CN106732787A - A kind of activation method of bauxite, bauxite catalyst and preparation method thereof - Google Patents
A kind of activation method of bauxite, bauxite catalyst and preparation method thereof Download PDFInfo
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- CN106732787A CN106732787A CN201611031402.3A CN201611031402A CN106732787A CN 106732787 A CN106732787 A CN 106732787A CN 201611031402 A CN201611031402 A CN 201611031402A CN 106732787 A CN106732787 A CN 106732787A
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- bauxite
- acid
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- catalyst
- organic acid
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- 229910001570 bauxite Inorganic materials 0.000 title claims abstract description 102
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000004913 activation Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 150000007524 organic acids Chemical class 0.000 claims abstract description 30
- 238000010306 acid treatment Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 150000001450 anions Chemical class 0.000 claims abstract description 7
- 150000001768 cations Chemical class 0.000 claims abstract description 5
- 239000013522 chelant Substances 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005360 mashing Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- -1 rare earth compound Chemical class 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 5
- 229910001593 boehmite Inorganic materials 0.000 claims description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 5
- 235000014655 lactic acid Nutrition 0.000 claims description 5
- 238000001935 peptisation Methods 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 claims description 3
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 229940116269 uric acid Drugs 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 244000248349 Citrus limon Species 0.000 claims description 2
- 235000005979 Citrus limon Nutrition 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 230000033228 biological regulation Effects 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 229910001608 iron mineral Inorganic materials 0.000 abstract description 4
- 238000001994 activation Methods 0.000 description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 18
- 239000011148 porous material Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000003213 activating effect Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 239000012467 final product Substances 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 150000007522 mineralic acids Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000010494 dissociation reaction Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000040710 Chela Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 150000001398 aluminium Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
- B01J35/613—10-100 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
- B01J35/633—Pore volume less than 0.5 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
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
- C10G47/26—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles suspended in the oil, e.g. slurries
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1077—Vacuum residues
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to bauxite activation field, and in particular to a kind of activation method of bauxite, comprise the following steps：Acid treatment, and stir-activating are carried out to bauxite with organic acid, then the bauxite activated after drying, roasting；Wherein, the organic acid has and ionizes in the solution, and the anion for ionizing out is presented the characteristic that multiple tooth Chelating Properties form chelate with bridging metal cation.Bauxite catalyst prepared present invention also offers a kind of utilization above method and preparation method thereof.The method that the present invention is provided can fully dissociate the iron mineral in bauxite, improve the catalytic performance of bauxite.
Description
Technical field
The present invention relates to bauxite activation field, and in particular to a kind of activation method of bauxite, bauxite catalyst and
Its preparation method.
Background technology
China's bauxite resource enriches, and bauxite is production metallic aluminium and aluminous refractory or aluminosilicate refractory fiber
Primary raw material.Bauxite is made up of the particle of some layer structures, is heat-treated or is aided with suitable additives through hydro-thermal, roasting
Row is modified, can prepare high-specific surface area, the activated alumina of larger pore volume, and activated alumina possesses good stability and price
Relatively low advantage, is typically used to catalyst field.
Contain alumino-silicate, high mechanical strength, the pore structure with the comparison rule for naturally occurring in bauxite.Contain simultaneously
There is the iron-bearing mineral that content is higher, be potential catalysis activity phase.But the iron-bearing mineral in bauxite is relatively advised with diaspore
Adjoining then is inlayed, and in fine pulse-like or parcel squamous layer circle, this irony dissociation inlayed is difficult, and crystal grain is larger, used as catalysis
Tend not to be sufficiently activated when agent is used.
Chinese patent literature (CN105032497A) discloses a kind of carbon monoxide transformation catalyst carrier, based on carrier
Catalyst and preparation method, the raw material components of catalyst carrier include modified bauxite 5-15 weight portions, aluminum oxide or intend thin water
Aluminium stone 40-60 weight portions, magnesia or magnesium hydroxide 20-40 weight portions, the modified bauxite are adopted and prepared with the following method：First
Acid treatment is carried out to natural bauxite, then is washed with distilled water to cleaning solution in neutrality, through filtering, being drying to obtain the modified aluminium
Tu Kuang, it is one or several the mixture in nitric acid, phosphoric acid, boric acid that the acid treatment uses acid.Use inorganic acid pair
Bauxite carries out acid treatment, is replaced with iron cation contained in bauxite material using the hydrogen ion in inorganic acid, so
NO3 -、PO3 3-、BO3 3-And Cl-Will be present in the form of impurity in final product, cause environmental pollution；On the other hand,
Even if using the inorganic acid of larger concentration, inorganic acid is still limited to the irony dissociation degree in bauxite, and the irony for dissolving
Poor dispersion, the pore volume aperture of modified bauxite is smaller to cause reactant molecule diffusion to there is steric hindrance, and catalytic efficiency is relatively low；Make
The original structure of bauxite can be also destroyed with inorganic acid, the later stage application of bauxite is influenceed.
The content of the invention
Therefore, the technical problem to be solved in the present invention is to be inlayed in bauxite in the activation process for overcome existing bauxite
Iron mineral dissociation it is difficult, bauxite can not give full play to the defect of catalytic performance, there is provided one kind can fully dissociate bauxite
In iron mineral, improve bauxite catalytic performance bauxite activation method.
A kind of activation method of bauxite, comprises the following steps：
Acid treatment, and stir-activating are carried out to bauxite with organic acid, then the alum clay activated after drying, roasting
Ore deposit；
Wherein, the organic acid has and ionizes in the solution, and the anion for ionizing out is presented multiple tooth Chelating Properties
The characteristic of chelate is formed with bridging metal cation.
In the activation method of described bauxite, the organic acid is the one kind in malonic acid, citric acid, acetic acid and lactic acid
Or several mixtures, the organic acid is preferably malonic acid.
In the activation method of described bauxite, the temperature of the stir-activating is 75~90 DEG C, the time of stir-activating
It is 0.5~1.5h.
In the activation method of described bauxite, the organic acid is 1.2~3 with the solid volume ratio of the liquid of the bauxite:
1, the concentration of the organic acid is 0.2~0.9mol/L.
In the activation method of described bauxite, the dry temperature is 80~100 DEG C, and the time is 9~12h, described
The temperature of roasting is 300~550 DEG C, and the time is 1~3.5h.
In the activation method of described bauxite, added in also including to the mixture after acid treatment after stir-activating and contained
One or more in aluminium base binding agent, expanding agent and acid modulating agent carry out mixing mashing.
In the activation method of described bauxite, the binding agent containing aluminium base is peptization boehmite and/or aluminum oxide
Colloidal sol；
The expanding agent is one or more in activated carbon, carbon black, uric acid, polyethylene glycol, cellulose and sesbania powder
Mixture；
The acid modulating agent be phosphorus-containing compound, fluorochemical, boron-containing compound, alkali metal-containing compound, containing alkali
Earth metal compound and the mixture containing one or more in rare earth compound.
The present invention also provides bauxite catalyst prepared by a kind of activation method using above-mentioned bauxite.
In described bauxite catalyst, the VIIIth race or VI B races metallic element are loaded with the bauxite catalyst.
The present invention also provides a kind of method for preparing above-mentioned bauxite catalyst, including：It is straight on bauxite after activation
The race of load regulation VIII or VI B races metallic element are connect, or
VIIIth race or VI B races metallic element are added to and mix mashing in the mixture after acid treatment, and stir-activating, then
Bauxite catalyst is obtained after drying, roasting.
Technical solution of the present invention, has the following advantages that：
1. in the activation method of the bauxite that the present invention is provided, acid treatment is carried out with organic acid to bauxite, it is described organic
Acid has and ionizes in the solution, and the anion that ionizes out is presented multiple tooth Chelating Properties with bridging metal cation formation chela
The characteristic of compound, so that organic acid ionizes out H in the solution+And the anion with sequestering power, H+With institute in bauxite
There is displacement reaction in the iron cation for containing, then the anion with sequestering power is complexed with the iron cation for cementing out
Reaction, forms soluble complex, is well dispersed in bauxite, improves the catalysis activity of bauxite.With reaction
Carrying out, the H that organic acid is ionized out+Concentration can be reduced gradually, and this will promote the multiple ionization of organic acid, whole reaction towards
Hydrolysis direction is carried out, and further increases organic ligand, the i.e. concentration of the anion with sequestering power so that complexing-dissociation
React the direction generated to complex compound to move, so as to enhance the solvability to bauxite, with the bauxite that fully dissociates
Iron mineral, and make its dispersed.
The H of organic acid ionization simultaneously+Radius is smaller, easily with the interlayer cation (Na of bauxite layer structure+、Ca2+And eight
Al in the body structure of face3+Deng) replace so that there is splitting in layer structure, the big lamellar structure of particle is changed into small
Lamellar structure, granularity diminishes, pore volume and aperture increases, improves the catalytic performance of bauxite.
2. in the activation method of the bauxite that the present invention is provided, bonded containing aluminium base to being added in the mixture after acid treatment
One or more in agent, expanding agent and acid modulating agent carry out mixing mashing, and they mutually act synergistically and further increase
The pore volume and average pore size of bauxite, while the range of application of bauxite catalyst is expanded, can be to different reactions
Thing plays catalytic effect.
3. in the bauxite catalyst that the present invention is provided, after organic acid for activating, layer structure becomes bright to natural bauxite
It is aobvious, with more open outer surface and larger pore volume, contribute to intensified response molecule to catalyst granules diffusion inside and urge
Change the accessibility of active phase, be more suitable for the catalyst of organic macromolecule reaction.Therefore, using organic acid for activating bauxite
Preparing catalyst will effectively extend range of application of the bauxite in catalytic field, for the deep development of bauxite provides one newly
Approach.
Specific embodiment
Embodiment 1
By 90g bauxite powder and 0.8mol/L malonic acid solution according to 1:2 solid-liquid volume ratio mixing, in 80 DEG C of stirrings
Activation mashing 1 hour.By the slurry of gained in 100 DEG C of dryings 9 hours, it is calcined 3 hours at 350 DEG C, obtains final product sample A.
Embodiment 2
Prepare the mixed solution of malonic acid and citric acid, the wherein concentration of malonic acid solution is 0.5mol/L, malonic acid with
The mol ratio of citric acid is 1:1, by 70g bauxite powder and malonic acid, citric acid mixed solution according to 1:1.2 solid-liquid
Product is beaten 0.5 hour than mixing in 90 DEG C of stir-activatings.Then well mixed alumina sol 15g, boric acid is added together
3g, activated carbon 4g are beaten to uniform.By the slurry of gained in 90 DEG C of dryings 10 hours, it is calcined 3.5 hours at 300 DEG C, is obtained final product
Sample B.
Embodiment 3
The mixed solution of malonic acid and acetic acid is prepared, the wherein concentration of malonic acid is 0.2mol/L, malonic acid and acetic acid
Mol ratio is 1:1, by 75g bauxite powder and malonic acid, acetic acid mixed solution according to 1:1.6 solid-liquid volume ratio mixing,
It is beaten 1.5 hours in 75 DEG C of stir-activatings.Then add together well mixed peptization boehmite 7.5g, cellulose 5g,
Phosphoric acid dihydro amine 0.5g is beaten to uniform.By the slurry of gained in 80 DEG C of dryings 12 hours, it is calcined 2 hours at 400 DEG C, is obtained final product
Sample C.
Embodiment 4
Sample B 25g are taken, is impregnated using equi-volume impregnating, by the WO containing sample 1.5wt%3Ammonium tungstate be configured to it is molten
Liquid, in adding prepared sample B, dipping 120 DEG C of dryings 2 hours after 12 hours are calcined 3 hours at 400 DEG C, and sample D is obtained.
Embodiment 5
The mixed solution of malonic acid and lactic acid is prepared, the wherein concentration of malonic acid is 0.6mol/L, malonic acid and lactic acid
Mol ratio is 1:3, by 80g bauxite powder and malonic acid, lactic acid mixed solution according to 1:2.5 solid-liquid volume ratio mixing,
It is beaten 1 hour in 85 DEG C of stir-activatings.Peptization boehmite is subsequently adding with alumina sol according to mass ratio 2：1 mixing
The MoO of the mixture 1wt% after mixed-powder 6g, uric acid 2g, the hydrogen amine 3g of phosphoric acid one, mashing containing activation3Ammonium molybdate 0.5g mix
Mashing is closed to uniform.By the slurry of gained in 100 DEG C of dryings 11 hours, it is calcined 2.5 hours at 500 DEG C, obtains final product sample E.
Embodiment 6
The mixed solution of malonic acid and citric acid is prepared, the wherein concentration of malonic acid is 0.9mol/L, malonic acid and lemon
The mol ratio of acid is 1:4, by 60g bauxite powder and malonic acid, citric acid mixed solution according to 1:3 solid-liquid volume ratio is mixed
Close, be beaten 1.5 hours in 90 DEG C of stir-activatings.Peptization boehmite is subsequently adding with alumina sol according to mass ratio 3：1
The mixed-powder 5g of mixing, sesbania powder 3g, boric acid 2g, ammonium molybdate 0.8g mixing mashing are to uniform.By the slurry of gained 80
DEG C drying 12 hours, is calcined 1 hour at 550 DEG C, obtains final product sample F.
Comparative example
By 90g bauxite powder and 0.8mol/L HNO3Solution is according to 1:2 solid-liquid volume ratio mixing, in 80 DEG C of stirrings
Activation mashing 1 hour.By the slurry of gained in 100 DEG C of dryings 9 hours, it is calcined 3 hours at 350 DEG C, obtains final product sample G.
Experimental example
The specific surface area of catalyst prepared by organic acid for activating bauxite and hole in the embodiment of the present invention 1~6 and comparative example
The measure of structure is enterprising in the full-automatic specific surface of Micrometric companies of U.S. ASAP 2020M types and micropore size distribution instrument
OK.Before test, first sample is vacuumized (less than 10 at 250 DEG C-5Torr) pre-process within 2 hours, then carried out under the conditions of liquid nitrogen
Nitrogen adsorption desorption is determined.Specific surface area is according to the calculating of Berrett-Emmett-Teller (BET) method, pore volume and average hole
Footpath distribution is calculated according to desorption branch according to Berret-Joyner-Halenda (BJH) model.
Catalyst prepared by the organic acid for activating bauxite in embodiment 1~6 and comparative example is tested, test result
It is shown in Table 1.
The specific surface area and pore structure test result of the embodiment 1~6 of table 1 and comparative example
Use the sample pore volume that mineral acid treatment natural bauxite is obtained and put down in can be seen that comparative example by the result of table 1
Equal aperture is smaller, reason be probably strong acid in dissolution irony, octahedra to Al-O and Si-O tetrahedrons composition sheet flaggy
Structure is damaged, and will be unfavorable for diffusion of the reactant of catalytic reaction on catalyst activity position, influences catalytic efficiency.
Compared with comparative example, specific surface area has dropped the sample that embodiment 1~6 is prepared using organic acid for activating bauxite
It is low, and pore volume has with average pore size and significantly increases.Its mechanism is probably, the H of organic acid ionization+Radius is smaller, easily with
Metal ion hair in bauxite seamed edge and interlayer, particularly surface fragility position such as vacancy position and dislocation band and lamellar spacing
Raw displacement, causes mineral structure to deform or avalanche so that the original more closely knit layer structure of bauxite carries out splitting,
The big chip architecture of grain is changed into small lamellar structure, and granularity diminishes, and pore volume and average pore size increase, and pore volume and average pore size increasing
Reduction degree of the big degree more than specific surface area.This is beneficial to diffusion of the reactant inside bauxite and in active sites
Catalytic reaction.
The present invention is adapted to suspension bed high-pressure hydrocracking performance and comments using catalyst obtained in organic acid for activating bauxite
Valency：
Appreciation condition：In autoclave reaction system, with decompression residuum as feedstock oil, obtained in organic acid for activating bauxite
Catalyst and vulcanizing agent are added in autoclave together.Nitrogen displacement is first used, then is passed through hydrogen, carried out under uniform temperature and pressure
Vulcanization and reaction, finally collect gaseous product and product liquid.Feedstock oil conversion ratio is calculated according to below equation and distillate is received
Rate, as the evaluation index of reaction effect：
Conversion ratio=520 DEG C following components quality (containing gas)/raw material oil quality × 100%
Gas recovery ratio=(feedstock oil-product liquid quality)/raw material oil quality × 100%
Liquid component quality below cut oil yield=520 DEG C/raw material oil quality × 100%
The evaluation result of catalyst is as shown in table 2 obtained in embodiment 1~6 and comparative example.
The evaluation result of the embodiment 1~6 of table 2 and catalyst obtained in comparative example
| Gas recovery ratio/% | Cut oil yield/% | Conversion ratio/% | |
| A | 10.5 | 82.6 | 93.1 |
| B | 10.4 | 84.3 | 94.7 |
| C | 10.5 | 84.1 | 94.6 |
| D | 8.8 | 87.5 | 96.3 |
| E | 8.6 | 87.9 | 96.5 |
| F | 8.4 | 87.4 | 95.8 |
| G | 22.5 | 60.3 | 82.8 |
From the evaluation result of table 2, comparative example G suspension bed mixed-phase cracking Hydrogenations are poor, show residual oil
After long chain hydrocarbons, cycloalkane and polycyclic aromatic hydrocarbon are through thermal cracking and catalytic cracking, cause further to split because can not in time be hydrogenated with saturation
Change, generate small molecule hydro carbons, cause gas recovery ratio higher.Reason is probably that strong acid treatment bauxite is made to original lamellar structure
Into destruction, and it is unfavorable for that the irony of dissolving is dispersed.
Catalyst mixed-phase cracking Hydrogenation prepared by the organic acid for activating bauxite of embodiment 1~6 is obviously improved,
Gas recovery ratio is substantially reduced, and cut oil yield is significantly improved.The a small amount of catalysis including the VIIIth race and VI B races metallic element of addition
Agent, bottoms conversion is further improved, its reason be probably activation irony in the form of chelate redisperse in the catalyst,
Particle is smaller, is conducive to improving catalytic performance.On the other hand, in the metallic element of addition and organic acid for activating natural bauxite
Fe elements there may be concerted catalysis effect.
Obviously, above-described embodiment is only intended to clearly illustrate example, and not to the restriction of implementation method.It is right
For those of ordinary skill in the art, can also make on the basis of the above description other multi-forms change or
Change.There is no need and unable to be exhaustive to all of implementation method.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (10)
1. a kind of activation method of bauxite, it is characterised in that comprise the following steps：
Acid treatment, and stir-activating are carried out to bauxite with organic acid, then the bauxite activated after drying, roasting；
Wherein, the organic acid has and ionizes in the solution, and the anion for ionizing out is presented multiple tooth Chelating Properties with bridge
Connection metal cation forms the characteristic of chelate.
2. the activation method of bauxite according to claim 1, it is characterised in that the organic acid is malonic acid, lemon
The mixture of one or more in acid, acetic acid and lactic acid, the organic acid is preferably malonic acid.
3. the activation method of bauxite according to claim 1 and 2, it is characterised in that the temperature of the stir-activating is
75~90 DEG C, the time of stir-activating is 0.5~1.5h.
4. according to the activation method of any described bauxite of claims 1 to 3, it is characterised in that the organic acid with it is described
The solid volume ratio of the liquid of bauxite is 1.2~3:1, the concentration of the organic acid is 0.2~0.9mol/L.
5. according to the activation method of any described bauxite of Claims 1 to 4, it is characterised in that the dry temperature is
80~100 DEG C, the time is 9~12h, and the temperature of the roasting is 300~550 DEG C, and the time is 1~3.5h.
6. according to the activation method of any described bauxite of Claims 1 to 5, it is characterised in that also wrapped after stir-activating
Include and mixed to one or more in addition binding agent containing aluminium base, expanding agent and acid modulating agent in the mixture after acid treatment
Close mashing.
7. the activation method of bauxite according to claim 6, it is characterised in that the binding agent containing aluminium base is that peptization is intended
Boehmite and/or alumina sol；
The expanding agent is the mixing of one or more in activated carbon, carbon black, uric acid, polyethylene glycol, cellulose and sesbania powder
Thing；
The acid modulating agent be phosphorus-containing compound, fluorochemical, boron-containing compound, alkali metal-containing compound, containing alkaline earth gold
Category compound and the mixture containing one or more in rare earth compound.
8. the bauxite catalyst for being prepared using the activation method of any described bauxite of claim 1~7.
9. bauxite catalyst according to claim 8, it is characterised in that be loaded with the VIIIth on the bauxite catalyst
Race or VI B races metallic element.
10. a kind of method of the bauxite catalyst prepared described in claim 9, it is characterised in that bauxite after activation
The upper race of direct load regulation VIII or VI B races metallic element, or
VIIIth race or VI B races metallic element are added to and mix mashing in the mixture after acid treatment, and stir-activating, then through dry
Bauxite catalyst is obtained after dry, roasting.
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