CN116081662A - Alumina and production method thereof - Google Patents
Alumina and production method thereof Download PDFInfo
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- CN116081662A CN116081662A CN202111269123.1A CN202111269123A CN116081662A CN 116081662 A CN116081662 A CN 116081662A CN 202111269123 A CN202111269123 A CN 202111269123A CN 116081662 A CN116081662 A CN 116081662A
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 144
- 230000032683 aging Effects 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 43
- 150000004645 aluminates Chemical class 0.000 claims abstract description 37
- 239000003960 organic solvent Substances 0.000 claims abstract description 37
- 239000013078 crystal Substances 0.000 claims abstract description 35
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 31
- 230000002378 acidificating effect Effects 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 238000009826 distribution Methods 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 72
- 239000007788 liquid Substances 0.000 claims description 69
- 238000003756 stirring Methods 0.000 claims description 38
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000003570 air Substances 0.000 claims description 18
- 239000012298 atmosphere Substances 0.000 claims description 18
- 239000012266 salt solution Substances 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 235000006481 Colocasia esculenta Nutrition 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 230000002431 foraging effect Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 240000004270 Colocasia esculenta var. antiquorum Species 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 claims 1
- 235000005985 organic acids Nutrition 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000012876 carrier material Substances 0.000 abstract description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 21
- 230000001105 regulatory effect Effects 0.000 description 19
- 239000003513 alkali Substances 0.000 description 17
- 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 15
- 229910052708 sodium Inorganic materials 0.000 description 15
- 239000011734 sodium Substances 0.000 description 15
- 230000001276 controlling effect Effects 0.000 description 14
- 239000002253 acid Substances 0.000 description 11
- 239000005711 Benzoic acid Substances 0.000 description 10
- 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 10
- 235000010233 benzoic acid Nutrition 0.000 description 10
- 238000004062 sedimentation Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- 239000008213 purified water Substances 0.000 description 9
- 239000012429 reaction media Substances 0.000 description 9
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 239000007863 gel particle Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- 244000205754 Colocasia esculenta Species 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000010742 number 1 fuel oil Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 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
- 241000640882 Condea Species 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005537 brownian motion Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007547 defect Effects 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
- 239000000295 fuel oil Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
Images
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- C01F7/34—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts
-
- 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
- C01F7/441—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by calcination
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses alumina and a production method thereof. The properties of the alumina provided by the invention are as follows: pore volume of 0.8-1.5 ml/g and specific surface area of 300-400 m 2 The pore size of the polymer/g may be less than or equal to 100nm. The method comprises the following steps: in the process of parallel flow neutralization and gel formation of the acidic aluminate solution I and the alkaline aluminate solution I, simultaneously adding an organic solvent and a polar metal seed crystal, and then settling and separating the gel formed by gel formation from the acidic aluminate solution II or the alkaline aluminate solutionAnd II, carrying out parallel flow neutralization and gel forming reaction, aging, drying and roasting to obtain the alumina. The alumina of the invention has the characteristics of large particle size, concentrated distribution, high specific surface area, large pore volume, large pore diameter, high purity and the like, and can be used as a carrier material of a poor-quality raw material hydrogenation catalyst.
Description
Technical Field
The invention relates to the field of alumina preparation, in particular to a method for continuously producing alumina.
Background
At present, the production mode of pseudo-boehmite mainly comprises an inorganic aluminum salt method and an organic aluminum salt method, and batch kettle reactors are adopted in the production process. Pseudo-boehmite is mainly prepared by a precipitation mechanism, wherein precipitation refers to a process of generating insoluble substances through chemical reaction in a liquid phase and forming a new solid phase to be settled out of the liquid phase. From classical theoretical analysis of precipitation, the precipitate formation process is divided into: (1) nucleation: because of the continuous collision motion of molecules or ions, the molecules in the local area are clustered, the aggregation is not only due to the collision among moving particles in the solution, but also the mutual adhesion of the moving particles through weak acting force (Van der Waals force), chemical bonds are generated through crystals, and the aggregation is solidified; (2) Crystal nucleus growth: cluster molecular particles are contacted with each other and combined to grow; wherein, the colloid is uniform, the particles are tiny, and the method has very strong effect on nucleation and crystal growth.
The coprecipitation method is a typical method for preparing aluminum hydroxide. The method is to prepare aluminum salt from raw materials by taking water as a medium, and then to control certain solution concentration, solution flow rate, temperature and reaction time, and to prepare the aluminum hydroxide by acid/alkali neutralization. However, the initial nuclei Al (OH) in the coprecipitation process 3 The polymer has complex structure, small molecular polarity and extremely small solubility, so that the aggregation rate is far higher than the orientation rate, and amorphous gelatinous precipitation is easy to generate, so that the polymer has low crystallinity, incomplete crystal form and unsatisfactory pore structure.
CN103787390a discloses a preparation method of pseudo-boehmite, comprising the following steps: (1) Performing gel forming reaction on the acidic aluminum salt solution and the alkaline solution, 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. The method is to prepare pseudo-boehmite by controlling the grain size by using ultrasonic waves with different frequencies during the gelling and aging.
In the prior art, although the grain size is controlled by different methods so as to prepare pseudo-boehmite with different pore structures and properties, how to prepare macroporous alumina with high specific surface area is an important subject of continuous and diligent research in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides alumina and a production method thereof, in particular to a method for continuously producing macroporous alumina. The alumina of the invention has the characteristics of large particle size, concentrated distribution, high specific surface area, large pore volume, large pore diameter, high purity and the like, and can be used as a carrier material of a poor-quality raw material hydrogenation catalyst.
In a first aspect the present invention provides an alumina having the following properties: pore volume is 0.8-1.5 ml/g; specific surface area of 300-400 m 2 The pore size of the polymer/g may be less than or equal to 100nm, preferably 150 to 250nm.
The particle size distribution of the alumina of the invention is as follows: the proportion of the crystal grains with the grain diameter smaller than 100 mu m is 0.5% -5.0%, the proportion of the crystal grains with the grain diameter of 100-200 mu m is 2.0% -5.0%, and the proportion of the crystal grains with the grain diameter larger than 200 mu m is 90.0% -95.0%.
The relative crystallinity of the alumina of the present invention is less than 90%, preferably 95% to 99%.
In a second aspect, the present invention provides a method for producing alumina, comprising:
(1) Adding an organic solvent, a polar metal seed crystal, an acidic aluminate solution I and an alkaline aluminate solution I into a first reaction kettle in parallel flow for neutralization and gel formation to obtain a generated liquid I;
(2) The obtained generated liquid I enters a settling tank for settling separation to obtain an upper layer, namely an organic solvent, and a lower layer, namely sol II;
(3) The sol II and the acidic aluminate solution II or the alkaline aluminate solution II flow in parallel and enter a second reaction kettle to be neutralized and gel to obtain a generated liquid III;
(4) The generated liquid III enters an aging kettle for aging;
(5) And (3) drying and roasting the ageing material obtained in the step (4) to obtain the alumina.
The production method of the alumina is preferably carried out in a continuous mode, wherein a plurality of settling tanks used in the step (2) and a plurality of ageing tanks used in the step (4) can be arranged, and the continuous production is switched.
In the method of the present invention, when alumina is continuously produced, preferably, the first reaction vessel in the step (1) is operated in such a manner that the produced liquid I is discharged from the first reaction vessel by overflow. When the first reaction kettle is started, preferably, an organic solvent and a polar metal seed crystal are firstly added as base solution, and then an acidic aluminate solution I and an alkaline aluminate solution I are added in parallel flow for neutralization and gel formation until the generated solution I starts to be discharged out of the first reaction kettle. Wherein the addition amount of the organic solvent in the base solution is 1/5-1/2 of the actual effective use volume of the first reaction kettle; when the generated liquid I starts to be discharged out of the first reaction kettle, the acidic aluminum salt solution I and the alkaline aluminum salt solution I in the first reaction kettle are prepared by using Al 2 O 3 The addition amount of the polar metal salt seed crystal accounts for 0.1 to 5.0 percent, preferably 0.5 to 4.0 percent based on the total mass.
In the method of the invention, when continuously producing alumina, preferably, the second reaction kettle in the step (3) adopts an overflow type operation mode for discharging the generated liquid III out of the second reaction kettle. When the second reaction kettle is started, preferably, the bottom water is added first, then the sol II and the acid aluminate solution II or the alkaline aluminate solution II are added in parallel flow for neutralization and gel formation, and the generated liquid III starts to be discharged out of the second reaction kettle. Wherein, the addition amount of the bottom water is 1/7-1/2, preferably 1/6-1/3 of the actual effective use volume of the second reaction kettle.
In the method of the invention, the organic solvent in the step (1) isThe organic matter which is not or slightly soluble in water can be one or more of alkane, alkene, organic alcohol, organic acid and the like, and preferably the carbon number of the organic matter is 5-12. Wherein the molecular structural formula of alkane is C n H 2n+2 (n is more than or equal to 5, preferably n=5-12), and at least one of pentane, hexane, dodecane and the like can be selected; the molecular structural formula of the olefin is C n H 2n (n is more than or equal to 5, preferably n=5-12), and at least one of pentene, hexene and the like can be selected; the organic alcohol is at least one selected from organic monohydric alcohol and organic polyalcohol, wherein the molecular structural formula of the organic monohydric alcohol is C n H 2n+2 O (n is more than or equal to 6, preferably n=6-12), and at least one of n-hexanol, n-heptanol and the like can be selected; wherein the molecular structural formula of the polyol is C n H 2n+2-x (OH) x (n is more than or equal to 6, preferably n=6-12, and x is more than or equal to 3), and at least one of polyhydric alcohols such as pentaerythritol, glycerol, trimethylolethane, xylitol, sorbitol and the like can be selected; the organic acid may be at least one of aliphatic or aromatic carboxylic acid, such as benzoic acid.
In the method of the invention, the polar metal seed crystal is selected from at least one of metal halogen compounds and metal sulfides, preferably one or more of AgCl, znS, cuS or HgS and the like.
In the method of the invention, the operation conditions of the first reaction kettle in the step (1) are as follows: the temperature is-15 to 15 ℃, preferably 0 to 15 ℃, the pressure is 1 to 10MPa, preferably 3 to 10MPa, and more preferably 3 to 9.5MPa. The pressure atmosphere can be one or more of air, nitrogen or inert gas. The reaction conditions for neutralizing and gelling in the step (1) are as follows: the pH is 2 to 6, preferably 2 to 5, and the reaction time is 10 to 180 minutes, preferably 10 to 60 minutes (when continuous production is employed, the reaction time is the residence time of the acidic aluminate solution I and the basic aluminate solution I into the first reaction vessel). The neutralization and gelling reaction is preferably carried out under stirring at a rate of from 100 to 500rad/min, preferably from 150 to 500rad/min.
In the process of the present invention, the acidic aluminum salt of step (1) may be selected from AlCl 3 、Al 2 (SO 4 ) 3 Or Al (NO) 3 One or more of them, preferably Al 2 (SO 4 ) 3 、AlCl 3 The acidic aluminum salt solution can be an aqueous solution. The concentration of the acidic aluminum salt aqueous solution is Al 2 O 3 Is 10-100 g/100ml. The alkaline aluminum salt is selected from NaAlO 2 Or KAlO 2 One or both, preferably NaAlO 2 . The alkaline aluminum salt solution may be an aqueous solution. The concentration of the alkaline aluminum salt aqueous solution is Al 2 O 3 Is 10-100 g/100ml.
In the method of the invention, the organic solvent and the polar metal seed crystal are added into the first reaction kettle in parallel, wherein the adding rate of the organic solvent is the ratio of the adding rate of the acid aluminate solution I to the adding rate of the alkaline aluminate solution I in terms of volume of the two to be 0.1:1 to 10:1, preferably 0.2:1 to 5:1, the addition rate of the polar metal seed crystal is that the acidic aluminate solution I and the alkaline aluminate solution I are added with Al 2 O 3 1 to 10% of the sum of the addition rates by mass, preferably 1 to 5%.
In the method of the invention, the particle size distribution of the sol II obtained in the step (2) is as follows: the proportion of the grains with the grain diameter smaller than 50nm is 0.5-5.0%, the proportion of the grains with the grain diameter of 50-100 nm is 2-5%, and the proportion of the grains with the grain diameter larger than 100nm is 90-95%. The relative crystallinity of the obtained sol II is less than or equal to 95%, preferably 95 to 98%.
In the method of the present invention, the operating conditions of the settling tank of step (2) are as follows: the temperature is-15 to 15 ℃, preferably 0 to 15 ℃, and the pressure is 1 to 10MPa, preferably 4 to 10MPa.
In the method, after the sedimentation in the step (2), the organic solvent on the upper layer can be recycled to the first reaction kettle for continuous use.
In the method of the invention, the operation conditions of the second reaction kettle in the step (3) are as follows: the temperature is 100 to 300 ℃, preferably 100 to 200 ℃, and the pressure is 1 to 10MPa, preferably 4 to 10MPa. Preferably, the operating pressure of the second reactor is at least 0.5MPa higher than the operating pressure of the first reactor. The reaction conditions for neutralizing and gelling in the step (3) are as follows: the pH is 7 to 12, preferably 7.5 to 10.0, and the reaction time is 10 to 180 minutes, preferably 10 to 120 minutes (when continuous production is employed, the reaction time is the residence time of the sol II and the acidic or basic aluminate solution II in the second reaction vessel). The neutralization and gelling reaction is preferably carried out under stirring at a rate of from 100 to 500rad/min, preferably from 200 to 500rad/min.
In the process of the present invention, the acidic aluminum salt of step (3) is selected from AlCl 3 、Al 2 (SO 4 ) 3 Or Al (NO) 3 At least one of the following, preferably Al 2 (SO 4 ) 3 、AlCl 3 And the like, and the acidic aluminum salt solution may be an aqueous solution. The concentration of the acidic aluminum salt aqueous solution is Al 2 O 3 Is 10-100 g/100ml. The alkaline aluminum salt is selected from NaAlO 2 Or KAlO 2 One or both, preferably NaAlO 2 The alkaline aluminum salt solution may be an aqueous solution. The concentration of the alkaline aluminum salt aqueous solution is Al 2 O 3 Is 10-100 g/100ml.
In the method of the present invention, the aging reaction conditions of step (4): the temperature is 200-400 ℃, the pressure is 15-20 MPa, and the aging time is 100-360 min, preferably 150-250 min; the aging is carried out under stirring conditions, preferably at a stirring speed of 500 to 800r/min.
In the method of the invention, the drying temperature in the step (5) 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 roasting temperature is 300-800 ℃, preferably 350-550 ℃, and the roasting time is 2-5 hours, preferably 2-4 hours. The roasting atmosphere is one or more of air, nitrogen or steam.
In a third aspect the invention provides alumina produced by the above method.
In a fourth aspect, the present invention provides the use of an alumina as described above in a hydrogenation catalyst support.
In the application of the invention, the hydrogenation catalyst can be a hydrogenation catalyst for treating inferior heavy oil, such as residual oil, wax oil, coal tar and liquefied coal oil, and can be used as a protective agent and/or a hydrogenation refining agent in the hydrogenation of the liquefied coal oil.
Compared with the prior art, the invention has the following beneficial effects:
1. in the method for producing alumina, firstly, an organic solvent which is not mutually soluble with water is used as a reaction medium, polar metal salt is used as a seed crystal, the neutralization reaction is carried out under higher pressure and lower reaction temperature, on one hand, the generated sol-gel particles are wrapped by hydrophilic hydroxyl on the surface, all sol-gel particles in the organic solvent which is not mutually soluble with water can not adhere to each other, under the action of the polar seed crystal, the characteristics of small molecule and large polarity and larger directional rate are utilized, so that crystal precipitation or colloidal particles with crystal structures are easy to form, on the other hand, the Brownian motion of sol-gel molecules or ions is reduced under higher pressure and lower temperature, the aggregation into cluster groups due to continuous collision of the particles is reduced, and the amorphous aluminum hydroxide is dissolved under the lower pH value, namely the acidic condition, so that the generated pseudo-boehmite is kept, the proper and complete crystal grains in the sol II are effectively controlled, the gel particles with complete crystal forms are fully aggregated under the conditions of high temperature, high pressure and high pH value, namely the alkaline condition, the crystal grains with complete crystal forms are fully-ordered, the crystal grains are formed, the crystal grains are fully aggregated, the crystal grains are fully-grown through the crystal precipitation grains are concentrated under the conditions, the high particle size distribution is greatly, and the alumina particle size is easy to form, and the alumina grains are concentrated, and the alumina particle size is large, and the alumina particle size is formed, and the alumina particle size is easy to be formed.
2. The alumina provided by the invention has the characteristics of large surface area, large pore volume, concentrated particle size distribution, high crystallinity and the like, and is particularly suitable for being used as a carrier of a hydrogenation catalyst and used as a protective agent and/or a hydrogenation refining agent for heavy and inferior raw materials such as residual oil, wax oil, coal liquefied oil, coal tar and the like.
Drawings
FIG. 1 is a schematic flow chart of a continuous alumina production process;
wherein, the reference numerals are as follows: i-a first reaction kettle; II, III-a sedimentation tank; IV-a second reaction kettle; v-aging the kettle; a-acidic aluminate solution I; b-basic aluminate solution I; c-polar metal seed; d-an organic solvent; e-setting tank II control valve; f-setting tank III control valve; g-sol II; h-acidic aluminate solution II or alkaline aluminate solution II; i-a second reaction kettle drain valve; j-overflow liquid; k-ageing cauldron drain valve.
Detailed Description
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.
The process (shown in figure 1) for continuously producing alumina provided by the invention comprises the following steps:
(1) Adding an organic solvent D, a polar metal seed crystal C, an acidic aluminate solution IA and an alkaline aluminate solution IB into a first reaction kettle I in parallel flow for neutralization and gel formation to obtain a generated liquid I;
(2) The obtained generated liquid I enters a sedimentation tank II or III for sedimentation, and is separated through a sedimentation tank II control valve E or a sedimentation tank III control valve F to obtain a lower layer, namely sol II G, and an upper layer, namely organic solvent;
(3) The sol II and an acidic or alkaline aluminate solution IIH flow into a second reaction kettle IV in parallel to carry out neutralization and gel forming reaction to obtain a generated liquid III;
(4) The generated liquid III passes through a second reaction kettle liquid discharge valve I, and overflow liquid J enters an ageing kettle V for ageing;
(5) And (3) discharging the aged material obtained in the step (4) through the control of an ageing kettle drain valve K, and then drying and roasting to obtain the alumina.
In the invention, the specific surface area and the pore volume are measured by adopting a low-temperature liquid nitrogen adsorption method; the particle size distribution was measured using a laser particle size distribution meter.
In the present invention, the crystallinity was measured by X-ray diffraction (XRD), wherein the crystallinity was 100% in SB powder (Condea, germany). XRD characterization was performed using a Japanese physics D/max2500 type X-ray diffractometer: cu K alpha rays, a graphite monochromator, a tube voltage of 40kV, a tube current of 80mA, a scanning range of 10-70 degrees, a step length of 0.01 degrees and a scanning frequency of 1 degree/min.
Example 1
The flow of alumina production in this example is shown in FIG. 1.
2L of n-hexanol was added as a reaction medium to 10L of the first reaction vessel I, 1.6g of AgCl was added, the pressure of the first reaction vessel I was adjusted to 5MPa, the temperature was 10℃and the atmosphere was air, 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 a first 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, reacting for a pH value of 2.5, after neutralization reaction for 15min, opening an overflow port control valve at the lower end to enable a generated liquid I to flow into a settling tank II, simultaneously adding n-hexanol and AgCl into the first reaction kettle I at the flow rates of 10mL/min and 0.1g/min respectively, switching to the settling tank III after the generated liquid volume in the settling tank II reaches 1/2, separating an organic solvent and sol II in the settling tank II, and recycling the organic solvent into the first reaction kettle I, wherein the property of sol II A is shown in table 1.
2.5L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to be 10MPa, the temperature is 180 ℃, and the stirring speed is 300rad/min. And opening a sol II feeding hole and an alkali liquor feeding hole at the upper end of the second reaction kettle, adding the sol II and a sodium metaaluminate solution with the concentration of 30g/100mL, wherein the flow rates of the sol II and the sodium metaaluminate solution are respectively 15mL/min and 20mL/min, adjusting the pH value of the reaction to 7.5, and discharging the generated solution III out of the second reaction kettle after neutralization reaction for 60 min.
The resulting solution III was fed into an aging vessel, the pressure of the aging vessel was adjusted to 15MPa, the temperature was 280℃and the stirring rate was 500rad/min, and after aging for 150min, it was dried by filtration at 150℃for 4 hours, and calcined at 400℃for 3 hours under an air atmosphere to give alumina A, the properties of which are shown in Table 2.
Example 2
The flow of alumina production in this example is shown in FIG. 1.
To 10L of the first reaction vessel I, 2.5L of cyclohexane was added as a reaction medium, 9g of ZnS was added, the pressure of the first reaction vessel I was adjusted to 7MPa, the temperature was 0℃and the atmosphere was air, and the stirring rate was 300rad/min. After the mixture is uniformly stirred, an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of a first 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 controlled to be 30mL/min and 25mL/min respectively, the reaction pH value is 5.0, after the neutralization reaction is carried out for 30min, a lower overflow port control valve is opened to enable a generated liquid I to flow into a settling tank II, cyclohexane and ZnS are added into the first reaction kettle I at the speed of 15mL/min and at the speed of 0.2g/min respectively, after the generated liquid volume in the settling tank II reaches 3/4, the generated liquid is switched to the settling tank III, an organic solvent in the settling tank II is separated from the sol II, the organic solvent can be recycled into the first reaction kettle I, and the properties of the sol II B are shown in the table 1.
3L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to 9MPa, the temperature is 180 ℃, and the stirring speed is 300rad/min. And opening a sol II feeding hole and an alkali liquor feeding hole at the upper end of the second reaction kettle, controlling the flow rates of the sol II with the concentration of 30g/100mL and the aluminum sulfate solution with the concentration of 25g/100mL to be respectively 20mL/min and 30mL/min, enabling the pH value of the reaction to be 9.5, and discharging the generated liquid III out of the second reaction kettle after the neutralization reaction is carried out for 120 min.
The resulting solution III was fed into an aging vessel, the pressure of the aging vessel was adjusted to 20MPa, the temperature was 250 ℃, the stirring rate was 500rad/min, and after aging for 180min, it was dried at 180℃for 5 hours by filtration, and after calcination at 350℃for 4 hours under an air atmosphere, alumina B was obtained, the properties of which are shown in Table 2.
Example 3
The flow of alumina production in this example is shown in FIG. 1.
5L of benzoic acid is added into a 10L first reaction kettle I as a reaction medium, 13g of CuS is added, the pressure of the first reaction kettle I is regulated to 8MPa, the temperature is 15 ℃, the atmosphere is air, and the stirring speed is 250rad/min. After stirring uniformly, opening an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first 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, reacting for a pH value of 4.5, after a neutralization reaction for 60min, opening an overflow port control valve at the lower end to enable a generated liquid I to flow into a settling tank II, simultaneously adding benzoic acid and CuS into the first reaction kettle I at the flow rates of 20mL/min and 0.5g/min respectively, switching to the settling tank III after the generated liquid volume in the settling tank II reaches 2/3, separating an organic solvent from the sol II in the settling tank II, and recycling the organic solvent into the first reaction kettle I, wherein the property of the sol II C is shown in the table 1.
3L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to 9.5MPa, the temperature is 200 ℃, and the stirring speed is 450rad/min. And opening a sol II feeding hole and an alkali liquor feeding hole at the upper end of the second reaction kettle, controlling the flow rates of the sol II and the 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 discharging the generated liquid III out of the second reaction kettle after neutralization reaction for 100 min.
Adding the generated liquid III into an aging kettle, regulating the pressure of the aging kettle to 15MPa, the temperature to 300 ℃, the stirring speed to 400rad/min, aging for 240min, drying for 3h at 200 ℃ by filtering, and roasting for 4h at 500 ℃ in an air atmosphere to obtain alumina C, wherein the properties are shown in Table 2.
Example 4
The flow of alumina production in this example is shown in FIG. 1.
4L of styrene is added into 10L of the first reaction kettle I as a reaction medium, 7g of HgS is added to regulate the pressure of the first reaction kettle I to 9MPa, the reaction temperature is 5 ℃, the atmosphere is air, and the stirring speed is 500rad/min. After stirring uniformly, opening an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first 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, reacting for a pH value of 3.5, after a neutralization reaction for 45min, opening an overflow port control valve at the lower end to enable a generated liquid I to flow into a high-pressure sedimentation tank II, simultaneously adding styrene and HgS into the high-pressure reaction kettle I at the rates of 30mL/min and 0.5g/min respectively, switching to the high-pressure sedimentation tank III after the generated liquid volume in the high-pressure sedimentation tank II reaches 4/5, separating an organic solvent and a sol II in the high-pressure sedimentation tank II, and recycling the organic solvent into the first reaction kettle I, wherein the property of the sol II D is shown in the table 1.
3L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to 10MPa, the temperature is 190 ℃, and the stirring speed is 450rad/min. And opening a sol II feeding hole and an alkali liquor feeding hole at the upper end of the second reaction kettle, controlling the flow rates of the sol II and the aluminum sulfate solution with the concentration of 45g/100mL to be 25mL/min and 40mL/min respectively, adjusting the pH value of the reaction to 7.5, and discharging the generated liquid III out of the second reaction kettle after neutralization reaction for 80 min.
The resulting solution III was fed into an aging vessel, the pressure of the aging vessel was adjusted to 20MPa, the temperature was 400 ℃, the stirring rate was 500rad/min, and after aging for 210min, it was dried by filtration at 180℃for 2 hours, and then calcined at 400℃for 3 hours under an air atmosphere to give alumina D, the properties of which are shown in Table 2.
Comparative example 1
The flow of alumina production in this example is shown in FIG. 1.
5L of benzoic acid is added as a reaction medium to 10L of the first reaction kettle I, 13g of CuS is added, the pressure of the first reaction kettle I is regulated to be normal, the temperature is 75 ℃, and the stirring speed is 250rad/min. After the mixture is uniformly stirred, an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first 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 controlled to be 20mL/min and 10mL/min respectively, the reaction pH value is 4.5, after the neutralization reaction is carried out for 60min, a lower overflow port control valve is opened to enable a generated liquid I to flow into a settling tank II, simultaneously benzoic acid and CuS are added into the first reaction kettle I at the flow rates of 20mL/min and 0.5g/min respectively, after the generated liquid volume in the settling tank II reaches 2/3, the generated liquid is switched to the settling tank III, an organic solvent in the settling tank II is separated from the sol II, the organic solvent can be recycled into the first reaction kettle I, and the properties of the sol II E are shown in the table 1.
3L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to be normal pressure, the temperature is 75 ℃, and the stirring speed is 450rad/min. And opening a sol II feeding hole and an alkali liquor feeding hole at the upper end of the second reaction kettle, controlling the flow rates of the sol II and the 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 discharging the generated liquid III out of the second reaction kettle after neutralization reaction for 100 min.
Adding the generated liquid III into an aging kettle, regulating the pressure of the aging kettle to be normal pressure, regulating the temperature to 75 ℃, stirring the mixture at the speed of 400rad/min, aging the mixture for 240min, drying the mixture at 200 ℃ for 3h through filtration, and roasting the mixture at 500 ℃ for 4h in an air atmosphere to obtain alumina E, wherein the properties are shown in Table 2.
Comparative example 2
The flow of alumina production in this example is shown in FIG. 1.
5L of purified water is added into 10L of a first reaction kettle I as a reaction medium, 13g of CuS is added, the pressure of the first reaction kettle I is regulated to 8MPa, the temperature is 15 ℃, the atmosphere is air, and the stirring speed is 250rad/min. After stirring uniformly, opening an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first 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, reacting for a pH value of 4.5, after a neutralization reaction for 60min, opening an overflow port control valve at the lower end to enable a generated liquid I to flow into a settling tank II, simultaneously adding benzoic acid and CuS into the first reaction kettle I at the flow rates of 20mL/min and 0.5g/min respectively, switching to the settling tank III after the generated liquid volume in the settling tank II reaches 2/3, separating an organic solvent from the sol II in the settling tank II, and recycling the organic solvent into the first reaction kettle I, wherein the property of the sol II F is shown in the table 1.
3L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to 9.5MPa, the temperature is 200 ℃, and the stirring speed is 450rad/min. And opening a sol II feeding hole and an alkali liquor feeding hole at the upper end of the second reaction kettle, controlling the flow rates of the sol II and the 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 discharging the generated liquid III out of the second reaction kettle after neutralization reaction for 100 min.
Adding the generated liquid III into an aging kettle, regulating the pressure of the aging kettle to 15MPa, the temperature to 300 ℃, the stirring speed to 400rad/min, aging for 240min, drying for 3h at 200 ℃ by filtering, and roasting for 4h at 500 ℃ in an air atmosphere to obtain aluminum oxide F, wherein the properties are shown in Table 2.
Comparative example 3
The flow of alumina production in this example is shown in FIG. 1.
5L of benzoic acid is added into a 10L first reaction kettle I as a reaction medium, the pressure of the first reaction kettle I is regulated to 8MPa, the temperature is 15 ℃, the atmosphere is air, and the stirring speed is 250rad/min. After stirring uniformly, opening an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first 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 20mL/min and 10mL/min respectively, reacting for a pH value of 4.5, after a neutralization reaction for 60min, opening an overflow port control valve at the lower end to enable a generated liquid I to flow into a settling tank II, simultaneously adding benzoic acid into the first reaction kettle I at the rate of 20mL/min, switching to the settling tank III after the generated liquid volume in the settling tank II reaches 2/3, separating an organic solvent from the sol II in the settling tank II, and recycling the organic solvent into the first reaction kettle I, wherein the property of the sol II G is shown in the table 1.
3L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to 9.5MPa, the temperature is 200 ℃, and the stirring speed is 450rad/min. And opening a sol II feeding hole and an alkali liquor feeding hole at the upper end of the second reaction kettle, controlling the flow rates of the sol II and the 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 discharging the generated liquid III out of the second reaction kettle after neutralization reaction for 100 min.
Adding the generated liquid III into an aging kettle, regulating the pressure of the aging kettle to 15MPa, the temperature to 300 ℃, the stirring speed to 400rad/min, aging for 240min, drying for 3h at 200 ℃ by filtering, and roasting for 4h at 500 ℃ in an air atmosphere to obtain alumina G, wherein the properties are shown in Table 2.
Comparative example 4
The flow of alumina production in this example is shown in FIG. 1.
5L of benzoic acid is added into a 10L first reaction kettle I as a reaction medium, 13g of CuS is added, the pressure of the first reaction kettle I is regulated to 8MPa, the temperature is 200 ℃, the atmosphere is air, and the stirring speed is 250rad/min. After stirring uniformly, opening an acid liquid feed inlet and an alkali liquid feed inlet at the upper end of the first 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, reacting for a pH value of 4.5, after a neutralization reaction for 60min, opening an overflow port control valve at the lower end to enable a generated liquid I to flow into a settling tank II, simultaneously adding benzoic acid and CuS into the first reaction kettle I at the flow rates of 20mL/min and 0.5g/min respectively, switching to the settling tank III after the generated liquid volume in the settling tank II reaches 2/3, separating an organic solvent from the sol II in the settling tank II, and recycling the organic solvent into the first reaction kettle I, wherein the properties of the sol II H are shown in the table 1.
3L of purified water is added into the second reaction kettle IV, the pressure of the second reaction kettle is regulated to 8.0MPa, the temperature is 200 ℃, and the stirring speed is 450rad/min. And opening a sol II feeding hole and an alkali liquor feeding hole at the upper end of the second reaction kettle, controlling the flow rates of the sol II and the 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 discharging the generated liquid III out of the second reaction kettle after neutralization reaction for 100 min.
Adding the generated liquid III into an aging kettle, regulating the pressure of the aging kettle to 15MPa, the temperature to 300 ℃, the stirring speed to 400rad/min, aging for 240min, drying for 3H at 200 ℃ by filtering, and roasting for 4H at 500 ℃ in an air atmosphere to obtain alumina H, wherein the properties are shown in Table 2.
TABLE 1 Properties of the sols II obtained in examples and comparative examples
| A | B | C | D | E | F | G | H | |
| Relative crystallinity,% | 98 | 96 | 95 | 97 | 80 | 89 | 90 | 85 |
| Particle size distribution, percent | ||||||||
| ＜50nm | 0.5 | 0.7 | 1.0 | 0.8 | 20.9 | 5.3 | 5.2 | 10.7 |
| 50～100nm | 4.9 | 4.8 | 4.6 | 5.0 | 45.8 | 16.9 | 15.9 | 20.7 |
| ＞100nm | 94.6 | 94.5 | 94.4 | 94.2 | 33.3 | 77.8 | 78.9 | 68.6 |
Table 2 properties of alumina obtained in examples and comparative examples
As can be seen from tables 1 and 2, the alumina provided by the invention has large specific surface area, high pore volume, large pore diameter, high crystallinity and concentrated grain distribution, and is very suitable for hydrotreating catalyst carriers for heavy inferior raw materials.
Claims (19)
1. An alumina having the following properties: pore volume is 0.8-1.5 ml/g; specific surface area of 300-400 m 2 The pore size of the polymer/g may be less than or equal to 100nm, preferably 150 to 250nm.
2. Alumina according to claim 1, characterized in that the alumina has a particle size distribution as follows: the proportion of the crystal grains with the grain diameter smaller than 100 mu m is 0.5% -5.0%, the proportion of the crystal grains with the grain diameter of 100-200 mu m is 2.0% -5.0%, and the proportion of the crystal grains with the grain diameter larger than 200 mu m is 90.0% -95.0%.
3. Alumina according to claim 1, wherein the relative crystallinity of the alumina is not less than 90%, preferably 95% to 99%.
4. A method of producing alumina comprising:
(1) Adding an organic solvent, a polar metal seed crystal, an acidic aluminate solution I and an alkaline aluminate solution I into a first reaction kettle in parallel flow for neutralization and gel formation to obtain a generated liquid I;
(2) The obtained generated liquid I enters a settling tank for settling separation to obtain an upper layer, namely an organic solvent, and a lower layer, namely sol II;
(3) The sol II and the acidic aluminate solution II or the alkaline aluminate solution II flow in parallel and enter a second reaction kettle to be neutralized and gel to obtain a generated liquid III;
(4) The generated liquid III enters an aging kettle for aging;
(5) And (3) drying and roasting the ageing material obtained in the step (4) to obtain the alumina.
5. The method according to claim 4, wherein the method is carried out in a continuous manner.
6. The production method according to claim 5, wherein a plurality of settling tanks used in the step (2) and aging tanks used in the step (4) are arranged for switching; the first reaction kettle in the step (1) adopts an overflow type operation mode for discharging the generated liquid I out of the first reaction kettle, and the second reaction kettle in the step (3) adopts an overflow type operation mode for discharging the generated liquid III out of the second reaction kettle.
7. The production method according to claim 5, wherein when the first reaction kettle is started up, an organic solvent and a polar metal seed crystal are added as a base solution, and then an acidic aluminate solution I and an alkaline aluminate solution I are added in parallel flow for neutralization and gel formation until a generated solution I starts to discharge from the first reaction kettle; wherein the addition amount of the organic solvent in the base solution is 1/5-1/2 of the actual effective use volume of the first reaction kettle; when the generated liquid I starts to be discharged out of the first reaction kettle, the acidic aluminum salt solution I and the alkaline aluminum salt solution I in the first reaction kettle are prepared by using Al 2 O 3 The addition amount of the polar metal salt seed crystal accounts for 0.1 to 5.0 percent, preferably 0.5 to 4.0 percent based on the total mass.
8. The production method according to claim 5, wherein when the second reaction kettle is started, the bottom water is added first, then the sol II and the acidic or alkaline aluminate solution II are added in parallel flow to neutralize and gel until the generated solution III starts to be discharged from the second reaction kettle; wherein, the addition amount of the bottom water is 1/7-1/2, preferably 1/6-1/3 of the actual effective use volume of the second reaction kettle.
9. The process according to any one of claims 4 to 8, wherein the organic solvent in step (1) is an organic substance which is not miscible or slightly soluble with water and is selected from one or more of alkanes, alkenes, organic alcohols, organic acids; preferably, the organic matter has a carbon number of 5 to 12.
10. The method according to any one of claims 4 to 8, wherein the polar metal seed is selected from one or more of AgCl, znS, cuS and HgS.
11. The process according to any one of claims 4 to 8, wherein the first reaction vessel of step (1) is operated under the following conditions: the temperature is-15 to 15 ℃, preferably 0 to 15 ℃, and the pressure is 1 to 10MPa, preferably 3 to 10MPa; the reaction conditions for neutralizing and gelling in the step (1) are as follows: the pH value is 2-6, preferably 2-5, and the reaction time is 10-180 minutes, preferably 10-60 minutes; the neutralization and gelling reaction is preferably carried out under stirring at a rate of from 100 to 500rad/min, preferably from 150 to 500rad/min.
12. The process according to any one of claims 4 to 8, wherein in step (1) or step (3), the acidic aluminum salt is selected from AlCl 3 、Al 2 (SO 4 ) 3 Or Al (NO) 3 One or more of them, preferably Al 2 (SO 4 ) 3 、AlCl 3 One or more of the acidic aluminum salt solution is an aqueous solution, and the concentration of the acidic aluminum salt solution is Al 2 O 3 Counting to be 10-100 g/100ml; the alkaline aluminum salt is selected from NaAlO 2 Or KAlO 2 One or both, preferably NaAlO 2 The alkaline aluminum salt solution is aqueous solution, and the concentration of the alkaline aluminum salt solution is Al 2 O 3 Is 10-100 g/100ml.
13. The production method according to any one of claims 4 to 8, wherein the organic solvent and the polar metal seed crystal are added to the first reaction vessel in parallel flow, wherein the addition rate of the organic solvent is such that the ratio of the addition rates of the acidic aluminate solution i and the basic aluminate solution i in terms of both volumes is 0.1:1 to 10:1, preferably 0.2:1 to 5:1, the addition rate of the polar metal seed crystal is that the acidic aluminate solution I and the alkaline aluminate solution I are added with Al 2 O 3 1 to 10% of the sum of the addition rates by mass, preferably 1 to 5%.
14. The process according to any one of claims 4 to 8, wherein the sol ii obtained in step (2) has a particle size distribution as follows: the proportion of the grains with the grain diameter smaller than 50nm is 0.5-5.0%, the proportion of the grains with the grain diameter of 50-100 nm is 2-5%, and the proportion of the grains with the grain diameter larger than 100nm is 90-95%; preferably, the relative crystallinity of the obtained sol II is less than 95%, preferably 95% to 98%.
15. The production process according to any one of claims 4 to 8, wherein the operating conditions of the settling tank of step (2) are as follows: the temperature is-15 to 15 ℃, preferably 0 to 15 ℃, and the pressure is 1 to 10MPa, preferably 4 to 10MPa.
16. The process according to any one of claims 4 to 8, wherein the second reactor of step (3) is operated under the following conditions: the temperature is 100-300 ℃, preferably 100-200 ℃, and the pressure is 1-10 MPa, preferably 4-10 MPa; the reaction conditions for neutralizing and gelling in the step (3) are as follows: the pH value is 7-12, preferably 7.5-10.0, and the reaction time is 10-180 minutes, preferably 10-120 minutes; the neutralization and gelling reaction is preferably carried out under stirring at a rate of from 100 to 500rad/min, preferably from 200 to 500rad/min.
17. The production method according to any one of claims 4 to 8, wherein in step (4), the aging reaction conditions are: the temperature is 200-400 ℃, the pressure is 15-20 MPa, and the aging time is 100-360 min, preferably 150-250 min; the aging is carried out under stirring conditions, preferably at a stirring speed of 500 to 800r/min.
18. The process according to any one of claims 4 to 8, wherein in step (5), the drying temperature is 100 to 450 ℃, preferably 150 to 400 ℃, and the drying time is 1 to 10 hours; the roasting temperature is 300-800 ℃, preferably 350-550 ℃, the roasting time is 2-5 hours, preferably 2-4 hours, and the roasting atmosphere is one or more of air, nitrogen or water vapor.
19. Alumina obtained by the production process according to any one of claims 4 to 18.
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