CN106732787B - 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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- 229910001570 bauxite Inorganic materials 0.000 title claims abstract description 99
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000004913 activation Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 150000007524 organic acids Chemical class 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 8
- -1 organic acid anion Chemical class 0.000 claims abstract description 8
- 238000012545 processing Methods 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
- 238000001994 activation Methods 0.000 claims description 25
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 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
- 239000002253 acid Substances 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 6
- 238000010009 beating Methods 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 229910052799 carbon Inorganic materials 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [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
- 238000002156 mixing Methods 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
- 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 11
- 229910001608 iron mineral Inorganic materials 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 14
- 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
- 239000010410 layer Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000011156 evaluation Methods 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
- 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
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000005360 mashing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 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
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- 238000010306 acid treatment Methods 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
- 230000006378 damage Effects 0.000 description 2
- 238000009792 diffusion process 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
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 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
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 150000001398 aluminium Chemical class 0.000 description 1
- 150000001412 amines Chemical class 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
- 230000008859 change Effects 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
- 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
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 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
- 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 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
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading 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 to activate field, and in particular to a kind of activation method of bauxite includes the following steps: to carry out sour processing, and stir-activating, then the bauxite activated after drying, roasting to bauxite with organic acid；Wherein, there is the organic acid anion for ionizing, and ionizing out in the solution the characteristic that multiple tooth Chelating Properties form chelate with bridging metal cation is presented.The present invention also provides a kind of bauxite catalyst and preparation method thereof using above method preparation.Method provided by the invention can sufficiently dissociate the iron mineral in bauxite, improve the catalytic performance of bauxite.
Description
Technical field
The present invention relates to bauxite to activate field, and in particular to a kind of activation method of bauxite, bauxite catalyst and
Preparation method.
Background technique
China's bauxite resource is abundant, and bauxite is production metallic aluminium and aluminous refractory or aluminosilicate refractory fiber
Primary raw material.Bauxite is made of the particle of some layer structures, through hydro-thermal, roasting be heat-treated or be aided with suitable additives into
Row is modified, and can prepare high-specific surface area, the activated alumina that large hole is held, and activated alumina has that stability is good and price
Relatively low advantage, is typically used to catalyst field.
Contain alumino-silicate in bauxite, high mechanical strength has the pore structure of the comparison rule naturally occurred.Contain simultaneously
There is the higher iron-bearing mineral of content, is potential catalytic activity phase.But the iron-bearing mineral in bauxite and diaspore are relatively advised
Adjoining then is inlayed, and in fine pulse-like or package squamous layer circle, this irony dissociation inlayed is difficult, and crystal grain is larger, as catalysis
Agent using when tend not to be sufficiently activated.
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 parts by weight, aluminium oxide or intend thin water
Aluminium stone 40-60 parts by weight, magnesia or magnesium hydroxide 20-40 parts by weight, the modified bauxite are prepared with the following method: first
Sour processing is carried out to natural bauxite, then is washed with distilled water to cleaning solution and is in neutrality, filtered, be drying to obtain the modified aluminium
Tu Kuang, the acid processing use acid for one of nitric acid, phosphoric acid, boric acid or several mixtures.Use inorganic acid pair
Bauxite carries out sour processing, is replaced using iron cation contained in the hydrogen ion and bauxite material in inorganic acid, in this way
NO3 -、PO3 3-、BO3 3-And Cl-It will be present in final product in the form of impurity, 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 dissolved
Poor dispersion, the hole appearance aperture of modified bauxite is smaller to cause reactant molecule to spread there are steric hindrance, and catalytic efficiency is lower；Make
The original structure that bauxite can be also destroyed with inorganic acid influences the later period application of bauxite.
Summary of the invention
Therefore, it is inlayed in bauxite the technical problem to be solved in the present invention is that overcoming in the activation process of existing bauxite
Iron mineral dissociate difficult, bauxite cannot give full play to the defect of catalytic performance, and bauxite can sufficiently be dissociated by providing one kind
In iron mineral, improve the activation method of the bauxite of the catalytic performance of bauxite.
A kind of activation method of bauxite, includes the following steps:
Sour processing, and stir-activating, then the alumina activated after drying, roasting are carried out to bauxite with organic acid
Mine；
Wherein, the organic acid has and ionizes in the solution, and multiple tooth Chelating Properties are presented in the anion ionized out
The characteristic of chelate is formed with bridging metal cation.
In the activation method of the bauxite, the organic acid is one of malonic acid, citric acid, acetic acid and lactic acid
Or several mixtures, the organic acid are preferably malonic acid.
In the activation method of the bauxite, the temperature of the stir-activating is 75~90 DEG C, the time of stir-activating
For 0.5~1.5h.
In the activation method of the bauxite, it is 1.2~3 that the liquid of the organic acid and the bauxite, which consolidates volume ratio:
1, the concentration of the organic acid is 0.2~0.9mol/L.
In the activation method of the bauxite, the temperature of the drying 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.
It further include being added to contain into acid treated mixture after stir-activating in the activation method of the bauxite
One or more of aluminium base binder, expanding agent and acid modulating agent are mixed with beating.
In the activation method of the bauxite, the binder containing aluminium base is peptization boehmite and/or aluminium oxide
Colloidal sol；
The expanding agent is one or more of active carbon, carbon black, uric acid, polyethylene glycol, cellulose and sesbania powder
Mixture；
The acidity modulating agent is phosphorus-containing compound, fluorochemical, boron-containing compound, alkali metal-containing compound, contains alkali
Earth metal compound and mixture containing one or more of rare earth compound.
The present invention also provides a kind of bauxite catalyst prepared by the activation method using above-mentioned bauxite.
In the bauxite catalyst, load has the VIIIth race or VI B race metallic element on the bauxite catalyst.
The present invention also provides a kind of methods for preparing above-mentioned bauxite catalyst, comprising: straight on bauxite after activation
VIII race of load regulation or VI B race metallic element are connect, or
VIIIth race or VI B race metallic element are added in acid treated mixture and are mixed with beating, and stir-activating, then
Bauxite catalyst is obtained after drying, roasting.
Technical solution of the present invention has the advantages that
1. in the activation method of bauxite provided by the invention, sour processing is carried out to bauxite with organic acid, it is described organic
There is acid the anion for ionizing, and ionizing out in the solution multiple tooth Chelating Properties are presented with bridging metal cation formation chela
The characteristic for closing object, so that organic acid be made to ionize out H in the solution+And the anion with sequestering power, H+With institute in bauxite
Displacement reaction occurs for the iron cation contained, and then the anion with sequestering power is complexed with the iron cation cemented out
Reaction forms soluble complex, is well dispersed in bauxite, improves the catalytic activity of bauxite.With reaction
Progress, the H that organic acid ionizes out+Concentration can gradually decrease, this will promote the multiple ionization of organic acid, entire reaction towards
It hydrolyzes direction to carry out, organic ligand, the i.e. concentration of the anion with sequestering power is further improved, so that complexing-dissociation
It is mobile to react the direction generated to complex compound, so that the solvability to bauxite is enhanced, sufficiently to dissociate in bauxite
Iron mineral, and keep its evenly 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 splitting occurs for layer structure, the big lamellar structure of particle is changed into small
Lamellar structure, granularity become smaller, and Kong Rong and aperture increases improve the catalytic performance of bauxite.
2. in the activation method of bauxite provided by the invention, it is added into acid treated mixture and is bonded containing aluminium base
One or more of agent, expanding agent and acid modulating agent are mixed with beating, they mutually act synergistically and further improve
The Kong Rongyu average pore size of bauxite, while the application range of bauxite catalyst is expanded, it can be to different reactions
Object plays catalytic effect.
3. in bauxite catalyst provided by the invention, for natural bauxite after organic acid for activating, layer structure becomes bright
It is aobvious, there is more open outer surface and large hole to hold, facilitate intensified response molecule to spreading inside catalyst granules and urge
The accessibility for changing active phase, is more suitable for the catalyst of organic macromolecule reaction.Therefore, using organic acid for activating bauxite
Bauxite will effectively be extended in the application range of catalytic field by preparing catalyst, provide one newly for the deep development of bauxite
Approach.
Specific embodiment
Embodiment 1
90g bauxite powder is mixed with 0.8mol/L malonic acid solution according to the solid-liquid volume ratio of 1:2, is stirred at 80 DEG C
Activation mashing 1 hour.Resulting slurry is 9 hours dry at 100 DEG C, 3 hours are roasted at 350 DEG C to get sample A.
Embodiment 2
Prepare malonic acid and citric acid mixed solution, wherein the concentration of malonic acid solution be 0.5mol/L, malonic acid with
The molar 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 uniformly mixed alumina sol 15g, boric acid are added together
3g, active carbon 4g are beaten to uniform.Resulting slurry is 10 hours dry at 90 DEG C, roasted at 300 DEG C 3.5 hours to get
Sample B.
Embodiment 3
The mixed solution of malonic acid and acetic acid is prepared, wherein the concentration of malonic acid is 0.2mol/L, malonic acid and acetic acid
Molar ratio is 1:1, and 75g bauxite powder is mixed with the mixed solution of malonic acid, acetic acid according to the solid-liquid volume ratio of 1:1.6,
It is beaten 1.5 hours in 75 DEG C of stir-activatings.Then be added together uniformly mixed peptization boehmite 7.5g, cellulose 5g,
Phosphoric acid dihydro amine 0.5g is beaten to uniform.Resulting slurry is 12 hours dry at 80 DEG C, roasted at 400 DEG C 2 hours to get
Sample C.
Embodiment 4
Sample B 25g is taken, is impregnated using equi-volume impregnating, by the WO of the 1.5wt% containing sample3Ammonium tungstate be configured to it is molten
Liquid is added in prepared sample B, and dipping 120 DEG C drying 2 hours after 12 hours roast 3 hours at 400 DEG C, sample D is made.
Embodiment 5
The mixed solution of malonic acid and lactic acid is prepared, wherein the concentration of malonic acid is 0.6mol/L, malonic acid and lactic acid
Molar ratio is 1:3, and 80g bauxite powder is mixed with the mixed solution of malonic acid, lactic acid according to the solid-liquid volume ratio of 1:2.5,
It is beaten 1 hour in 85 DEG C of stir-activatings.Then it is added what peptization boehmite was mixed with alumina sol according to mass ratio 2:1
The MoO of mixture 1wt% after mixed-powder 6g, uric acid 2g, one hydrogen amine 3g of phosphoric acid, mashing containing activation3Ammonium molybdate 0.5g it is mixed
It closes and is beaten to uniform.Resulting slurry is 11 hours dry at 100 DEG C, 2.5 hours are roasted at 500 DEG C to get sample E.
Embodiment 6
The mixed solution of malonic acid and citric acid is prepared, wherein the concentration of malonic acid is 0.9mol/L, malonic acid and lemon
The molar ratio of acid is 1:4, and 60g bauxite powder and the mixed solution of malonic acid, citric acid are mixed according to the solid-liquid volume ratio of 1:3
It closes, is beaten 1.5 hours in 90 DEG C of stir-activatings.Then peptization boehmite and alumina sol is added according to mass ratio 3:1
Mixed mixed-powder 5g, sesbania powder 3g, boric acid 2g, ammonium molybdate 0.8g are mixed with beating to uniform.By resulting slurry 80
DEG C dry 12 hours, 1 hour is roasted at 550 DEG C to get sample F.
Comparative example
By 90g bauxite powder and 0.8mol/L HNO3Solution is mixed according to the solid-liquid volume ratio of 1:2, is stirred at 80 DEG C
Activation mashing 1 hour.Resulting slurry is 9 hours dry at 100 DEG C, 3 hours are roasted at 350 DEG C to get sample G.
Experimental example
The specific surface area for the catalyst that in the embodiment of the present invention 1~6 and comparative example prepared by organic acid for activating bauxite and hole
The measurement of structure is enterprising in the full-automatic specific surface of Micrometric company, U.S. ASAP 2020M type and micropore size distribution instrument
Row.Before test, first sample is vacuumized at 250 DEG C (less than 10-5Torr it) pre-processes within 2 hours, then is carried out under the conditions of liquid nitrogen
The measurement of nitrogen adsorption desorption.Specific surface area is calculated according to Berrett-Emmett-Teller (BET) method, pore volume and average hole
Diameter distribution is calculated according to desorption branch according to Berret-Joyner-Halenda (BJH) model.
The catalyst of organic acid for activating bauxite preparation in Examples 1 to 6 and comparative example is tested, test result
It is shown in Table 1.
The specific surface area and pore structure test result of 1 Examples 1 to 6 of table and comparative example
The sample well Rong Yuping obtained in comparative example it can be seen from 1 result of table using mineral acid treatment natural bauxite
Equal aperture is smaller, and reason may be strong acid when dissolving out irony, octahedra to Al-O and Si-O tetrahedron composition sheet plate layer
Structure damages, and will be unfavorable for diffusion of the reactant of catalysis reaction on catalyst activity position, influences catalytic efficiency.
Using the sample of organic acid for activating bauxite preparation compared with comparative example, specific surface area is dropped Examples 1 to 6
It is low, and Kong Rongyu average pore size has and significantly increases.Its mechanism may be the H of organic acid ionization+Radius is smaller, easily with
Metal ion hair in bauxite seamed edge and interlayer, especially surface fragility position such as vacancy position and dislocation band and lamellar spacing
Raw displacement leads to mineral structure deformation 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 becomes smaller, and Kong Rongyu average pore size increases, and the increasing of Kong Rongyu average pore size
Big degree is greater than the reduction degree of specific surface area.This is beneficial to diffusion of the reactant inside bauxite and in active sites
Catalysis reaction.
The present invention is adapted to suspension bed high-pressure hydrocracking performance using catalyst made from organic acid for activating bauxite and comments
Valence:
Evaluation condition: in autoclave reaction system, using decompression residuum as made from feedstock oil, organic acid for activating bauxite
Catalyst and vulcanizing agent are added in autoclave together.It is first replaced with nitrogen, then is passed through hydrogen, carried out under certain temperature and pressure
Vulcanization and reaction, finally collect gaseous product and product liquid.Feedstock oil conversion ratio is calculated according to the following formula and distillate is received
Rate, the evaluation index as 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%
Fraction oil yield=520 DEG C or less liquid component quality/raw material oil quality × 100%
The evaluation result of catalyst made from Examples 1 to 6 and comparative example is as shown in table 2.
The evaluation result of catalyst made from 2 Examples 1 to 6 of table and comparative example
| Gas recovery ratio/% | Fraction 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 |
By the evaluation result of table 2 it is found that comparative example G suspension bed mixed-phase cracking Hydrogenation is poor, residual oil is shown
Long chain hydrocarbons, cycloalkane and polycyclic aromatic hydrocarbon are after thermal cracking and catalytic cracking, because that hydrogen saturation cannot be added in time to cause further to split
Change, generates small molecule hydro carbons, cause gas recovery ratio higher.Reason may be that strong acid treatment bauxite makes original lamellar structure
At destruction, and the irony for being unfavorable for dissolution is evenly dispersed.
The catalyst mixed-phase cracking Hydrogenation of Examples 1 to 6 organic acid for activating bauxite preparation is obviously improved,
Gas recovery ratio is substantially reduced, and fraction oil yield significantly improves.The a small amount of catalysis including the VIIIth race and VI B race metallic element of addition
Agent, bottoms conversion further increase, reason may be activation irony in the form of chelate redisperse in the catalyst,
Particle is smaller, is conducive to improve catalytic performance.On the other hand, in the metallic element of addition and organic acid for activating natural bauxite
There may be concerted catalysis effects for Fe element.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (7)
1. a kind of activation method of bauxite, which comprises the steps of:
Sour processing, and stir-activating, then the bauxite activated after drying, roasting are carried out to bauxite with organic acid；
Wherein, the organic acid has and ionizes in the solution, and multiple tooth Chelating Properties are presented with bridge in the anion ionized out
Join the characteristic that metal cation forms chelate；
The organic acid is the mixture of one or more of malonic acid, citric acid, acetic acid and lactic acid；The stir-activating
Temperature is 75 ~ 90 DEG C, and the time of stir-activating is 0.5 ~ 1.5h；The liquid of the organic acid and the bauxite consolidates volume ratio and is
1.2 ~ 3:1, the concentration of the organic acid are 0.2 ~ 0.9mol/L；The temperature of the drying is 80 ~ 100 DEG C, and the time is 9 ~ 12h,
The temperature of the roasting is 300 ~ 550 DEG C, and the time is 1 ~ 3.5h.
2. the activation method of bauxite according to claim 1, which is characterized in that the organic acid is malonic acid.
3. the activation method of bauxite according to claim 1, which is characterized in that after stir-activating further include at acid
One or more of binder containing aluminium base, expanding agent and acid modulating agent are added in mixture after reason to be mixed with beating.
4. the activation method of bauxite according to claim 3, which is characterized in that the binder containing aluminium base is quasi- for peptization
Boehmite and/or alumina sol；
The expanding agent is the mixing of one or more of active carbon, carbon black, uric acid, polyethylene glycol, cellulose and sesbania powder
Object；
The acidity modulating agent is phosphorus-containing compound, fluorochemical, boron-containing compound, alkali metal-containing compound, contains alkaline earth gold
Belong to compound and the mixture containing one or more of rare earth compound.
5. the bauxite catalyst of the activation method preparation using any bauxite of claim 1 ~ 4.
6. bauxite catalyst according to claim 5, which is characterized in that load has the VIIIth on the bauxite catalyst
Race or VI B race metallic element.
7. a kind of method for preparing bauxite catalyst as claimed in claim 6, which is characterized in that on bauxite after activation
Direct VIII race of load regulation or VI B race metallic element, or
VIIIth race or VI B race metallic element are added in acid treated mixture and are mixed with beating, and stir-activating, then through dry
Bauxite catalyst is obtained after dry, roasting.
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