metal salt in the step (1) is AgCl; the low temperature and high pressure conditions described in step (1) are: the temperature is-15 to 15 ℃ and the pressure is 1 to 10MPa; the reaction temperature in the step (2) is 100-300 ℃, and the reaction pressure is 5-15 MPa; step (3) the aging reaction conditions: the temperature is 300-500 ℃, the aging pressure is 15-20 MPa, and the aging time is 60-360 minutes.
2. The method according to claim 1, characterized in that: the alkane is of the formula C n H 2n+2 One or more of n is more than or equal to 5 alkane; the olefin has a molecular formula of C n H 2n One or more of n is greater than or equal to 5 olefins; the molecular formula of the organic alcohol is C n H 2n+2 Monohydric alcohol with O, n being more than or equal to 6 and molecular formula of C n H 2n+2-x (OH) x One or more of polyols wherein x is greater than or equal to 3; the organic acid is one or more of aliphatic and/or aromatic carboxylic acids.
3. The method according to claim 1, characterized in that: the alkane is one or more of pentane, hexane or dodecane; the olefin is pentene and/or hexene; the organic alcohol is one or more of n-hexanol, n-heptanol and glycerin.
4. The method according to claim 1, characterized in that: the addition amount of the organic solvent in the step (1) is 1/5-1/2 of the volume of the reaction vessel.
5. The method according to claim 1, characterized in that: the metal salt is added in the amount of Al in the acidic aluminum salt and the alkaline aluminum salt in the step (1) 2 O 3 0.1 to 5 percent of the mass of the composition.
6. The method according to claim 1, characterized in that: the low temperature and high pressure conditions of the step (1) are as follows: the temperature is 0-15 ℃ and the pressure is 5-10 MPa.
7. The method according to claim 1, characterized in that: the pH value of the neutralization gel forming reaction in the step (1) is 2-6, and the reaction time is 10-180 minutes.
8. The method according to claim 1, characterized in that: the acid aluminum salt aqueous solution I in the step (1) is AlCl 3 、Al 2 (SO 4 ) 3 Or Al (NO) 3 ) 3 One or more of the aqueous solutions, the concentration of the aqueous acidic aluminum salt solution being Al 2 O 3 The flow rate is 10-80 mL/min and the flow rate is 10-100 g/100 mL.
9. The method according to claim 1, characterized in that: the alkaline aluminum salt aqueous solution in the step (1) is selected from NaAlO 2 Or KAlO 2 One or two of the aqueous solutions, the concentration of the alkaline aluminum salt aqueous solution being Al 2 O 3 The flow rate is 10-80 mL/min and the flow rate is 10-100 g/100 mL.
10. The method according to claim 1, characterized in that: the particle size distribution of the sol obtained by separation in the step (1) is as follows: the proportion of the particle diameter less than 50nm is 0.5% -1%, the proportion of the particle diameter of 50-100 nm is 2% -5%, and the proportion of the particle diameter more than 100nm is 94% -97%; the crystallinity is less than 95%.
11. The method according to claim 1, characterized in that: the bottom water added in the step (2) is 1/5-1/2 of the volume of the reaction vessel.
12. The method according to claim 1, characterized in that: the reaction temperature in the step (2) is 150-250 ℃, and the reaction pressure is 10-15 MPa.
13. The method according to claim 1, characterized in that: the reaction pressure in the step (2) is 1-5 MPa higher than the reaction pressure in the step (1).
14. The method according to claim 1, characterized in that: the acid aluminum salt aqueous solution II in the step (2) is AlCl 3 、Al 2 (SO 4 ) 3 Or Al (NO) 3 ) 3 One or more of the aqueous solutions, the concentration of the acid aluminum salt aqueous solution II is Al 2 O 3 The flow rate is 10-80 mL/min and the flow rate is 10-100 g/100 mL; the alkaline aluminum salt aqueous solution II is selected from NaAlO 2 Or KAlO 2 One or two of the aqueous solutions, the concentration of the alkaline aluminum salt aqueous solution being Al 2 O 3 The flow rate is 10-80 mL/min and the flow rate is 10-100 g/100 mL.
15. The method according to claim 1, characterized in that: the pH value of the neutralization gel forming 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 gel forming reaction time is 60-120 minutes.
16. The method according to claim 1, characterized in that: the aging temperature in the step (3) is 100-250 ℃ higher than the reaction temperature in the step (2).
17. The method according to claim 1, characterized in that: the drying temperature 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.
18. An alumina material characterized by: the material has the following properties: pore volume is 0.95-1.2 mL g -1 The method comprises the steps of carrying out a first treatment on the surface of the The specific surface area is 290-350 m 2 ·g -1 The method comprises the steps of carrying out a first treatment on the surface of the A pore diameter of less than 80nm; crystallinity less than 90%; the particle size distribution is as follows: the proportion of the particle size less than 50 mu m is 0.5% -1%, the proportion of the particle size of 50-100 mu m is 2% -5%, and the proportion of the particle size more than 100 mu m is 94% -97%.
19. The alumina material of claim 18, wherein: the material has the following properties: the pore diameter of the nanometer glass is 80-100 nm; the crystallinity is 95-99%.
20. Use of an alumina material according to claim 18 or 19 in the preparation of a heavy oil hydroprocessing catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010728985.5A CN114057211B (en) | 2020-07-27 | 2020-07-27 | Preparation method of alumina material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010728985.5A CN114057211B (en) | 2020-07-27 | 2020-07-27 | Preparation method of alumina material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114057211A CN114057211A (en) | 2022-02-18 |
| CN114057211B true CN114057211B (en) | 2023-07-28 |
Family
ID=80226545
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010728985.5A Active CN114057211B (en) | 2020-07-27 | 2020-07-27 | Preparation method of alumina material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114057211B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116081662A (en) * | 2021-10-29 | 2023-05-09 | 中国石油化工股份有限公司 | Alumina and production method thereof |
Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0909981A1 (en) * | 1997-10-15 | 1999-04-21 | Agfa-Gevaert N.V. | Light-sensitive silver halide photographic materials comprising zeolites |
| CN100999328A (en) * | 2006-01-10 | 2007-07-18 | 中国石油化工股份有限公司 | Pseudo thin allophane and its preparation method |
| CN102234124A (en) * | 2010-04-30 | 2011-11-09 | 中国石油化工股份有限公司 | Pseudoboehmite containing transition metal components and aluminum oxide prepared from same |
| CN102730724A (en) * | 2012-05-31 | 2012-10-17 | 江苏晶晶新材料有限公司 | Preparation process for large pore volume and light bulk density activated alumina |
| CN102836747A (en) * | 2011-06-23 | 2012-12-26 | 中国石油化工股份有限公司 | Preparation method for alumina oxide carrier |
| CN102906013A (en) * | 2010-03-22 | 2013-01-30 | 布莱阿姆青年大学 | Method for making highly porous, stable metal oxide with a controlled pore structure |
| CN103372441A (en) * | 2012-04-13 | 2013-10-30 | 中国石油化工股份有限公司 | Preparation method of methanol synthesis catalyst |
| CN103717785A (en) * | 2011-02-02 | 2014-04-09 | 阿德文尼拉企业有限公司 | Solution derived nanocomposite precursor solutions, methods for making thin films and thin films made by such methods |
| CN104003353A (en) * | 2014-05-29 | 2014-08-27 | 中国科学院合肥物质科学研究院 | Preparation method for metal non-close arrangement spherical nanoparticle array |
| CN104058425A (en) * | 2014-06-20 | 2014-09-24 | 烟台万润精细化工股份有限公司 | Preparation method of SAPO-34 molecular sieve |
| CN104649307A (en) * | 2013-11-25 | 2015-05-27 | 中国石油化工股份有限公司 | Preparation method of aluminium oxide dry glue |
| AU2015246122A1 (en) * | 2010-03-18 | 2015-11-12 | Blacklight Power, Inc. | Electrochemical hydrogen-catalyst power system |
| CN105585036A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司大连石油化工研究院 | Preparation method of pseudo-boehmite with high purity and high crystallization degree |
| CN106673037A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Preparation method of pseudo-boehmite |
| CN106744813A (en) * | 2016-11-28 | 2017-05-31 | 陕西师范大学 | A kind of method that fullerene crystal is cultivated in supermolecular gel medium |
| CN109019637A (en) * | 2018-08-07 | 2018-12-18 | 东北大学 | A method of flower-like structure zinc oxide is prepared using middle-low grade zinc oxide ore |
| CN109663475A (en) * | 2019-01-24 | 2019-04-23 | 大连理工大学 | A kind of preparation method of copper sulfide mercury removal agent |
| CN109721087A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of boehmite and preparation method thereof |
-
2020
- 2020-07-27 CN CN202010728985.5A patent/CN114057211B/en active Active
Patent Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0909981A1 (en) * | 1997-10-15 | 1999-04-21 | Agfa-Gevaert N.V. | Light-sensitive silver halide photographic materials comprising zeolites |
| CN100999328A (en) * | 2006-01-10 | 2007-07-18 | 中国石油化工股份有限公司 | Pseudo thin allophane and its preparation method |
| AU2015246122A1 (en) * | 2010-03-18 | 2015-11-12 | Blacklight Power, Inc. | Electrochemical hydrogen-catalyst power system |
| CN102906013A (en) * | 2010-03-22 | 2013-01-30 | 布莱阿姆青年大学 | Method for making highly porous, stable metal oxide with a controlled pore structure |
| CN102234124A (en) * | 2010-04-30 | 2011-11-09 | 中国石油化工股份有限公司 | Pseudoboehmite containing transition metal components and aluminum oxide prepared from same |
| CN103717785A (en) * | 2011-02-02 | 2014-04-09 | 阿德文尼拉企业有限公司 | Solution derived nanocomposite precursor solutions, methods for making thin films and thin films made by such methods |
| CN102836747A (en) * | 2011-06-23 | 2012-12-26 | 中国石油化工股份有限公司 | Preparation method for alumina oxide carrier |
| CN103372441A (en) * | 2012-04-13 | 2013-10-30 | 中国石油化工股份有限公司 | Preparation method of methanol synthesis catalyst |
| CN102730724A (en) * | 2012-05-31 | 2012-10-17 | 江苏晶晶新材料有限公司 | Preparation process for large pore volume and light bulk density activated alumina |
| CN104649307A (en) * | 2013-11-25 | 2015-05-27 | 中国石油化工股份有限公司 | Preparation method of aluminium oxide dry glue |
| CN104003353A (en) * | 2014-05-29 | 2014-08-27 | 中国科学院合肥物质科学研究院 | Preparation method for metal non-close arrangement spherical nanoparticle array |
| CN104058425A (en) * | 2014-06-20 | 2014-09-24 | 烟台万润精细化工股份有限公司 | Preparation method of SAPO-34 molecular sieve |
| CN105585036A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司大连石油化工研究院 | Preparation method of pseudo-boehmite with high purity and high crystallization degree |
| CN106673037A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Preparation method of pseudo-boehmite |
| CN106744813A (en) * | 2016-11-28 | 2017-05-31 | 陕西师范大学 | A kind of method that fullerene crystal is cultivated in supermolecular gel medium |
| CN109721087A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of boehmite and preparation method thereof |
| CN109019637A (en) * | 2018-08-07 | 2018-12-18 | 东北大学 | A method of flower-like structure zinc oxide is prepared using middle-low grade zinc oxide ore |
| CN109663475A (en) * | 2019-01-24 | 2019-04-23 | 大连理工大学 | A kind of preparation method of copper sulfide mercury removal agent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114057211A (en) | 2022-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100477939B1 (en) | Mehtod for preparing single craystalline cerium oxide powders | |
| US8658127B2 (en) | Method of manufacturing mesoporous zeolite agglomerates | |
| CN100999328B (en) | Pseudo thin allophane and its preparation method | |
| US4085068A (en) | Hydrodenitrogenation and hydrocracking catalyst | |
| JPH042307B2 (en) | ||
| CN114057211B (en) | Preparation method of alumina material | |
| WO2001056951A1 (en) | Alumina composition, method for preparation thereof and use thereof | |
| CN107849176A (en) | Inorganic porous skeleton layered double-hydroxide core-shell material is as the catalyst carrier in vinyl polymerization | |
| CN106732496A (en) | A kind of high activity amorphous silica-alumina, the hydrocracking catalyst with it as carrier and their preparation method | |
| CN114057213B (en) | Preparation method of macroporous alumina material | |
| CN108212224B (en) | Boehmite catalyst carrier and preparation method thereof | |
| CN101172617A (en) | Method for synthesizing nano type A molecular sieve | |
| JP2021151942A (en) | Porous silica alumina particles and method for producing the same | |
| CN107758688A (en) | The nanometer aggregation plate-like modenite of different compactness | |
| CN116081662A (en) | Alumina and production method thereof | |
| CN113996308B (en) | Preparation method of heavy oil hydrogenation catalyst | |
| CN112516993B (en) | Preparation method of alumina carrier | |
| CN115920961A (en) | Preparation method of silicon-containing pseudo-boehmite slurry | |
| CN116081664A (en) | Macroporous alumina and its production process | |
| CN116440887A (en) | Modified alumina and production method thereof | |
| CN116060023A (en) | Hydrogenation catalyst and preparation method thereof | |
| CN114073962B (en) | Preparation method of bulk phase hydrogenation catalyst | |
| CN116443905A (en) | Modified alumina and method for producing the same | |
| JPH0217932A (en) | Modified inorganic particle and preparation thereof | |
| JP2003221223A (en) | Silica |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231228 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |