CN106747591B - A kind of macropore holds the preparation method of alumina support - Google Patents
A kind of macropore holds the preparation method of alumina support Download PDFInfo
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- CN106747591B CN106747591B CN201611029989.4A CN201611029989A CN106747591B CN 106747591 B CN106747591 B CN 106747591B CN 201611029989 A CN201611029989 A CN 201611029989A CN 106747591 B CN106747591 B CN 106747591B
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- alumina
- water
- amorphous alumina
- solid phase
- auxiliary agent
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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 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 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 31
- 238000000465 moulding Methods 0.000 claims abstract description 14
- 239000007790 solid phase Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 25
- 229920003023 plastic Polymers 0.000 claims description 20
- 239000012752 auxiliary agent Substances 0.000 claims description 13
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 11
- 239000001099 ammonium carbonate Substances 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 10
- 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
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 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
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 235000013877 carbamide Nutrition 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 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 description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 235000010980 cellulose Nutrition 0.000 claims description 2
- -1 hydroxypropyl Chemical group 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 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
- 235000013312 flour Nutrition 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 17
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 238000000227 grinding Methods 0.000 description 7
- 230000001404 mediated effect Effects 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 241000219782 Sesbania Species 0.000 description 5
- 239000004411 aluminium Substances 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 5
- 239000011148 porous material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000003921 oil 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
- 238000004898 kneading Methods 0.000 description 3
- 235000010981 methylcellulose Nutrition 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000005504 petroleum refining Methods 0.000 description 3
- 239000000047 product Substances 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
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 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
- 229920002134 Carboxymethyl cellulose Polymers 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
- 206010013786 Dry skin Diseases 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
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 150000001875 compounds Chemical class 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
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process 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
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 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
- 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
- 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
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
Abstract
The present invention provides the preparation method that a kind of macropore holds alumina support, including amorphous alumina is turned crystalline substance through solid phase under Additive, mediates, molding, obtains alumina support through drying, roasting.The alumina support of the method for the present invention preparation has the characteristics that method is simple, water consumption is small, low in cost, Kong Rong great, high mechanical strength, is suitable for multiple catalysts field, the oil hydrogenation catalyst field held in particular for macropore.
Description
Technical field
The invention belongs to field of inorganic material preparing technology, are related to a kind of preparation method of macropore appearance alumina support, more specifically
Say, the present invention relates to it is a kind of amorphous alumina and auxiliary agent solid phase turned brilliant, mediate, molding, it is dry, roast aluminium oxide be made
The method of carrier.
Background technique
It is wide since aluminium oxide has the characteristics that large specific surface area, pore structure are controllable, thermal stability is good, adsorption capacity is strong
It is general to be used as catalyst, catalyst carrier and adsorbent etc..When aluminium oxide is as catalyst or carrier, property is to entire catalyst
Performance play very important effect.Generally require the crystallinity of aluminium oxide should be higher, impurity content is answered lower, should be had suitable
Suitable specific surface area, Kong Rong and aperture, while also there is certain acidity and acid strength.
Usually, it needs to design specific surface area as high as possible as catalyst and the aluminium oxide of catalyst carrier, with
Catalytic site and active concentration is set to reach maximum, but in practical ranges, the relationship 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, one of the most common metal are 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 will lead to the pore plugging of catalyst bed and reduction is urged
The agent service life.A large amount of metal deposits on catalyst tend to make catalyst poisoning or inactivation.To prevent or slow down catalyst
Poisoning or inactivation, it is necessary to sufficiently large hole is diffused, but improve hole while will reduce specific surface area.
Studies have shown that although hole of the diameter lower than 6nm can increase the active portion digit of certain silica/alumina hydrogenation catalysts
Amount, but these positions can be completely clogged with soot first, lead to active reduction.Meanwhile if being greater than 10% total pore volume in catalyst
It is occupied by the hole that aperture is greater than 60nm (macropore), then the mechanical crushing strength and catalytic activity of the catalyst can reduce.
Therefore, preparation is suitable for that the high-specific surface area of catalyst carrier, pore size distribution be moderate and the aluminium oxide of hydrothermally stable becomes numerous loads
The target of body researcher.
Petroleum refining and petrochemical industry alumina support usually have following three kinds of methods: most commonly to intend thin water aluminium
Stone is raw material, through extruded moulding, drying, roasting, cylindrical or bar shaped aluminium oxide is made, or increase shaping after extruded moulding and make
Grain process, is made spherical or other shapes aluminium oxide, which is most widely used；Second method is that aluminium hydroxide quickly takes off
The resulting amorphous alumina of water is raw material, rolls molding through rotary drum, health, drying, roasts obtained ball-aluminium oxide, this kind of production
Product are typically used as adsorbent；Have again and boehmite is exactly prepared as aluminium glue, is instilled hot oil column or oil ammonia column through aging
Ball-aluminium oxide is made in processing, dry, roasting.
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 refers to that German Condea company succeeds in developing a kind of with high-purity aluminium skimmings and higher alcohol
(n-amyl alcohol, n-hexyl alcohol) is the high-quality boehmite of raw material production, and production includes 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 is as made from gibbsite quick burning as another important source material for preparing alumina support
With ρ-or χ-crystal structure aluminium oxide, most significant characteristic is with high porosity and low cost, but activated alumina
Have the shortcomings that limit its it is widely applied several, if activated alumina is unstable due to its high free energy, is in high response, by
In the fast dewatering method for forming activated alumina, crystal form is amorphous.
CN1088397C patent discloses a kind of preparation method of 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 is obtained, is filtered, washed, does
Dry, crushing, molding obtain target product.CN1057443A, which is disclosed, is passed through inclined sodium chlorate solution for sour gas, subsequent aging,
Washing is separated by solid-liquid separation, the method that dry, molding prepares alumina support.CN1762579A discloses a kind of macropore appearance aluminium oxide
Preparation method, be using one of water, Organic Alcohol or aqueous solution of organic solvent miscible with water as solvent, by aluminium salt and
Cyclodextrin is added aqueous slkali to pH value and is more than or equal to 6 in wherein, then through washing, drying, crushing, molding and etc. preparation
Alumina support out.US3223483 reports amorphous alumina and rolls the method that molding prepares low sodium ball-aluminium oxide, but should
Ball-aluminium oxide hole made from method holds usually lower.
Existing extruded moulding method consumes a large amount of soda acids firstly the need of obtained boehmite, whole process, generates very
More high-salt wastewaters, carrier forming process need to dry twice, that is, primary drying need to be carried out by preparing quasi- rich diaspore powder, mediate,
It needs to carry out redrying after extruded moulding, and forming process is larger to the hole appearance loss of powder.Amorphous alumina rolls molding
Gained carrying alumina body opening appearance is smaller, is mainly used for adsorbent, is not suitable for use in the oil hydrogenation agent carrier for needing macropore to hold.
Summary of the invention:
The object of the present invention is to provide a kind of simple and easy-to-use especially suitable for heavy oil, residual hydrogenation macropore appearance aluminium oxide
The preparation method of carrier.Dry, pulverizing process is reduced during method preparation, a kind of easy to operate, low in cost, product is provided
The preparation method of alumina support with biggish Kong Rong.
The present invention is a kind of preparation method of alumina support, it is characterised in that is sequentially included the following steps:
A) amorphous alumina, auxiliary agent and a certain amount of water are sufficiently mixed, wherein the partial size of amorphous alumina is 5~50
μm, one of the decomposable alkaline matter of auxiliary agent in urea, ammonium carbonate, ammonium hydrogen carbonate, methylamine, ethylenediamine or several
Kind, it controls amorphous alumina and auxiliary agent mass ratio is 0.5:1~10:1, control the mass ratio of amorphous alumina and water
For 1:1~10:1；
B) mixed material is ground into the brilliant reaction of progress solid phase turn, solid phase turns the crystalline substance reaction time as 1~36h；
C) add water to mix reaction product, extrusion aid is added, be kneaded into plastic, control aluminium oxide and water ratio in plastic
Example is 1:5~5:1, and extrusion aid additional amount is the 0.1~20% of quality of alumina；
D) above-mentioned plastic is subjected to extruded moulding, drying, roasts to obtain alumina support.
Method according to the present invention, it is characterised in that:
A) amorphous alumina, auxiliary agent and a certain amount of water are sufficiently mixed, wherein the partial size of amorphous alumina preferably 5~
20 μm, auxiliary agent is selected from one or more of urea, carbonic acid ammonia, ammonium hydrogen carbonate, controls amorphous alumina and auxiliary agent ratio is
1:1~5:1, the ratio for controlling amorphous alumina and water is 2:1~5:1；
B) mixed material is ground and carries out solid phase and turn brilliant reaction, solid phase turn milled processed equipment used in crystalline substance be selected from ball mill,
Superfine mill, Ball-stirring mill etc. are used for one or more of equipment that powder crushes, solid phase turn the brilliant reaction time be 6~for 24 hours；
C) add water to mix reaction product, extrusion aid is added, be kneaded into plastic, control aluminium oxide and water ratio in plastic
Example is 2:3~3:2, and extrusion aid additional amount is the 0.5~5% of quality of alumina；
D) drying process of shaping carrier is 80~120 DEG C 5~24 hours dry, and roasting process is 450~700 DEG C of roastings
3~8 hours.
Method according to the present invention, it is characterised in that: extrusion aid is selected from sesbania powder, methylcellulose, hydroxypropyl first
One or more of base cellulose, carboxymethyl cellulose, 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, mild condition, low energy consumption, and carrying alumina body opening appearance obtained is big, intensity is high, abrasion are low, is
A kind of method of low cost preparation high-performance alumina support.
Specific embodiment
Embodiment 1
Amorphous alumina, 120g urea and 150g water that 300g partial size is 12 μm are sufficiently mixed, then by mixture
Material is packed into ball mill grinding and reacts 12 hours, then takes out ground material, and 5g sesbania powder is added, adds water 150g, is mediating
It is mediated in machine and obtains plastic, the cylinder that 3mm is made through being pressed through orifice plate is 8 hours dry at 120 DEG C, and 550 DEG C of roastings 5 are small
When obtain cylindrical shaped alumina carrier, specific surface, Kong Rong, aperture, partial size, intensity index are shown in Table 1.
Embodiment 2
Amorphous alumina, 90g urea and 100g water that 300g partial size is 12 μm are sufficiently mixed, then by mixed material
It is packed into ball mill grinding to react 12 hours, then takes out ground material, 5g sesbania powder is added, adds water 220g, in kneader
Middle kneading obtains plastic, the cylinder that 3mm is made through being pressed through orifice plate, 8 hours dry at 120 DEG C, and 550 DEG C roast 5 hours
Cylindrical shaped alumina carrier is obtained, specific surface, Kong Rong, aperture, partial size, intensity index are shown in Table 1.
Embodiment 3
Amorphous alumina, 60g urea and 60g water that 300g partial size is 20 μm are sufficiently mixed, then by mixed material
It is packed into ball mill grinding to react 24 hours, then takes out ground material, 2g sodium carboxymethylcellulose is added, adds water 180g,
It is mediated in kneader and obtains plastic, the cylinder that 3mm is made through being pressed through orifice plate is 8 hours dry at 120 DEG C, 600 DEG C of roastings
It burns 5 hours and obtains cylindrical shaped alumina carrier, specific surface, Kong Rong, aperture, partial size, intensity index are shown in Table 1.
Embodiment 4
Amorphous alumina, 300g ammonium hydrogen carbonate and 100g water that 300g partial size is 5 μm are sufficiently mixed, it then will mixing
Material is packed into ball mill grinding and reacts 12 hours, then takes out ground material, and 10g sesbania powder is added, adds water 350g, is pinching
It is mediated in conjunction machine and obtains plastic, the cylinder that 3mm is made through being pressed through orifice plate is 12 hours dry at 100 DEG C, 600 DEG C of roastings
Cylindrical shaped alumina carrier is obtained within 5 hours, specific surface, Kong Rong, aperture, partial size, intensity index are shown in Table 1.
Embodiment 5
Amorphous alumina, 200g ammonium hydrogen carbonate and 100g water that 300g partial size is 5 μm are sufficiently mixed, it then will mixing
Material is packed into superfine mill griding reaction 36 hours, then takes out ground material, and 15g methylcellulose is added, adds water
340g is mediated in kneader and is obtained plastic, and the cylinder that 3mm is made through being pressed through orifice plate is 12 hours dry at 100 DEG C,
700 DEG C of roastings obtain cylindrical shaped alumina carrier in 5 hours, and specific surface, Kong Rong, aperture, partial size, intensity index are shown in Table 1.
Embodiment 6
Amorphous alumina, 60g methylamine and 100g water that 300g partial size is 12 μm are sufficiently mixed, then by mixed material
It is packed into Ball-stirring mill griding reaction 24 hours, then takes out ground material, 1.5g methylcellulose is added, adds water 150g,
It is mediated in kneader and obtains plastic, the cylinder that 3mm is made through being pressed through orifice plate is 24 hours dry at 80 DEG C, 700 DEG C of roastings
Cylindrical shaped alumina carrier is obtained within 3 hours, specific surface, Kong Rong, aperture, partial size, intensity index are shown in Table 1.
Embodiment 7
Amorphous alumina, 100g ethylenediamine and 100g water that 300g partial size is 5 μm are sufficiently mixed, then by mixture
Material is packed into ball mill grinding and reacts 1 hour, then takes out ground material, and 5g starch is added, adds water 120g, in kneader
Kneading obtains plastic, the cylinder that 3mm is made through being pressed through orifice plate, 5 hours dry at 120 DEG C, and 450 DEG C obtain for roasting 8 hours
To cylindrical shaped alumina carrier, specific surface, Kong Rong, aperture, partial size, intensity index are shown in Table 1.
Embodiment 8
Amorphous alumina, 100g ethylenediamine and 100g water that 300g partial size is 12 μm are sufficiently mixed, it then will mixing
Material is packed into ball mill grinding and reacts 12 hours, then takes out ground material, and 10g hydroxypropyl methyl cellulose is added, adds
Water 120g is mediated in kneader and is obtained plastic, the cylinder that 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 specific surface, Kong Rong, aperture, partial size, intensity index are shown in Table 1.
Embodiment 9
Amorphous alumina, 300g ammonium hydrogen carbonate and 300g water that 300g partial size is 12 μm are sufficiently mixed, will then be mixed
It closes material to be packed into Ball-stirring mill griding reaction 24 hours, then takes out ground material, 1.5g polyvinyl alcohol is added, adds water
148g is mediated in kneader and is obtained plastic, and the cylinder that 3mm is made through being pressed through orifice plate is 8 hours dry at 120 DEG C,
550 DEG C of roastings obtain cylindrical shaped alumina carrier in 5 hours, and specific surface, Kong Rong, aperture, partial size, intensity index are shown in Table 1.
Embodiment 10
Amorphous alumina, 30g urea and 30g water that 300g partial size is 12 μm are sufficiently mixed, then by mixed material
It is packed into ball mill grinding to react 12 hours, then takes out ground material, 5g sesbania powder is added, adds water 200g, in kneader
Middle kneading obtains plastic, the cylinder that 3mm is made through being pressed through orifice plate, 8 hours dry at 120 DEG C, and 550 DEG C roast 5 hours
Cylindrical shaped alumina carrier is obtained, specific surface, Kong Rong, aperture, partial size, intensity index are shown in Table 1.
The different embodiment resulting vehicle pore structures of table 1 and intensity index
。
Claims (3)
1. the preparation method that a kind of macropore holds alumina support, it is characterised in that sequentially include the following steps:
A) amorphous alumina, auxiliary agent and a certain amount of water are sufficiently mixed, wherein the partial size of amorphous alumina is 5~50 μm,
Decomposable alkaline matter one or more of of the auxiliary agent in urea, ammonium carbonate, ammonium hydrogen carbonate, methylamine, ethylenediamine, control
Amorphous alumina and auxiliary agent mass ratio processed is 0.5:1~10:1, and the mass ratio for controlling amorphous alumina and water is 1:1
~10:1；
B) mixed material is ground into the brilliant reaction of progress solid phase turn, solid phase turns the crystalline substance reaction time as 1~36h；
C) solid phase is turned brilliant reaction product adds water to mix, and extrusion aid is added, and is kneaded into plastic, control in plastic aluminium oxide with
Water quality ratio is 1:5~5:1, and extrusion aid additional amount is the 0.1~20% of quality of alumina；
D) above-mentioned plastic is subjected to extruded moulding, drying, roasts to obtain alumina support.
2. according to 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 partial size of amorphous alumina is 5~20 μm,
Auxiliary agent is selected from one or more of urea, ammonium carbonate, ammonium hydrogen carbonate, and controlling amorphous alumina and auxiliary agent mass ratio is 1:
1~5:1, the mass ratio for controlling amorphous alumina and water is 2:1~5:1；
B) mixed material is ground and carries out solid phase and turns brilliant reaction, solid phase turns milled processed equipment used in crystalline substance and is selected from ball mill, ultra-fine
One or more of equipment of flour mill, Ball-stirring mill, solid phase turn the brilliant reaction time be 6~for 24 hours；
C) add water to mix reaction product, extrusion aid is added, be kneaded into plastic, control aluminium oxide and water quality ratio in plastic
Example is 2:3~3:2, and extrusion aid additional amount is the 0.5~5% of quality of alumina；
D) drying process of shaping carrier is 80~120 DEG C 5~24 hours dry, and roasting process is 450~700 DEG C of roastings 3~8
Hour.
3. according to the method for claim 1, it is characterised in that: extrusion aid is selected from sesbania powder, methylcellulose, hydroxypropyl first
One or more of base cellulose, sodium carboxymethylcellulose, starch, polyvinyl alcohol.
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| CN110935458B (en) * | 2018-09-25 | 2022-04-08 | 中国石油化工股份有限公司 | Preparation method of 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 |
| 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 |
| 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 |
| CN111298782B (en) * | 2018-12-12 | 2022-08-12 | 中国石油化工股份有限公司 | Integral honeycomb cordierite carrier and preparation method thereof |
| 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 |
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| 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 |
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| 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 |
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