CN106747591A - A kind of preparation method of big pore volume alumina support - Google Patents
A kind of preparation method of big pore volume alumina support Download PDFInfo
- Publication number
- CN106747591A CN106747591A CN201611029989.4A CN201611029989A CN106747591A CN 106747591 A CN106747591 A CN 106747591A CN 201611029989 A CN201611029989 A CN 201611029989A CN 106747591 A CN106747591 A CN 106747591A
- Authority
- CN
- China
- Prior art keywords
- alumina
- water
- amorphous alumina
- solid phase
- pore volume
- 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.)
- Granted
Links
- 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 47
- 239000011148 porous material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 21
- 239000007790 solid phase Substances 0.000 claims abstract description 15
- 238000007493 shaping process Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 24
- 229920003023 plastic Polymers 0.000 claims description 20
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 14
- 239000012752 auxiliary agent Substances 0.000 claims description 13
- 206010013786 Dry skin Diseases 0.000 claims description 12
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 10
- 239000001099 ammonium carbonate Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 6
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- 229920000609 methyl cellulose Polymers 0.000 claims description 4
- 239000001923 methylcellulose Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 235000010980 cellulose Nutrition 0.000 claims description 2
- -1 hydroxypropyl Chemical group 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims 1
- 239000001768 carboxy methyl cellulose Substances 0.000 claims 1
- 235000013312 flour Nutrition 0.000 claims 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 16
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 5
- 238000004898 kneading Methods 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 230000001404 mediated effect Effects 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000004411 aluminium Substances 0.000 description 6
- 241000219782 Sesbania Species 0.000 description 5
- 229910001593 boehmite Inorganic materials 0.000 description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000010981 methylcellulose Nutrition 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000005504 petroleum refining Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002171 ethylene diamines Chemical class 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- KOFYJLDYJOEMNZ-UHFFFAOYSA-M [Al+3].[O-2].[Al+3].[OH-].[Al+3] Chemical compound [Al+3].[O-2].[Al+3].[OH-].[Al+3] KOFYJLDYJOEMNZ-UHFFFAOYSA-M 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940084030 carboxymethylcellulose calcium Drugs 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000003956 methylamines Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002370 organoaluminium group Chemical group 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/063—Preparing or treating the raw materials individually or as batches
- C04B38/0635—Compounding ingredients
- C04B38/0645—Burnable, meltable, sublimable materials
-
- B01J35/615—
-
- B01J35/635—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Abstract
The present invention provides a kind of preparation method of big pore volume alumina support, including amorphous alumina is turned into crystalline substance through solid phase under Additive, and kneading, shaping obtain alumina support through drying, roasting.Alumina support prepared by the inventive method has that method is simple, water consumption is small, with low cost, pore volume is big, high mechanical strength the characteristics of, be suitable for multiple catalysts field, in particular for the oil hydrogenation catalyst field of big pore volume.
Description
Technical field
The invention belongs to field of inorganic material preparing technology, it is related to a kind of preparation method of big pore volume alumina support, more specifically
Say, amorphous alumina and auxiliary agent solid phase are turned brilliant the present invention relates to one kind, are mediated, shaping, dry, roasting is obtained aluminum oxide
The method of carrier.
Background technology
Have that specific surface area is big, pore structure is controllable, heat endurance good due to aluminum oxide, high adsorption capacity the features such as, it is wide
It is general as catalyst, catalyst carrier and adsorbent etc..When aluminum oxide is as catalyst or carrier, its property is to whole catalyst
Performance play very important effect.Typically require that the crystallinity of aluminum oxide should be higher, impurity content should be relatively low, should have suitable
Suitable specific surface area, pore volume and aperture, while also to have certain acidity and acid strength.
As a rule, the aluminum oxide as catalyst and catalyst carrier needs design specific surface area as high as possible, with
Catalytic site and the concentration of activity is set to reach maximum, but in practical ranges, the relation in specific surface area and aperture is opposition
's.Especially in petroleum refining, with the increasingly in poor quality of petroleum resources, there are a large amount of organo-metallic compounds in feedstock oil
And asphalitine, most common of which metal is nickel, vanadium and iron.These metals are highly detrimental to various petroleum refining operations, such as add
Hydrogen cracking, hydrodesulfurization and catalytic cracking.These metals and asphalitine can cause the pore plugging of beds and reduction is urged
The agent life-span.A large amount of metal deposits on catalyst tend to make catalyst poisoning or inactivation.To prevent or slowing down catalyst
Poisoning or inactivation, it is necessary to sufficiently large hole is diffused, but will reduce specific surface area while improving hole.
Research shows, although hole of the diameter less than 6nm can increase the active portion digit of some silica/alumina hydrogenation catalysts
Measure, but these positions can be completely clogged with soot first, cause active reduction.Meanwhile, if being more than 10% total pore volume in catalyst
Hole by aperture more than 60nm (macropore) is occupied, then the mechanical crushing strength and catalysis activity of the catalyst can be reduced.
Therefore, the high-specific surface area, moderate and hydrothermally stable the aluminum oxide of pore size distribution that are suitable for catalyst carrier are prepared as numerous loads
The target of body researcher.
Petroleum refining generally has following three kinds of methods with petrochemical industry alumina support：Most commonly intending thin water aluminium
Stone is raw material, through extruded moulding, drying, roasting, cylinder or bar shaped aluminum oxide is obtained, or increase shaping is made after extruded moulding
Grain operation, is obtained spherical or other shapes aluminum oxide, and the method is most widely used；Second method is that aluminium hydroxide quickly takes off
Amorphous alumina obtained by water is raw material, and shaping, health, drying, the prepared ball-aluminium oxide of roasting, this kind of product are rolled through rotary drum
Product are typically used as adsorbent；Have again and boehmite is exactly prepared as aluminium glue, instilled deep fat post or oil ammonia column through aging
Treatment, dry, roasting are obtained ball-aluminium oxide.
As preparing the most important raw material of alumina support --- the production method of boehmite is broadly divided into Organic Alcohol
Aluminium method and inorganic neutralisation.Organo-aluminium alcoholate method refer to German Condea companies succeed in developing one kind with high-purity aluminium skimmings and higher alcohol
(n-amyl alcohol, n-hexyl alcohol) be raw material production high-quality boehmite, its production include aluminum hydroxide-aluminum oxide-aluminium -ol aluminium-
The cyclic process of aluminium hydroxide.Domestic boehmite production mainly uses inorganic neutralisation, including alkaline process, acid system and double aluminium
Method.Amorphous alumina, as another important source material for preparing alumina support, is as obtained in gibbsite quick burning
Aluminum oxide with ρ-or χ-crystal structure, most significant characteristic is but the activated alumina with high porosity and low cost
With its wide variety of some shortcoming is limited, such as activated alumina it is unstable due to its free energy high, in high response, by
In the fast dewatering method for forming activated alumina, its crystal formation is unbodied.
CN1088397C patents disclose a kind of preparation method of the alumina support for being suitable as heavy-oil hydrogenation catalyst,
A kind of aluminum contained compound solution is contacted with a kind of precipitant solution, the slurries containing aluminium hydroxide are obtained, filtered, wash, done
Dry, crushing, shaping obtain target product.CN1057443A is disclosed and for sour gas to be passed through inclined sodium chlorate solution, then aging,
The method that washing, separation of solid and liquid, drying, shaping prepare alumina support.CN1762579A discloses a kind of big pore volume aluminum oxide
Preparation method, be organic solvent with water, Organic Alcohol or miscible with water the aqueous solution in it is a kind of as solvent, by aluminium salt and
Cyclodextrin adds aqueous slkali to pH value to be more than or equal to 6 in wherein, then through washing, dry, crush, it is prepared by the step such as shaping
Go out alumina support.US3223483 reports amorphous alumina and rolls the method that shaping prepares low sodium ball-aluminium oxide, but should
Ball-aluminium oxide pore volume is typically each relatively low obtained in method.
Existing extruded moulding method consumes a large amount of soda acids firstly the need of prepared boehmite, whole process, produces very
Many high-salt wastewaters, carrier forming process needs to dry twice, that is, preparing the rich diaspore powder of plan need to carry out primary drying, mediate,
Need to carry out redrying after extruded moulding, and pore volume loss of the forming process to powder is larger.Amorphous alumina rolls shaping
Gained alumina support pore volume is smaller, is mainly used in adsorbent, is not suitable for use in needing the oil hydrogenation agent carrier of big pore volume.
The content of the invention：
It is an object of the invention to provide a kind of simplicity it is easy-to-use be particularly well-suited to heavy oil, residual hydrogenation with big pore volume aluminum oxide
The preparation method of carrier.The method reduces dry, pulverizing process during preparing, there is provided a kind of simple to operate, with low cost, product
The preparation method of the alumina support with larger pore volume.
The present invention is a kind of preparation method of alumina support, is carried out according to the following steps：
A) amorphous alumina, auxiliary agent and a certain amount of water are sufficiently mixed, wherein the particle diameter of amorphous alumina is 5~50
μm, auxiliary agent is selected from the one kind or several in the decomposable alkaline matter in urea, ammonium carbonate, ammonium hydrogen carbonate, methylamine, ethylenediamine
Kind, it is 0.5 to control amorphous alumina and auxiliary agent mass ratio:1~10:1, control the mass ratio of amorphous alumina and water
It is 1:1~10:1；
B) mixed material grinding is carried out into solid phase and turns brilliant reaction, the solid phase turn brilliant reaction time is 1~36h；；
C) solid phase is turned into brilliant product to add water mixing, adds extrusion aid, be kneaded into plastic, oxidation in control plastic
Aluminium and water ratio are 1:5~5:1, extrusion aid addition is the 0.1~20% of quality of alumina；
D) above-mentioned plastic carried out into extruded moulding, drying, be calcined to obtain alumina support.
According to method of the present invention, preferably include：
A) amorphous alumina, auxiliary agent and a certain amount of water are sufficiently mixed, wherein the particle diameter of amorphous alumina preferably 5~
20 μm, auxiliary agent is selected from one or more in urea, carbonic acid ammonia, ammonium hydrogen carbonate, controls amorphous alumina and the auxiliary agent ratio to be
1:1~5:1, the ratio for controlling amorphous alumina and water is 2:1~5:1；
B) mixed material grinding is carried out into solid phase and turns brilliant reaction, solid phase turn brilliant milled processed equipment used be selected from ball mill,
One or more equipment that superfine mill, Ball-stirring mill etc. are crushed for powder, solid phase turns the crystalline substance reaction time for 6~24h；
C) product is added water mixing, adds extrusion aid, be kneaded into plastic, aluminum oxide and water ratio in control plastic
Example is 2:3~3:2, extrusion aid addition is the 0.5~5% of quality of alumina；
D) drying process of shaping carrier is 80~120 DEG C of dryings 5~24 hours, and roasting process is 450~700 DEG C of roastings
3~8 hours.
According to method of the present invention, it is characterised in that：Extrusion aid is selected from sesbania powder, methylcellulose, hydroxypropyl first
One or more in base cellulose, carboxymethylcellulose calcium, starch, polyvinyl alcohol.
The method of the invention is a kind of to turn brilliant straight forming through solid phase by amorphous alumina and prepare alumina support
Method, whole process is simple and easy to apply, mild condition, energy consumption are low, and obtained alumina support pore volume is big, intensity is high, abrasion are low, is
A kind of method that low cost prepares high-performance alumina support.
Specific embodiment
Embodiment 1
Amorphous alumina, 120g urea and 150g water that 300g particle diameters are 12 μm are sufficiently mixed, then by mixture
Material loads ball mill grinding and reacts 12 hours, then takes out ground material, adds 5g sesbania powders, and add water 150g, is mediating
Mediated in machine and obtain plastic, the cylinder of 3mm is made through being pressed through orifice plate, in 120 DEG C of dryings 8 hours, 550 DEG C of roastings 5 were small
When obtain cylindrical shaped alumina carrier, its specific surface, pore volume, aperture, particle diameter, intensity index are shown in Table 1.
Embodiment 2
Amorphous alumina, 90g urea and 100g water that 300g particle diameters are 12 μm are sufficiently mixed, then by mixed material
Load ball mill grinding to react 12 hours, then take out ground material, add 5g sesbania powders, add water 220g, in kneader
Middle kneading obtains plastic, and the cylinder of 3mm is made through being pressed through orifice plate, and in 120 DEG C of dryings 8 hours, 550 DEG C were calcined 5 hours
Cylindrical shaped alumina carrier is obtained, its specific surface, pore volume, aperture, particle diameter, intensity index are shown in Table 1.
Embodiment 3
Amorphous alumina, 60g urea and 60g water that 300g particle diameters are 20 μm are sufficiently mixed, then by mixed material
Load ball mill grinding to react 24 hours, then take out ground material, add 2g sodium carboxymethylcelluloses, add water 180g,
Mediated in kneader and obtain plastic, the cylinder of 3mm is made through being pressed through orifice plate, in 120 DEG C of dryings 8 hours, 600 DEG C of roastings
Burning obtains cylindrical shaped alumina carrier in 5 hours, and its specific surface, pore volume, aperture, particle diameter, intensity index are shown in Table 1.
Embodiment 4
Amorphous alumina, 300g ammonium hydrogen carbonate and 100g water that 300g particle diameters are 5 μm are sufficiently mixed, then will mixing
Material loads ball mill grinding and reacts 12 hours, then takes out ground material, adds 10g sesbania powders, and add water 350g, is pinching
Mediated in conjunction machine and obtain plastic, the cylinder of 3mm is made through being pressed through orifice plate, in 100 DEG C of dryings 12 hours, 600 DEG C of roastings 5
Hour obtains cylindrical shaped alumina carrier, and its specific surface, pore volume, aperture, particle diameter, intensity index are shown in Table 1.
Embodiment 5
Amorphous alumina, 200g ammonium hydrogen carbonate and 100g water that 300g particle diameters are 5 μm are sufficiently mixed, then will mixing
Material loads superfine mill griding reaction 36 hours, then takes out ground material, adds 15g methylcellulose, adds water
340g, is mediated in kneader and obtains plastic, and the cylinder of 3mm is made through being pressed through orifice plate, in 100 DEG C of dryings 12 hours,
700 DEG C of roastings obtain cylindrical shaped alumina carrier in 5 hours, and its specific surface, pore volume, aperture, particle diameter, intensity index are shown in Table 1.
Embodiment 6
Amorphous alumina, 60g methylamines and 100g water that 300g particle diameters are 12 μm are sufficiently mixed, then by mixed material
Load Ball-stirring mill griding reaction 24 hours, then take out ground material, add 1.5g methylcellulose, add water 150g,
Mediated in kneader and obtain plastic, the cylinder of 3mm is made through being pressed through orifice plate, in 80 DEG C of dryings 24 hours, 700 DEG C of roastings
Obtain cylindrical shaped alumina carrier within 3 hours, its specific surface, pore volume, aperture, particle diameter, intensity index are shown in Table 1.
Embodiment 7
Amorphous alumina, 100g ethylenediamines and 100g water that 300g particle diameters are 5 μm are sufficiently mixed, then by mixture
Material loads ball mill grinding and reacts 1 hour, then takes out ground material, adds 5g starch, and add water 120g, in kneader
Kneading obtains plastic, and the cylinder of 3mm is made through being pressed through orifice plate, in 120 DEG C of dryings 5 hours, 450 DEG C of roastings 8 hours
To cylindrical shaped alumina carrier, its specific surface, pore volume, aperture, particle diameter, intensity index are shown in Table 1.
Embodiment 8
Amorphous alumina, 100g ethylenediamines and 100g water that 300g particle diameters are 12 μm are sufficiently mixed, then will mixing
Material loads ball mill grinding and reacts 12 hours, then takes out ground material, adds 10g hydroxypropyl methyl celluloses, plus
Water 120g, is mediated in kneader and obtains plastic, and the cylinder of 3mm is made through being pressed through orifice plate, small in 120 DEG C of dryings 12
When, 500 DEG C of roastings obtain cylindrical shaped alumina carrier in 8 hours, and its specific surface, pore volume, aperture, particle diameter, intensity index are shown in Table 1.
Embodiment 9
Amorphous alumina, 300g ammonium hydrogen carbonate and 300g water that 300g particle diameters are 12 μm are sufficiently mixed, then will be mixed
Compound material loads Ball-stirring mill griding reaction 24 hours, then takes out ground material, adds 1.5g polyvinyl alcohol, adds water
148g, is mediated in kneader and obtains plastic, and the cylinder of 3mm is made through being pressed through orifice plate, in 120 DEG C of dryings 8 hours,
550 DEG C of roastings obtain cylindrical shaped alumina carrier in 5 hours, and its specific surface, pore volume, aperture, particle diameter, intensity index are shown in Table 1.
Embodiment 10
Amorphous alumina, 30g urea and 30g water that 300g particle diameters are 12 μm are sufficiently mixed, then by mixed material
Load ball mill grinding to react 12 hours, then take out ground material, add 5g sesbania powders, add water 200g, in kneader
Middle kneading obtains plastic, and the cylinder of 3mm is made through being pressed through orifice plate, and in 120 DEG C of dryings 8 hours, 550 DEG C were calcined 5 hours
Cylindrical shaped alumina carrier is obtained, its specific surface, pore volume, aperture, particle diameter, intensity index are shown in Table 1.
The different embodiment resulting vehicle pore structures of table 1 and intensity index
Claims (3)
1. a kind of preparation method of big pore volume alumina support, it is characterised in that carry out according to the following steps：
A) amorphous alumina, auxiliary agent and a certain amount of water are sufficiently mixed, wherein the particle diameter of amorphous alumina is 5~50 μm,
Auxiliary agent is selected from one or more in the decomposable alkaline matter in urea, ammonium carbonate, ammonium hydrogen carbonate, methylamine, ethylenediamine, control
Amorphous alumina processed and auxiliary agent mass ratio are 0.5:1~10:1, it is 1 with the mass ratio of water to control amorphous alumina:1
~10:1；
B) mixed material grinding is carried out into solid phase and turns brilliant reaction, the solid phase turn brilliant reaction time is 1~36h；；
C) solid phase is turned into brilliant product to add water mixing, adds extrusion aid, be kneaded into plastic, in control plastic aluminum oxide and
Water quality ratio is 1:5~5:1, extrusion aid addition is the 0.1~20% of quality of alumina；
D) above-mentioned plastic carried out into extruded moulding, drying, be calcined to obtain alumina support.
2. in accordance with the method for claim 1, it is characterised in that：
A) amorphous alumina, auxiliary agent and a certain amount of water are sufficiently mixed, wherein the particle diameter of amorphous alumina is 5~20 μm,
Selected from one or more in urea, carbonic acid ammonia, ammonium hydrogen carbonate, it is 1 to control amorphous alumina and auxiliary agent mass ratio to auxiliary agent:
1~5:1, it is 2 with the mass ratio of water to control amorphous alumina:1~5:1；
B) mixed material grinding is carried out into solid phase and turns brilliant reaction, solid phase turns brilliant milled processed equipment used and is selected from ball mill, ultra-fine
One or more equipment of flour mill, Ball-stirring mill, solid phase turns the crystalline substance reaction time for 6~24h；
C) product is added water mixing, adds extrusion aid, be kneaded into plastic, aluminum oxide and water quality ratio in control plastic
Example is 2:3~3:2, extrusion aid addition is the 0.5~5% of quality of alumina；
D) drying process of shaping carrier is 80~120 DEG C of dryings 5~24 hours, and roasting process is 450~700 DEG C of roastings 3~8
Hour.
3. in accordance with the method for claim 1, it is characterised in that：Extrusion aid is selected from sesbania powder, methylcellulose, hydroxypropyl first
One or more in base cellulose, sodium carboxymethylcellulose, starch, polyvinyl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611029989.4A CN106747591B (en) | 2016-11-15 | 2016-11-15 | A kind of macropore holds the preparation method of alumina support |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611029989.4A CN106747591B (en) | 2016-11-15 | 2016-11-15 | A kind of macropore holds the preparation method of alumina support |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106747591A true CN106747591A (en) | 2017-05-31 |
| CN106747591B CN106747591B (en) | 2019-07-19 |
Family
ID=58970426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611029989.4A Active CN106747591B (en) | 2016-11-15 | 2016-11-15 | A kind of macropore holds the preparation method of alumina support |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106747591B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110935458A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Preparation method of hydrodemetallization catalyst |
| CN110935468A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Preparation method of residual oil hydrodemetallization catalyst |
| CN110935469A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Preparation method of high-activity hydrodemetallization catalyst |
| CN111097460A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Residual oil hydrodemetallization catalyst and preparation method thereof |
| CN111097459A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Residual oil hydrodemetallization catalyst and preparation method thereof |
| CN111298782A (en) * | 2018-12-12 | 2020-06-19 | 中国石油化工股份有限公司 | Integral honeycomb cordierite carrier and preparation method thereof |
| CN111686748A (en) * | 2019-03-13 | 2020-09-22 | 中国石油化工股份有限公司 | Preparation method of residual oil hydrodemetallization catalyst |
| CN113769723A (en) * | 2021-09-18 | 2021-12-10 | 北京化工大学 | Low-density spherical alumina and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4613585A (en) * | 1983-08-04 | 1986-09-23 | Nikki-Universal Co., Ltd. | Process of preparing alumina for use in catalyst carrier |
| CN1714937A (en) * | 2004-06-29 | 2006-01-04 | 中国石油化工股份有限公司 | Great pore volume formed aluminium oxide carrier and its preparing method |
| CN102861616A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Preparation method of alumina supporter with concentrated hole distribution |
| CN105753027A (en) * | 2016-01-26 | 2016-07-13 | 广西壮族自治区化工研究院 | Method for preparing solid phases of gamma-Al2O3 carriers with high specific surface areas |
-
2016
- 2016-11-15 CN CN201611029989.4A patent/CN106747591B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4613585A (en) * | 1983-08-04 | 1986-09-23 | Nikki-Universal Co., Ltd. | Process of preparing alumina for use in catalyst carrier |
| CN1714937A (en) * | 2004-06-29 | 2006-01-04 | 中国石油化工股份有限公司 | Great pore volume formed aluminium oxide carrier and its preparing method |
| CN102861616A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Preparation method of alumina supporter with concentrated hole distribution |
| CN105753027A (en) * | 2016-01-26 | 2016-07-13 | 广西壮族自治区化工研究院 | Method for preparing solid phases of gamma-Al2O3 carriers with high specific surface areas |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110935469B (en) * | 2018-09-25 | 2022-04-05 | 中国石油化工股份有限公司 | Preparation method of high-activity hydrodemetallization catalyst |
| CN110935468A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Preparation method of residual oil hydrodemetallization catalyst |
| CN110935469A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Preparation method of high-activity hydrodemetallization catalyst |
| CN110935468B (en) * | 2018-09-25 | 2022-06-07 | 中国石油化工股份有限公司 | Preparation method of residual oil hydrodemetallization catalyst |
| CN110935458A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Preparation method of hydrodemetallization catalyst |
| CN111097459B (en) * | 2018-10-25 | 2022-06-07 | 中国石油化工股份有限公司 | Residual oil hydrodemetallization catalyst and preparation method thereof |
| CN111097459A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Residual oil hydrodemetallization catalyst and preparation method thereof |
| CN111097460A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Residual oil hydrodemetallization catalyst and preparation method thereof |
| CN111097460B (en) * | 2018-10-25 | 2022-06-07 | 中国石油化工股份有限公司 | Residual oil hydrodemetallization catalyst and preparation method thereof |
| CN111298782A (en) * | 2018-12-12 | 2020-06-19 | 中国石油化工股份有限公司 | Integral honeycomb cordierite carrier and preparation method thereof |
| CN111686748A (en) * | 2019-03-13 | 2020-09-22 | 中国石油化工股份有限公司 | Preparation method of residual oil hydrodemetallization catalyst |
| CN111686748B (en) * | 2019-03-13 | 2022-06-07 | 中国石油化工股份有限公司 | Preparation method of residual oil hydrodemetallization catalyst |
| CN113769723A (en) * | 2021-09-18 | 2021-12-10 | 北京化工大学 | Low-density spherical alumina and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106747591B (en) | 2019-07-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106747591B (en) | A kind of macropore holds the preparation method of alumina support | |
| US4016106A (en) | Preparation of catalysts of predetermined pore size distribution and pore volume | |
| CN102049265B (en) | Hydrotreating catalyst and preparation method thereof | |
| CN100363470C (en) | Slag oil hydro-demetallization catalyst and its preparing method | |
| CN105983443B (en) | A kind of alumina supporter and preparation method thereof | |
| JP4818163B2 (en) | Alumina support, hydrodemetallation catalyst using the same, and production method thereof | |
| CN102923744A (en) | Preparation method for aluminum oxide by direct forming method | |
| EP2772308B1 (en) | Hydrogenation catalyst and method for producing same | |
| CN101255360A (en) | Process for slurry phase hydroconversion of heavy hydrocarbon feeds and/or coal using a supported catalyst | |
| CN102849763A (en) | Solid phase preparation method for gamma-alumina with gradient distribution holes | |
| CN105174293B (en) | A kind of preparation method for the boehmite that pore-size distribution is concentrated | |
| US4016108A (en) | Preparation of catalysts of predetermined pore size distribution and pore volume | |
| CN102861618B (en) | Preparation method of alumina supporter | |
| CN103657667A (en) | Preparation method for novel heavy oil hydrogenization demetallization catalyst adopting macroporous structures | |
| CN103041870B (en) | Alumina supporter, and preparation method and application thereof | |
| EP3074486B1 (en) | A process for the catalytic conversion of micro carbon residue content of heavy hydrocarbon feedstocks and a low surface area catalyst composition for use therein | |
| US4145316A (en) | Preparation of catalysts of predetermined pore size distribution and pore volume | |
| CN104549427B (en) | A kind of high-quality industrial chemicals hydrocracking catalyst and preparation method thereof | |
| US4016107A (en) | Preparation of catalysts of predetermined pore size distribution and pore volume | |
| CN103285935B (en) | Hydrogenation protection catalyst and preparation method thereof | |
| JPH0613095B2 (en) | Highly stable method for producing hydrotreating catalyst | |
| CN104646072B (en) | A kind of preparation method of carrier of hydrogenating catalyst | |
| CN104646071B (en) | A kind of clean method for preparing of carrier of hydrogenating catalyst | |
| CN100589876C (en) | A titanium-containing aluminum hydroxide and preparation method thereof | |
| CN104338527A (en) | Heavy oil hydrogenation diasphaltene catalyst, and preparation method and application thereof |
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 | ||
| CB02 | Change of applicant information |
Address after: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Applicant after: China Offshore Oil Group Co., Ltd. Applicant after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE CO., LTD. Applicant after: CNOOC Energy Development Co., Ltd. Address before: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Applicant before: China National Offshore Oil Corporation Applicant before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE CO., LTD. Applicant before: CNOOC Energy Development Co., Ltd. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |