CN106824194A - A kind of integral alumina supported ferric catalyst based on vapour deposition process - Google Patents
A kind of integral alumina supported ferric catalyst based on vapour deposition process Download PDFInfo
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- CN106824194A CN106824194A CN201710040300.6A CN201710040300A CN106824194A CN 106824194 A CN106824194 A CN 106824194A CN 201710040300 A CN201710040300 A CN 201710040300A CN 106824194 A CN106824194 A CN 106824194A
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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 135
- 239000003054 catalyst Substances 0.000 title claims abstract description 118
- 238000005137 deposition process Methods 0.000 title claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 98
- 238000000034 method Methods 0.000 claims abstract description 51
- 239000002243 precursor Substances 0.000 claims abstract description 50
- 238000002360 preparation method Methods 0.000 claims abstract description 48
- 229910052742 iron Inorganic materials 0.000 claims abstract description 47
- 238000000465 moulding Methods 0.000 claims abstract description 47
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000654 additive Substances 0.000 claims abstract description 32
- 230000000996 additive effect Effects 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 26
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 25
- 239000010703 silicon Substances 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 16
- 230000008021 deposition Effects 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000002788 crimping Methods 0.000 claims description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000012512 characterization method Methods 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000002441 X-ray diffraction Methods 0.000 claims description 9
- 239000011812 mixed powder Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000004898 kneading Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229920002907 Guar gum Polymers 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 235000010417 guar gum Nutrition 0.000 claims description 5
- 239000000665 guar gum Substances 0.000 claims description 5
- 229960002154 guar gum Drugs 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 2
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- 241000219782 Sesbania Species 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 229910052878 cordierite Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000012256 powdered iron Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/615—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
Abstract
The invention belongs to be catalyzed with sorbing material and technical field, be related to a kind of integral alumina supported ferric catalyst based on vapour deposition process, including method for preparing catalyst and product feature.Wherein preparation method uses the following raw material：Silicon source, the first additive, the second additive, acid solution；Use monolithic substrate mould；Use two closed containers and an open container；Comprise the steps of：Step one, prepare molding precursor；The assembling of step 2, molding precursor and mould；Step 3, to molding precursor apply pressure；Step 4, the drying of formed blocks and roasting；The deposition of step 5, ferrocene on monolithic substrate；Step 6, the roasting of post-depositional first paragraph；Step 7, the roasting of post-depositional second segment.After completing step 7, the catalyst prod of gained has following characteristics：Integral alumina supported ferric catalyst specific surface area is higher, iron mass percent is up to 0.3 ~ 11 %；The microcosmic upper high degree of dispersion of iron component.
Description
Technical field
The invention belongs to be catalyzed with sorbing material and technical field, be related to a kind of monoblock type based on vapour deposition process to aoxidize
Aluminium supported ferric catalyst, in particular it relates to a kind of sunk by combining the gas phase of the preparation of integral alumina carrier and iron component
The support type monoblock type iron catalyst that product is prepared, including method for preparing catalyst and product feature.
Background technology
During the production of numerous chemical products, energy substance production and environmental protection, catalytic reaction technique is whole
The core of technical process, and the key problem of catalytic reaction technique is the performance of catalyst.In practical application, solid catalysis
Agent is most common catalyst type of service, and solid catalyst can be divided into graininess or powdered catalytic from macroscopic form
Agent, integral catalyzer and the catalyst with given shape.Most common of which is graininess or powder catalyst.From
Catalyst activity component（Transition metal component is most commonly seen）Existence form on see, solid catalyst can be divided into support type
With unsupported catalyst.In order to improve the utilization ratio of active component, solid catalyst is generally made into support type.Its
In, the material for carrying active component is referred to as catalyst carrier, or referred to as carrier；The catalysis after catalytic active component is loaded
Agent is referred to as loaded catalyst.The active charcoal of common high specific surface carrier, molecular sieve, porous aluminum oxide etc..Monoblock type
With particle or powder catalyst morphological differences substantially, in actual use, integral catalyzer is whole larger with one for catalyst
The form of block occurs, and it has some clear advantages compared with the latter.For example, the former with the latter is compared, its catalyst filling
It is more convenient with reclaiming, running cost is substantially reduced, especially the separation costs of catalyst and product；For fixed bed reactors
In, the former often has less pressure drop.Support type integral catalyzer is a focus in catalyticing research and application.Due to
Catalysis has certain similitude with adsorption process, and porous material load active component is also commonly used for adsorption process.Correlation is produced
Product can be described as load type adsorbing agent, and it is also more common in production of energy, environmental protection.Particle or fine catalyst are in suitable bar
Can be used as particle or powder sorbent under part；Integral catalyzer can be used as monoblock type adsorbent.
Load typed iron catalyst is a kind of important industrial catalyst, can be used for Fischer-Tropsch-synthesis, the catalysis oxidation of alkane,
The Chemical Manufactures such as denitration and environmentally friendly process.For particle or powdered iron catalyst, currently for integral supported type
The preparation method of iron catalyst is also few, and especially whole block is all the situation of iron catalyst.For example L. Xu et al. are in document
(Materials Research Bulletin[J], 2014, Vol. 59, page 254-260.) in report a kind of iron
The gas-phase deposition process for preparing of catalyst, the method is generally fairly simple, cost is relatively low.But the method cannot be applied to it is whole
The preparation of body formula catalyst.The method another problem is that using N2Used as carrier gas, carrier gas is inevitably by the presoma of iron
Take preparation facilities out of, although avoid the treatment of waste liquid, but introduce exhaust-gas treatment link.Patent CN105148914A is disclosed
A kind of Fe2O3/Al2O3/ cordierite catalyst and preparation method thereof, obtains can be used for the integral catalyzer of denitration.The catalysis
Agent is prepared comprising the step being coated in using Alumina gel on cordierite surface.Although specific letter of the invention without correlation specific surface area
Breath, but because cordierite specific surface area is relatively low, therefore whole specific surface area of catalyst will be by larger limitation.For support type
For catalyst, the decentralization of active component is most important for catalysis activity；Absorbed from X-ray diffraction, pulse, transmit electricity
The characterization methods such as sub- microscope can obtain relevant information.From foregoing invention, reader learns the deployment conditions of related iron component.
For the preparation of integral supported iron catalyst, also there is the skill of this improvement preparation method in this area
Art demand, especially prepares high-specific surface area, high ferro component decentralization, the demand of the process of low cost operation.
The content of the invention
In order to overcome the problems of prior art, the present invention to provide a kind of monoblock type oxidation based on vapour deposition process
Aluminium supported ferric catalyst, including preparation method and product feature；The technology path of its preparation process be first pass through compression forming-
The process combination of program roasting prepares integral alumina carrier, is then prepared by the combination of-two roastings of vapour deposition whole
Body formula alumina load iron catalyst.The method can with high-specific surface area, it is microcosmic on possess nanoscale duct, active component iron group
Divide the integral alumina supported ferric catalyst of microcosmic upper high degree of dispersion；The preparation method is come without expensive device, raw material simultaneously
Source is simple, more friendly environment, safe operation, cost are relatively low.
Realizing the concrete technical scheme of above-mentioned technology path is：
A kind of integral alumina supported ferric catalyst based on vapour deposition process, including integral alumina supported ferric catalyst
Preparation method and integral alumina supported ferric catalyst product feature；Wherein integral alumina supported ferric catalyst preparation side
Method uses the following raw material：
Silicon source：The one kind in aluminium hydroxide, boehmite, or above two material arbitrary proportion mixture；
First additive：It is the one kind in sesbania powder, sesbania gum, guar gum, cation guar gum, sodium alginate, or it is above-mentioned
The mixture of material arbitrary proportion；
Second additive：Be ethanol, propyl alcohol, butanol, ethylene glycol, propane diols, polyethylene glycol, polyvinyl alcohol, glucose, fructose,
Sucrose, maltose, cellobiose, granularity are less than the carbon black of 60 mesh, granularity less than the one kind in the water soluble starch of 60 mesh,
Or the mixture of above-mentioned substance arbitrary proportion；
Acid solution：A kind of aqueous solution, contains nitric acid, sulfuric acid, hydrochloric acid, acetic acid, oxalic acid, phosphoric acid, citric acid, maleic acid, tartaric acid
In one or more materials, the pH value of the aqueous solution is in the range of 0.0 ~ 4.0.
Above-mentioned integral alumina supported ferric catalyst preparation method, uses monolithic substrate mould；The shaping mould
Tool includes the part of mould first, the part of mould second and the part of mould the 3rd；The part of mould first includes a cylindrical cavity；
The part of mould second includes mould the second part crimping section and mould the second part pressure-bearing part；Mould the second part press section
The geometry divided is cylinder, and it has a compressive plane, and the geometry of the compressive plane is circle；The part of mould second holds
Laminate section has a pressure-bearing surface；The part of mould the 3rd includes the part crimping section of mould the 3rd and the part pressure-bearing portion of mould the 3rd
Point；The geometry of the part crimping section of mould the 3rd is cylinder, and it has a compressive plane, the geometry of the compressive plane
It is circle；The part pressure-bearing part of mould the 3rd has a pressure-bearing surface；The compressive plane and mould of mould the second part crimping section
The axial direction of the cylindrical cavity that the compressive plane of the 3rd part crimping section can be included from the part of mould first is put into.
Above-mentioned integral alumina supported ferric catalyst preparation method, using two closed containers, is referred to as first close
Close container and the second closed container；The feature of the two closed containers is all that can open wide to be put into other objects rear closed, is
Object is put into be confined in container；Use an open container, referred to as the first open container.
Above-mentioned integral alumina supported ferric catalyst preparation method, by using above-mentioned raw materials and main device, its
Preparation process is comprised the steps of：
Step one, prepare molding precursor；
The assembling of step 2, molding precursor and mould；
Step 3, to molding precursor apply pressure；
Step 4, the drying of formed blocks and roasting；
The deposition of step 5, ferrocene on monolithic substrate；
Step 6, the roasting of post-depositional first paragraph；
Step 7, the roasting of post-depositional second segment.
The specific method of above-mentioned seven steps is as follows：
Step one, prepare molding precursor；Specific method is as follows：
Silicon source, the first additive, second additive of certain mass are taken, wherein the quality of the first additive is silicon source quality
0.01 ~ 0.1 times, the quality of the second additive is 0 ~ 0.2 times of silicon source quality；Three kinds of materials uniformly mix, and are mixed
Powder；Acid solution is then poured slowly into mixed-powder, dough is formed, the quality of wherein acid solution is silicon source quality
0.5 ~ 1.3 times；Kneading is carried out to dough by hand or banded extruder so that silicon source therein, the first addition
Thing, the second additive, acid solution further uniformly mix, and form a moulded pottery not yet put in a kiln to bake, do not have obvious droplet formation on moulded pottery not yet put in a kiln to bake；By upper
State the moulded pottery not yet put in a kiln to bake referred to as molding precursor that mixture kneading is obtained.
The assembling of step 2, molding precursor and mould；Specific method is as follows：
Molding precursor is filled in the cylindrical cavity that the part of mould first of monolithic substrate mould is included, is molded
The quality of precursor is in 2 ~ 400 g ranges；Mould the second part crimping section and the part crimping section of mould the 3rd are distinguished
The both sides of the cylindrical cavity included from the part of mould first are put into；Load molding precursor material requested and place mould second
The order of part or the part of mould the 3rd is not limited；Compressive plane, the part of mould the 3rd extruding when mould the second part crimping section
Partial compressive plane is collectively forming an airtight cavity with the cylindrical empty cavity wall that the part of mould first is included, and will be above-mentioned
Molding precursor is enclosed in the airtight cavity, completes to load step.
Step 3, to molding precursor apply pressure；Specific method is as follows：
The molding precursor that will be assembled is combined with monolithic substrate mould and is placed on a hydraulic press, the part of mould second
Pressure-bearing surface is contacted with the pressure-bearing surface of the part of mould the 3rd with the applying press member of hydraulic press so that hydraulic press pressure applied
Above-mentioned two pressure-bearing surface can be acted on；The pressure size of applying is in the range of 0.1 ~ 5 MPa；It is 20 to apply pressure time
s ~ 40 min；Then it is removed from the molds the molding precursor after being pressurized and obtains formed blocks.
Step 4, the drying of formed blocks and roasting；Specific method is as follows：
Operation is dried to formed blocks described in step 3, part volatility moisture is left formed blocks with other materials,
Until the dried quality of formed blocks is less than 75% before drying；Drying process including but not limited to drying, dry in atmosphere
Drying in case or Muffle furnace, dry in vacuum drying chamber, dry in drier, blowing drying, daylight is dried, infrared lamp is dried,
The operations such as centrifuge drying, or any combination of aforesaid operations is operated；Formed blocks are placed in into one afterwards has temperature programmed control
It is calcined in the heater of function；The atmosphere of roasting is air, or purity oxygen, or any oxygenous ratio is mixed more than 20%
Close gas；Temperature and time relation in program roasting includes three temperature controlling stages, is referred to as the first temperature control rank
Section, second temperature control stage and the 3rd temperature controlling stages；First temperature controlling stages have an initial temperature, and its value is
20 ~ 150 oCertain value in the range of C, with a final temperature, its value is 300 ~ 700oCertain value in the range of C, from
Initial temperature is to final temperature average ramp rate 0.5 ~ 8oIn the range of C/min；First temperature controlling stages it is total when
Between in the range of 30 min ~ 12 h；The second temperature control stage has an initial temperature, and its value is 300 ~ 700oC models
Certain interior value is enclosed, with a final temperature, its value is also 300 ~ 700oCertain value in the range of C, from initial temperature to
Final temperature average ramp rate is -2 ~ 2oIn the range of C/min；The total time in second temperature control stage is in 1 ~ 6 h
In the range of；3rd temperature controlling stages have an initial temperature, and its value is 300 ~ 700oCertain value in the range of C, has
One final temperature, its value is 20 ~ 150oCertain value in the range of C, changes from initial temperature to final temperature mean temperature
Rate is -8 ~ -0.5oIn the range of C/min；The total time of the 3rd temperature controlling stages is in the range of 2 ~ 24 h；Afterwards, it is molded
Block is converted into integral alumina carrier.
The deposition of step 5, ferrocene on monolithic substrate；Specific method is as follows：
The ferrocene powder of certain mass is taken, the quality of wherein ferrocene is integral alumina carrier quality described in step 4
0.004 ~ 2 times；Integral alumina carrier described in ferrocene powder and step 4 is respectively put into the first closed container
And carry out closed；Wherein integral alumina carrier is positioned over somewhere as a block, and ferrocene powder is with sub-circular
Shape be looped around around integral alumina carrier；Integral alumina carrier and two cyclopentadienyls will according to the method described above have been held
First closed container of iron powder is entirely positioned in a heater, and the first closed container is heated, heating-up temperature
80 ~ 190oIn the range of C；Heat time is in the range of 20 min ~ 12 h；Complete integral alumina carrier after heating
Change into ferrocene-integral alumina carrier complexes.
Step 6, the roasting of post-depositional first paragraph；Specific method is as follows：
Ferrocene described in step 5-integral alumina carrier complexes are transferred to the second closed appearance from the first closed container
Device；Second closed container is entirely positioned in a heater, and the second closed container is heated, heating-up temperature exists
180 ~ 270 oIn the range of C；Heat time is in the range of 20 min ~ 12 h.
Step 7, the roasting of post-depositional second segment；Specific method is as follows：
Ferrocene described in step 6-integral alumina carrier complexes are transferred to first and opened wide from the second closed container and is held
Device；First open container is entirely positioned in a heater, and the first open container is heated, heating-up temperature exists
300 ~ 800 oIn the range of C, the heat time is 30 min ~ 24 h.
After completing step 7, whole preparation process is finished, and ferrocene-integral alumina carrier complexes are converted into entirety
Formula alumina load iron catalyst product；The product can be used for follow-up sign, catalytic reaction, adsorption process or other use
On the way.The present invention by being characterized to obtained integral alumina supported ferric catalyst product, bear by the integral alumina
Supported ferric catalyst also has following product feature simultaneously：
（1）, single integral alumina supported ferric catalyst block quality up to 1 ~ 110 g；
（2）, integral alumina supported ferric catalyst specific surface area up to 130 ~ 500 m2/g；
（3）, on integral alumina supported ferric catalyst iron mass percent up to 0.3 ~ 11 %；
（4）, integral alumina supported ferric catalyst X-ray diffraction peak only wrap salic SPECTROSCOPIC CHARACTERIZATION, and be free of
SPECTROSCOPIC CHARACTERIZATION on iron component.
The above-mentioned SPECTROSCOPIC CHARACTERIZATION of aluminum oxide is known for those skilled in the art, therefore need not be given herein.It is above-mentioned（3）
（4）2 points combine explanation, and on the basis of with considerable iron component load capacity, iron component has dispersion very high on microcosmic
Degree.It is noted that the characterization test method of the present invention and non-protected product, but the product obtained by the protection present invention is due
Feature.Characterization test method used by this product is all method that those skilled in the art commonly use.
It is noted that the characterization test method of the present invention and non-protected product, but the product obtained by the protection present invention
Due feature.Characterization test method used by this product is all method that those skilled in the art commonly use.
In above-mentioned relevant second additive, the representation of " 60 mesh " that moieties contain, used this area for
A kind of idiomatic expression method of grain or powdered solid substance particle size.In the art, " mesh number " represents a tool
There is the grid number contained by the screen cloth per inch for being uniformly distributed co-ordination.Certain particle can illustrate this by such screen cloth
Particle size is less than the size of the defined of related mesh number.For example, a screen cloth for 60 mesh, if having being uniformly distributed co-ordination,
The grid number that each inch contains is 60；If certain particle can be can be expressed as the particle size and be less than by such screen cloth
60 mesh, specifically, size is less than 1 inch/60=2.54 cm/60=0.0423 cm.
Ferrocene is a kind of organic compound of iron content, and its molecular formula is FeC10H10, or Fe (C5H5)2。
Hydraulic press is the usual means in industry and laboratory research, refers to one kind with liquid as working media, is used for
Energy or pressure is transmitted to realize polytechnic machine.The present invention realizes applying one to being extruded object both sides using hydraulic press
Fixed pressure, the particular type specification for hydraulic press does not do any limitation.
" operation is dried to formed blocks described in step 3 " in for above-mentioned steps four, it should be noted that in ability
In domain or even in various fields, it is a kind of common routine that the solid matter of moisture content or other volatile materials is dried
Operation.The basic object of drying process is part or all of moisture or other volatile materials is left solid.Usual solids
Matter is dried, and in addition to being placed in and being dried naturally in air, can also be dried up using hair-dryer, oven for drying, and infrared lamp dries
Dry, the sun is dried, vacuum drying chamber drying, is placed in drier and the operating method such as is dried, or aforesaid operations is any
Combination operation.Therefore, if be dried to formed blocks using above-mentioned any one operation or various operative combinations so that
The dried mass ratio of formed blocks is reduced to 75% or less before drying, and equivalence operation is belonged in the present invention.
" having the heater of temperature programmed control function " described in above-mentioned steps four is catalyst, solid material preparation field
In commonly use a kind of equipment, i.e., the Temperature-time relation that its temperature that can be realized in a heater is previously set according to certain
Curvilinear motion；The concrete form freedom of heater, can be but not limited to tube furnace, Muffle furnace, baking oven, electric furnace etc..
Average ramp rate is defined as follows in above-mentioned steps four：If in certain moment t1When thermometric object temperature value
It is T1, in another moment t2When thermometric object temperature value be T2, wherein t2In t1Afterwards, then from t1To t2This period
Interior, average ramp rate can be expressed as the business of temperature change value and time change value, i.e. (T2-T1)/(t2-t1).If warm
Degree is with Celsius' thermometric scaleoC or thermodynamic scale K is unit, and the time, the unit of average ramp rate was in units of minoC/
Min or K/min.HereoC/min is identical with the value of K/min.It is clear that also having other normal due to temperature and time
With unit, those skilled in the art can voluntarily carry out the conversion of unit.
Above-mentioned second closed container can be different closed with another container of the first closed container, or first
Container will participate in the container being continuing with after ferrocene is removed after the operation for completing " step 5 ".3rd closed container can
Be different from the first closed container it is close with another container, or the first closed container of the second closed container or second
Close a part for container.
" specific surface area " of material is the basic conception in Surface Science, is also the conventional physical quantity in this area, is referred to
It is the size of surface area that the material of unit mass has.This area measure side conventional for material " specific surface area "
Method is based on low temperature nitrogen adsorption-desorption isothermal, then by Brunauer-Emmett-Teller method substance for calculations
Specific surface area（Result is frequently referred to BET specific surface area）；Such Adsorption and desorption isotherms can also obtain the hole contained by solid matter
The information such as size and distribution situation, especially nanoscale Jie view hole road size and the information of distribution.
The positive effect of the present invention is as follows：
（1）The preparation process is simple of integral alumina supported ferric catalyst, raw material are cheap, and running cost is low, are suitable for big
Large-scale production.
（2）Preparation technology is environment-friendly, and in addition to using a certain amount of inorganic acid or organic acid, other materials is substantially all
It is nontoxic, non-corrosiveness material；And the inorganic acid and organic acid listed by technical scheme are all more conventional chemical substances, it makes
It is that those skilled in the art know with method, points for attention；Kneading step is nearly free from waste liquid, and hereafter the step of also do not produce
Raw waste liquid and waste gas, pollute small.
（4）Most integral catalyzer totality specific surface area is relatively low（Often it is less than<20 m2/g）, and monoblock type of the invention
The specific surface area of alumina load iron catalyst may be up to 150 ~ 500 m2/g.Product also has substantial amounts of nanoscale Jie view hole
Road, makes it have good catalysis, adsorption applications prospect.
Brief description of the drawings
Fig. 1 is monolithic substrate mould schematic diagram；
In figure：1 is the part of mould first；2 is the part of mould second；3 is the part of mould the 3rd；4 is that the part of mould first is wrapped
The cylindrical cavity for containing；5 be the part of mould first the axis comprising cylindrical cavity；6 is mould the second part crimping section；
7 is mould the second part pressure-bearing part；8 is the compressive plane of mould the second part crimping section；9 is mould the second part pressure-bearing portion
The pressure-bearing surface for dividing；10 is the part crimping section of mould the 3rd；11 is the part pressure-bearing part of mould the 3rd；12 is the part of mould the 3rd
The compressive plane of crimping section；13 is the pressure-bearing surface of the part pressure-bearing part of mould the 3rd；It is enclosed within the cylinder that the first part is included
Molding precursor 14 inside shape cavity 4；8th, 9,12,13 4 directions of arrow are also represented when mould is integrally extruded it by external force
Afterwards, the Impact direction of mould is illustrated.
Fig. 2 is the schematic diagram of each material placement figure in the first closed container when iron component gas phase is deposited（Vertical section figure）；
In figure：I, the first closed container；II, integral alumina carrier lay down location；III, ferrocene annular stack lay down location.
Fig. 3 is the schematic diagram of each material placement figure in the first closed container when iron component gas phase is deposited（Top view figure）；
In figure：I, the first closed container；II, integral alumina carrier lay down location；III, ferrocene annular stack lay down location.
Specific embodiment
Embodiment one,
A kind of integral alumina supported ferric catalyst based on vapour deposition process, including integral alumina supported ferric catalyst
Preparation method and integral alumina supported ferric catalyst product feature；Wherein integral alumina supported ferric catalyst preparation side
Method uses the following raw material：
Silicon source：Aluminium hydroxide；
First additive：Sesbania powder is mixed with guar gum with mass ratio 5 to 1；
Second additive：Ethanol；
Acid solution：PH value is 0.5 nitric acid and oxalic acid mixed aqueous solution, and wherein the ratio between material mole of nitric acid and oxalic acid is 1:
1。
Integral alumina supported ferric catalyst preparation method described in the present embodiment, uses monolithic substrate shaping mould
Tool；During mould work as shown in Figure 1；The mould includes the first part of mould 1, the second part of mould 2 and mould
Has the 3rd part 3；The part of mould first includes a cylindrical cavity 4；The second part of mould 2 is extruded comprising the part of mould second
Part 6 and mould the second part pressure-bearing part 7；The geometry of the second part of mould crimping section 6 is cylinder, and it has one
Individual compressive plane 8, the geometry of the compressive plane 8 is circle；Mould the second part pressure-bearing part 7 has a pressure-bearing surface 9；Mould
3rd part 3 includes the part crimping section 10 of mould the 3rd and the part pressure-bearing part 11 of mould the 3rd；The part of mould the 3rd is extruded
The geometry of part 10 is cylinder, and it has a compressive plane 12, and the geometry of the compressive plane 12 is circle；Mould
Three part pressure-bearing parts 11 have a pressure-bearing surface 13；The compressive plane 8 of mould the second part crimping section and the part of mould the 3rd
The axial direction of the cylindrical cavity that the compressive plane 12 of crimping section can be included from the part of mould first is put into.
The size of the cylindrical cavity 4 that the part of mould first is included is：Cylindrical bottom is the circle of a diameter of 60 mm
Shape, a height of 35 mm of cylinder.
Integral alumina supported ferric catalyst preparation method described in the present embodiment, uses two closed containers, difference
Referred to as the first closed container and the second closed container；The two closed containers be all with lid, closeing the lid can be with closed, whole
Body is all the vessel of glass material；Use an open container, referred to as the first open container；It is a glass for opening.
Integral alumina supported ferric catalyst preparation method described in the present embodiment, by using above-mentioned raw materials and master
Device is wanted, its preparation process is comprised the steps of：
Step one, prepare molding precursor；
The assembling of step 2, molding precursor and mould；
Step 3, to molding precursor apply pressure；
Step 4, the drying of formed blocks and roasting；
The deposition of step 5, ferrocene on monolithic substrate；
Step 6, the roasting of post-depositional first paragraph；
Step 7, the roasting of post-depositional second segment.
The specific method of above-mentioned seven steps is as follows：
Step one, prepare molding precursor；Specific method is as follows：
Silicon source, the first additive, second additive of certain mass are taken, wherein silicon source quality is 100 g；The matter of the first additive
Amount is 0.05 times of silicon source quality, and the quality of the second additive is 0.08 times of silicon source quality；Three kinds of materials uniformly mix, and obtain
Mixed-powder；Acid solution is then poured slowly into mixed-powder, dough is formed, the quality of wherein acid solution is silicon source
0.85 times of quality；Kneading is carried out to dough by hand or banded extruder so that silicon source therein, the first addition
Thing, the second additive, acid solution further uniformly mix, and form a moulded pottery not yet put in a kiln to bake, do not have obvious droplet formation on moulded pottery not yet put in a kiln to bake；By upper
State the moulded pottery not yet put in a kiln to bake referred to as molding precursor that mixture kneading is obtained.
The assembling of step 2, molding precursor and mould；Specific method is as follows：
Molding precursor is filled in the cylindrical cavity 4 that first part of mould 1 of monolithic substrate mould is included, such as
Shown in the mark 14 of accompanying drawing 1；The quality of molding precursor is 19.4 g；By the second part of mould crimping section 6 and mould the 3rd 0
The both sides of the cylindrical cavity 4 that part crimping section 10 is included from the part of mould first are respectively charged into；Needed for filling molding precursor
Material is not limited with the order for placing the part of mould second or the part of mould the 3rd；When the compressive plane of mould the second part crimping section
8th, the inwall of cylindrical cavity 4 that the compressive plane 12 of the part crimping section of mould the 3rd is included with the part of mould first is collectively forming
One airtight cavity, and above-mentioned molding precursor is enclosed in the airtight cavity（As shown at 14）, complete to load step.
Step 3, to molding precursor apply pressure；Specific method is as follows：
The molding precursor that will be assembled is combined with monolithic substrate mould and is placed on a hydraulic press, the part of mould second
Pressure-bearing surface 9 is contacted with the pressure-bearing surface 13 of the part of mould the 3rd with the applying press member of hydraulic press so that what hydraulic press was applied
Pressure can act on above-mentioned two pressure-bearing surface；Pressure direction is as shown in 9,13 two arrows of accompanying drawing 1；The pressure size of applying
In the range of 0.1 ~ 5 MPa；Applying pressure time is 20 s ~ 40 min；Then it is removed from the molds the shaping after being pressurized
Precursor obtains formed blocks.
Step 4, the drying of formed blocks and roasting；Specific method is as follows：
Operation is dried to formed blocks described in step 3, part volatility moisture is left formed blocks with other materials,
Until the dried quality of formed blocks is 69% before drying；The present embodiment is using the drying means for drying naturally in atmosphere；
Formed blocks are placed in a heater with temperature programmed control function are afterwards calcined；The atmosphere of roasting is air；Journey
Temperature and time relation in sequence roasting includes three temperature controlling stages, is referred to as the first temperature controlling stages, the second temperature
Degree control stage and the 3rd temperature controlling stages；First temperature controlling stages have an initial temperature, and its value is 60oC, tool
There is a final temperature, its value is 650oC, from initial temperature to final temperature average ramp rate 3.3oC/min scopes
It is interior；The total time of the first temperature controlling stages is 3.0 h；The second temperature control stage has an initial temperature, and its value is 650oC, with a final temperature, its value is also 650oC, is 0 from initial temperature to final temperature average ramp rateoC/
min；It is 5 h that second temperature controls the total time in stage；3rd temperature controlling stages have an initial temperature, and its value is 650oC, with a final temperature, its value is 30 ~ 150oC, is -0.7 from initial temperature to final temperature average ramp rateoC；The total time of the 3rd temperature controlling stages is 14 h；Afterwards, formed blocks are converted into integral alumina carrier.
The deposition of step 5, ferrocene on monolithic substrate；Specific method is as follows：
The ferrocene powder of certain mass is taken, the quality of wherein ferrocene is integral alumina carrier quality described in step 4
1.5 times；Ferrocene powder is respectively put into the first closed container and carried out with the integral alumina carrier described in step 4
It is closed；Wherein integral alumina carrier is positioned over somewhere as a block, and ferrocene powder is with the shape of sub-circular
It is looped around around integral alumina carrier；Integral alumina carrier and ferrocene powder will according to the method described above have been held
The first closed container be entirely positioned in a heater, and the first closed container is heated, heating-up temperature is 105oC；Heat time is in the range of 8 h；Integral alumina carrier changes into ferrocene-integral alumina load after completing heating
Nanocrystal composition.
Step 6, the roasting of post-depositional first paragraph；Specific method is as follows：
Ferrocene described in step 5-integral alumina carrier complexes are transferred to the second closed appearance from the first closed container
Device；Second closed container is entirely positioned in a heater, and the second closed container is heated, heating-up temperature is
195 oC；Heat time is 4.5 h.
Step 7, the roasting of post-depositional second segment；Specific method is as follows：
Ferrocene described in step 6-integral alumina carrier complexes are transferred to first and opened wide from the second closed container and is held
Device；First open container is entirely positioned in a heater, and the first open container is heated, heating-up temperature exists
450 oIn the range of C, the heat time is 8 h.
After completing step 7, whole preparation process is finished, and ferrocene-integral alumina carrier complexes are converted into entirety
Formula alumina load iron catalyst product；The integral alumina supported ferric catalyst also has following product feature simultaneously：
（1）, single integral alumina supported ferric catalyst block quality be 5.6 g；
（2）, integral alumina supported ferric catalyst specific surface area up to 195 m2/g；
（3）, on integral alumina supported ferric catalyst iron mass percent up to 2.1 %；
（4）, integral alumina supported ferric catalyst X-ray diffraction peak only wrap salic SPECTROSCOPIC CHARACTERIZATION, and be free of
SPECTROSCOPIC CHARACTERIZATION on iron component.
It is above-mentioned（3）（4）2 points combine explanation, and on the basis of with considerable iron component load capacity, iron component is on microcosmic
With decentralization very high.See in principle, if the microscopic particles of iron component can obtain its X-ray in 5 more than nm spread out
Penetrate peak.The assay method of the specific surface area of integral alumina supported ferric catalyst is foregoing low temperature nitrogen adsorption-desorption etc.
Warm collimation method；Tested by same sign, while it has also been found that, integral alumina supported ferric catalyst is also situated between with a large amount of nanoscales
View hole road, its bore dia average is about 8 ~ 9 nm.
Embodiment two,
Other are with embodiment one, difference：
Using monolithic substrate mould, the cylindrical bottom of wherein cylindrical cavity 4 is the circle of a diameter of 100 mm, circle
A height of 35 mm of cylindricality.
The assembling of step 2, molding precursor and mould；Wherein, the quality of molding precursor is 55.0 g.
The deposition of step 5, ferrocene on monolithic substrate；First closed container is heated, and heating-up temperature is 130oC。
After completing step 7, whole preparation process is finished, and ferrocene-integral alumina carrier complexes are converted into entirety
Formula alumina load iron catalyst product；The integral alumina supported ferric catalyst also has following product feature simultaneously：
（1）, single integral alumina supported ferric catalyst block quality be 12.5 g；
（2）, integral alumina supported ferric catalyst specific surface area up to 182 m2/g；
（3）, on integral alumina supported ferric catalyst iron mass percent up to 4.6 %；
（4）, integral alumina supported ferric catalyst X-ray diffraction peak only wrap salic SPECTROSCOPIC CHARACTERIZATION, and be free of
SPECTROSCOPIC CHARACTERIZATION on iron component.
Embodiment three,
Other are with embodiment one, difference：
The assembling of step 2, molding precursor and mould；Wherein, the quality of molding precursor is 15.1 g.
Step 4, the drying of formed blocks and roasting；The atmosphere being wherein calcined is purity oxygen；Wherein the first temperature control stage has
There is an initial temperature, its value is 40oC, with a final temperature, its value is 350oC；First temperature control stage is warm from starting
It is 2.1 to spend final temperature average ramp rateoC/min；The total time in the first temperature control stage is 2.5 h；Second temperature control rank
Section has an initial temperature, and its value is 350oC, with a final temperature, its value is 700oC；Second temperature control stage is from
Beginning temperature to final temperature average ramp rate be 1oC/min；It is 5.8 h that second temperature controls the total time in stage；3rd
The temperature control stage has an initial temperature, and its value is 700oC, with a final temperature, its value is 30oC, the 3rd temperature control rank
Section is -0.55 from initial temperature to final temperature average ramp rateoC/min；The total time in the 3rd temperature control stage is 20.3
h。
The deposition of step 5, ferrocene on monolithic substrate；First closed container is heated, and heating-up temperature is 130oC。
After completing step 7, whole preparation process is finished, and ferrocene-integral alumina carrier complexes are converted into entirety
Formula alumina load iron catalyst product；The integral alumina supported ferric catalyst also has following product feature simultaneously：
（1）, single integral alumina supported ferric catalyst block quality be 3.5 g；
（2）, integral alumina supported ferric catalyst specific surface area up to 202 m2/g；
（3）, on integral alumina supported ferric catalyst iron mass percent up to 4.8 %；
（4）, integral alumina supported ferric catalyst X-ray diffraction peak only wrap salic SPECTROSCOPIC CHARACTERIZATION, and be free of
SPECTROSCOPIC CHARACTERIZATION on iron component.
Example IV,
Other are with embodiment one, difference：
Second additive：Carbon black of the granularity less than 60 mesh；
The deposition of step 5, ferrocene on monolithic substrate；The quality of ferrocene is that integral alumina described in step 4 is carried
1.0 times of weight；Heated in the first closed container, heating-up temperature is 130oC。
Step 7, the roasting of post-depositional second segment；And the first open container is heated, heating-up temperature is 700oC,
Heat time is 4 h.
After completing step 7, whole preparation process is finished, and ferrocene-integral alumina carrier complexes are converted into entirety
Formula alumina load iron catalyst product；The integral alumina supported ferric catalyst also has following product feature simultaneously：
（1）, single integral alumina supported ferric catalyst block quality be 5.9 g；
（2）, integral alumina supported ferric catalyst specific surface area up to 180 m2/g；
（3）, on integral alumina supported ferric catalyst iron mass percent up to 4.6 %；
（4）, integral alumina supported ferric catalyst X-ray diffraction peak only wrap salic SPECTROSCOPIC CHARACTERIZATION, and be free of
SPECTROSCOPIC CHARACTERIZATION on iron component.
Embodiment five,
Other are with embodiment one, difference：
First additive：Sesbania powder；
The assembling of step 2, molding precursor and mould；Wherein, the quality of molding precursor is 20.1 g.
By the sign to obtained integral alumina carrier, integral alumina carrier also has the characteristics that：
Step 3, to molding precursor apply pressure；The pressure size for wherein applying is 1.5 MPa；Applying pressure time is 2 h.
Complete after step 4, formed blocks are converted into final products integral alumina carrier；Preparation process is completed.
After completing step 7, whole preparation process is finished, and ferrocene-integral alumina carrier complexes are converted into entirety
Formula alumina load iron catalyst product；The integral alumina supported ferric catalyst also has following product feature simultaneously：
（1）, single integral alumina supported ferric catalyst block quality be 5.7 g；
（2）, integral alumina supported ferric catalyst specific surface area up to 210 m2/g；
（3）, on integral alumina supported ferric catalyst iron mass percent up to 2.3 %；
（4）, integral alumina supported ferric catalyst X-ray diffraction peak only wrap salic SPECTROSCOPIC CHARACTERIZATION, and be free of
SPECTROSCOPIC CHARACTERIZATION on iron component.
Embodiment six,
Other are with embodiment three, difference：
First additive：Sesbania powder；
Second additive：Ethylene glycol；
Acid solution：Aqueous solution of nitric acid, its pH value is 0.3.
Step one, prepare molding precursor；Specific method is as follows：
Silicon source, the first additive, second additive of certain mass are taken, wherein silicon source quality is 105 g；Wherein the first additive
Quality be 0.02 times of silicon source quality, the quality of the second additive is 0.02 times of silicon source quality；Three kinds of materials uniformly mix,
Obtain mixed-powder；Acid solution is then poured slowly into mixed-powder, dough is formed, the quality of wherein acid solution is
0.9 times of silicon source quality.
The assembling of step 2, molding precursor and mould；Wherein, the quality of molding precursor is 20.0 g.
After completing step 7, whole preparation process is finished, and ferrocene-integral alumina carrier complexes are converted into entirety
Formula alumina load iron catalyst product；The integral alumina supported ferric catalyst also has following product feature simultaneously：
（1）, single integral alumina supported ferric catalyst block quality be 6.5 g；
（2）, integral alumina supported ferric catalyst specific surface area up to 230 m2/g；
（3）, on integral alumina supported ferric catalyst iron mass percent up to 4.9 %；
（4）, integral alumina supported ferric catalyst X-ray diffraction peak only wrap salic SPECTROSCOPIC CHARACTERIZATION, and be free of
SPECTROSCOPIC CHARACTERIZATION on iron component.
Claims (9)
1. a kind of integral alumina supported ferric catalyst based on vapour deposition process, including integral alumina load iron is catalyzed
Agent preparation method and integral alumina supported ferric catalyst product feature, it is characterised in that wherein integral alumina load
Iron catalyst preparation method uses the following raw material：
Silicon source：The one kind in aluminium hydroxide, boehmite, or above two material arbitrary proportion mixture；
First additive：It is the one kind in sesbania powder, sesbania gum, guar gum, cation guar gum, sodium alginate, or it is above-mentioned
The mixture of material arbitrary proportion；
Second additive：Be ethanol, propyl alcohol, butanol, ethylene glycol, propane diols, polyethylene glycol, polyvinyl alcohol, glucose, fructose,
Sucrose, maltose, cellobiose, granularity are less than the carbon black of 60 mesh, granularity less than the one kind in the water soluble starch of 60 mesh,
Or the mixture of above-mentioned substance arbitrary proportion；
Acid solution：A kind of aqueous solution, contains nitric acid, sulfuric acid, hydrochloric acid, acetic acid, oxalic acid, phosphoric acid, citric acid, maleic acid, tartaric acid
In one or more materials, the pH value of the aqueous solution is in the range of 0.0 ~ 4.0；
Above-mentioned integral alumina supported ferric catalyst preparation method, uses monolithic substrate mould；The mould bag
Include the part of mould first, the part of mould second and the part of mould the 3rd；The part of mould first includes a cylindrical cavity；Mould
Second part includes mould the second part crimping section and mould the second part pressure-bearing part；Mould the second part crimping section
Geometry is cylinder, and it has a compressive plane, and the geometry of the compressive plane is circle；Mould the second part pressure-bearing portion
Dividing has a pressure-bearing surface；The part of mould the 3rd includes the part crimping section of mould the 3rd and the part pressure-bearing part of mould the 3rd；
The geometry of the part crimping section of mould the 3rd is cylinder, and it has a compressive plane, and the geometry of the compressive plane is
It is circular；The part pressure-bearing part of mould the 3rd has a pressure-bearing surface；The compressive plane of mould the second part crimping section and mould the
The axial direction of the cylindrical cavity that the compressive plane of three part crimping sections can be included from the part of mould first is put into；
Above-mentioned integral alumina supported ferric catalyst preparation method, using two closed containers, is referred to as the first closed appearance
Device and the second closed container；The feature of the two closed containers is all that can open wide to be put into other objects rear closed, is to be put into
Object is confined in container；Use an open container, referred to as the first open container；
Above-mentioned integral alumina supported ferric catalyst preparation method, by using above-mentioned raw materials and main device, its preparation
Process is comprised the steps of：
Step one, prepare molding precursor；
The assembling of step 2, molding precursor and mould；
Step 3, to molding precursor apply pressure；
Step 4, the drying of formed blocks and roasting；
The deposition of step 5, ferrocene on monolithic substrate；
Step 6, the roasting of post-depositional first paragraph；
Step 7, the roasting of post-depositional second segment.
2. the integral alumina supported ferric catalyst based on vapour deposition process according to claim 1, it is characterised in that
The specific method of the step of its preparation method one is as follows：
Silicon source, the first additive, second additive of certain mass are taken, wherein the quality of the first additive is silicon source quality
0.01 ~ 0.1 times, the quality of the second additive is 0 ~ 0.2 times of silicon source quality；Three kinds of materials uniformly mix, and are mixed
Powder；Acid solution is then poured slowly into mixed-powder, dough is formed, the quality of wherein acid solution is silicon source quality
0.5 ~ 1.3 times；Kneading is carried out to dough by hand or banded extruder so that silicon source therein, the first addition
Thing, the second additive, acid solution further uniformly mix, and form a moulded pottery not yet put in a kiln to bake, do not have obvious droplet formation on moulded pottery not yet put in a kiln to bake；By upper
State the moulded pottery not yet put in a kiln to bake referred to as molding precursor that mixture kneading is obtained.
3. the integral alumina supported ferric catalyst based on vapour deposition process according to claim 1, it is characterised in that
The specific method of the step of its preparation method two is as follows：
Molding precursor is filled in the cylindrical cavity that the part of mould first of monolithic substrate mould is included, is molded
The quality of precursor is in 2 ~ 400 g ranges；Mould the second part crimping section and the part crimping section of mould the 3rd are distinguished
The both sides of the cylindrical cavity included from the part of mould first are put into；Load molding precursor material requested and place mould second
The order of part or the part of mould the 3rd is not limited；Compressive plane, the part of mould the 3rd extruding when mould the second part crimping section
Partial compressive plane is collectively forming an airtight cavity with the cylindrical empty cavity wall that the part of mould first is included, and will be above-mentioned
Molding precursor is enclosed in the airtight cavity, completes to load step.
4. the integral alumina supported ferric catalyst based on vapour deposition process according to claim 1, it is characterised in that
The specific method of the step of its preparation method three is as follows：
The molding precursor that will be assembled is combined with monolithic substrate mould and is placed on a hydraulic press, the part of mould second
Pressure-bearing surface is contacted with the pressure-bearing surface of the part of mould the 3rd with the applying press member of hydraulic press so that hydraulic press pressure applied
Above-mentioned two pressure-bearing surface can be acted on；The pressure size of applying is in the range of 0.1 ~ 5 MPa；It is 20 to apply pressure time
s ~ 40 min；Then it is removed from the molds the molding precursor after being pressurized and obtains formed blocks.
5. the integral alumina supported ferric catalyst based on vapour deposition process according to claim 1, it is characterised in that
The specific method of the step of its preparation method four is as follows：
Operation is dried to formed blocks described in step 3, part volatility moisture is left formed blocks with other materials,
Until the dried quality of formed blocks is less than 75% before drying；Drying process including but not limited to drying, dry in atmosphere
Drying in case or Muffle furnace, dry in vacuum drying chamber, dry in drier, blowing drying, daylight is dried, infrared lamp is dried,
The operations such as centrifuge drying, or any combination of aforesaid operations is operated；Formed blocks are placed in into one afterwards has temperature programmed control
It is calcined in the heater of function；The atmosphere of roasting is air, or purity oxygen, or any oxygenous ratio is mixed more than 20%
Close gas；Temperature and time relation in program roasting includes three temperature controlling stages, is referred to as the first temperature control rank
Section, second temperature control stage and the 3rd temperature controlling stages；First temperature controlling stages have an initial temperature, and its value is
20 ~ 150 oCertain value in the range of C, with a final temperature, its value is 300 ~ 700oCertain value in the range of C, from
Initial temperature is to final temperature average ramp rate 0.5 ~ 8oIn the range of C/min；First temperature controlling stages it is total when
Between in the range of 30 min ~ 12 h；The second temperature control stage has an initial temperature, and its value is 300 ~ 700oC models
Certain interior value is enclosed, with a final temperature, its value is also 300 ~ 700oCertain value in the range of C, from initial temperature to
Final temperature average ramp rate is -2 ~ 2oIn the range of C/min；The total time in second temperature control stage is in 1 ~ 6 h
In the range of；3rd temperature controlling stages have an initial temperature, and its value is 300 ~ 700oCertain value in the range of C, has
One final temperature, its value is 20 ~ 150oCertain value in the range of C, changes from initial temperature to final temperature mean temperature
Rate is -8 ~ -0.5oIn the range of C/min；The total time of the 3rd temperature controlling stages is in the range of 2 ~ 24 h；Afterwards, it is molded
Block is converted into integral alumina carrier.
6. the integral alumina supported ferric catalyst based on vapour deposition process according to claim 1, it is characterised in that
The specific method of the step of its preparation method five is as follows：
The ferrocene powder of certain mass is taken, the quality of wherein ferrocene is integral alumina carrier quality described in step 4
0.004 ~ 2 times；Integral alumina carrier described in ferrocene powder and step 4 is respectively put into the first closed container
And carry out closed；Wherein integral alumina carrier is positioned over somewhere as a block, and ferrocene powder is with sub-circular
Shape be looped around around integral alumina carrier；Integral alumina carrier and two cyclopentadienyls will according to the method described above have been held
First closed container of iron powder is entirely positioned in a heater, and the first closed container is heated, heating-up temperature
80 ~ 190oIn the range of C；Heat time is in the range of 20 min ~ 12 h；Complete integral alumina carrier after heating
Change into ferrocene-integral alumina carrier complexes.
7. the integral alumina supported ferric catalyst based on vapour deposition process according to claim 1, it is characterised in that
The specific method of the step of its preparation method six is as follows：
Ferrocene described in step 5-integral alumina carrier complexes are transferred to the second closed appearance from the first closed container
Device；Second closed container is entirely positioned in a heater, and the second closed container is heated, heating-up temperature exists
180 ~ 270 oIn the range of C；Heat time is in the range of 20 min ~ 12 h.
8. the integral alumina supported ferric catalyst based on vapour deposition process according to claim 1, it is characterised in that
The specific method of the step of its preparation method seven is as follows：
Ferrocene described in step 6-integral alumina carrier complexes are transferred to first and opened wide from the second closed container and is held
Device；First open container is entirely positioned in a heater, and the first open container is heated, heating-up temperature exists
300 ~ 800 oIn the range of C, the heat time is 30 min ~ 24 h；After completing step 7, whole preparation process is finished, two cyclopentadienyls
Iron-integral alumina carrier complexes are converted into integral alumina supported ferric catalyst product.
9. the integral alumina supported ferric catalyst based on vapour deposition process according to claim 1, the catalyst is also
There is following product feature simultaneously：（1）The quality of single integral alumina supported ferric catalyst block is up to 1 ~ 110 g；
（2）The specific surface area of integral alumina supported ferric catalyst is up to 130 ~ 500 m2/g；（3）Integral alumina load iron
The mass percent of iron is up to 0.3 ~ 11 % on catalyst；（4）The X-ray diffraction of integral alumina supported ferric catalyst
Peak only wraps salic SPECTROSCOPIC CHARACTERIZATION, and is free of the SPECTROSCOPIC CHARACTERIZATION on iron component.
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| CN108686701A (en) * | 2018-05-15 | 2018-10-23 | 中国石油大学(华东) | Iron catalyst for destruction of phenol prepares and reaction process |
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