CN106732600A - A kind of enhanced integral alumina supported ferric catalyst of high-specific surface area - Google Patents
A kind of enhanced integral alumina supported ferric catalyst of high-specific surface area Download PDFInfo
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- CN106732600A CN106732600A CN201710042024.7A CN201710042024A CN106732600A CN 106732600 A CN106732600 A CN 106732600A CN 201710042024 A CN201710042024 A CN 201710042024A CN 106732600 A CN106732600 A CN 106732600A
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- Prior art keywords
- mould
- catalyst
- precursor
- temperature
- pressure
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 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 40
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000002243 precursor Substances 0.000 claims abstract description 62
- 239000000463 material Substances 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 43
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- 238000000465 moulding Methods 0.000 claims abstract description 32
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 31
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052742 iron Inorganic materials 0.000 claims abstract description 30
- 239000000654 additive Substances 0.000 claims abstract description 27
- 230000000996 additive effect Effects 0.000 claims abstract description 27
- 230000003319 supportive effect Effects 0.000 claims abstract description 25
- 238000012512 characterization method Methods 0.000 claims abstract description 17
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- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
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- 239000002184 metal Substances 0.000 claims description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 7
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- 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
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- 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 description 4
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- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
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- 239000004277 Ferrous carbonate Substances 0.000 claims description 2
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
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- 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
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- 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
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- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
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- 150000001412 amines Chemical class 0.000 claims description 2
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- FUSJZTVOKYJFPI-UHFFFAOYSA-N cyclopentane;iron;5-methylcyclopenta-1,3-diene Chemical compound [Fe].[CH-]1[CH-][CH-][CH-][CH-]1.C[C-]1C=CC=C1 FUSJZTVOKYJFPI-UHFFFAOYSA-N 0.000 claims description 2
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 2
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- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
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- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
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Classifications
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- 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
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- 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
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- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
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- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B30—PRESSES
- B30B—PRESSES IN GENERAL
- B30B11/00—Presses specially adapted for forming shaped articles from material in particulate or plastic state, e.g. briquetting presses, tabletting presses
- B30B11/22—Extrusion presses; Dies therefor
- B30B11/221—Extrusion presses; Dies therefor extrusion dies
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Abstract
The invention belongs to catalysis technical field, it is related to a kind of enhanced integral alumina supported ferric catalyst of high-specific surface area, comprising method for preparing catalyst and catalyst prod feature.Wherein preparation method uses the following raw material：Aluminum precursor, iron precursor, the first additive, the second additive, acid solution, supportive material：Use integral catalyzer mould；Comprise the steps of：First, molding precursor is prepared；2nd, inclusion enclave is loaded；3rd, pressure is applied to inclusion enclave；4th, the program roasting of formed blocks.The method products obtained therefrom is also provided simultaneously with following characteristics：The quality of single catalyst block is up to 1 ~ 100 g；The overall specific surface area of catalyst is 150 ~ 550 m2/g；Ferro element mass content in single catalyst block is up to 0.3 ~ 15 %；The X ray diffraction peaks of catalyst only wrap salic SPECTROSCOPIC CHARACTERIZATION, and are free of the SPECTROSCOPIC CHARACTERIZATION on iron component.Product has application prospect.
Description
Technical field
The invention belongs to catalysis technical field, it is related to a kind of enhanced integral alumina load iron of high-specific surface area to be catalyzed
Agent and preparation method thereof, in particular it relates to iron precursor, supportive material and the one-shot forming of alumina precursor moulded pottery not yet put in a kiln to bake are tool by one kind
There is enhanced integral alumina supported ferric catalyst of high-specific surface area and preparation method thereof.
Background technology
Numerous industrial processes include catalytic reaction process, especially chemical products production, energy substance production with
And during environmental protection.In the catalyst of commercial Application, carrier-borne transition metal catalysts are a very common types.
Iron is the most a kind of transition metal of content in the earth's crust, is also one of material that the mankind use earliest, is also filled in catalytic process
As important role.For example, load typed iron catalyst is usually used in Fischer-Tropsch-synthesis, the catalysis oxidation of alkane, denitration, catalysis peroxide
Change the significant process such as hydrogen decomposition.Sometimes a kind of co-catalyst is also served as to be used in conjunction with other active metal components.Support type is urged
Agent can be divided into urging for particle or powdered iron catalyst, integral catalyzer, and given shape from macroscopic form
Agent.Integral catalyzer has some obvious advantages for particle or powdered iron catalyst.But currently for
The preparation method of integral supported sections catalyst is also few, and especially whole block is all the situation of iron catalyst.
A kind of Fe disclosed in patent CN105148914A2O3/Al2O3/ cordierite catalyst and preparation method thereof, obtaining can
For the integral catalyzer of denitration.The catalyst preparation includes the step being coated in using Alumina gel on cordierite surface.Although
Specifying information of the invention without related specific surface area, but because cordierite specific surface area is relatively low, therefore whole catalyst ratio
Surface area will be by larger limitation.For loaded catalyst, the decentralization of active component is for catalysis activity to closing weight
Will；Relevant information can be obtained from characterization methods such as X-ray diffraction, pulse absorption, transmission electron microscopes.From foregoing invention,
Reader cannot learn the deployment conditions of related iron component.The document of Beijing University of Chemical Technology's report【Chen Nengzhan etc., LaAl1-xFexO3/
Al2O3The preparation of/FeCrAl catalyst and its to methyl hydride combustion catalytic performance, is catalyzed journal, volume 2005,26,11 phases, page 1017】
In describe one kind with the component metals of iron content three as active component, the monoblock type iron with aluminum oxide and FeCrAl as binary vector
Method for preparing catalyst.The method first coats alumina slurry on FeCrAl alloy sheets, after drying, impregnates by LaAl1- xFexO3The slurry that powder is made.The method is similar with above-mentioned patent, due to containing an alloy sheet, will largely effect on catalyst
Overall surface area.For Metal Distribution, although active component may have in alumina support space preferably divides
Divergence, but from whole catalyst block, FeCrAl alloy sheets occupy larger space, the active component point of whole catalyst
Cloth is uneven.
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 the low process of high-specific surface area, high ferro component decentralization, high mechanical strength, running cost
Demand.
The content of the invention
The present invention proposes enhanced integral alumina supported ferric catalyst of a kind of high-specific surface area and preparation method thereof,
Its technology path is first to make aluminum oxide and iron precursor mixing moulded pottery not yet put in a kiln to bake, then obtains precursor with support by adding supportive material
Property material inclusion enclave, then by mould compression forming, then the technology path of product is obtained by the roasting of fine program.
By the technology path can obtain high-specific surface area, it is microcosmic on possess nanoscale duct, high mechanical properties monoblock type aoxidize
Aluminium supported ferric catalyst；Simultaneously the preparation method without expensive device, raw material sources simple, more friendly environment, safe operation, into
This is relatively low.Realizing the concrete technical scheme of above-mentioned technology path is：
A kind of enhanced integral alumina supported ferric catalyst of high-specific surface area, produces comprising method for preparing catalyst and catalyst
Product feature；Wherein method for preparing catalyst uses the following raw material：
Aluminum precursor：One kind of aluminium hydroxide, boehmite, or above-mentioned substance arbitrary proportion mixture；
Iron precursor：Be frerrous chloride, iron chloride, ferrous nitrate, ferric nitrate, ferrous sulfate, ferric sulfate, ferrous acetate, ferric acetate,
Ferrous carbonate, ferric carbonate, ferrous oxalate, ferric oxalate, ferric acetyl acetonade, ferrocene, methyl ferrocene, ethyl dicyclopentadienyl iron, second two
One kind in amine tetraacethyl-iron complex, or above-mentioned substance arbitrary proportion mixture；
First additive：It is sesbania powder, sesbania gum, guar gum, cation guar gum, sodium alginate, carboxymethylcellulose calcium, carboxylic second
One kind in base cellulose, sodium carboxymethylcellulose, sodium hydroxyethlcellulose, galactomannans, or above-mentioned substance is any
The mixture of ratio；
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；
Supportive material：One kind in wire, bonding jumper, sheet metal, wire netting or carbon fiber, or the above-mentioned type material
It is applied in combination with arbitrary proportion；The material of wherein metal be one kind in iron, stainless steel, copper, chromium, nickel, zinc, aluminium, titanium, manganese or
Alloy material based on above-mentioned material；Metal material species can be one kind of above-mentioned material, or various with arbitrary proportion group
Conjunction is used；For wire, bonding jumper or carbon fiber, its stretched length is not less than 1 cm；For sheet metal or wire netting
For, its circumference projected area is not less than 0.1 cm2。
Above-mentioned method for preparing catalyst, uses integral catalyzer mould；The mould includes mould the 1st
Part, 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 is included
Mould the second part crimping section and mould the second part pressure-bearing part；The geometry of mould the second part crimping section is circle
Cylinder, it has a compressive plane, and the geometry of the compressive plane is circle；Mould the second part pressure-bearing part has one and holds
Pressure 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 part of mould the 3rd
The geometry of crimping section is cylinder, and it has a compressive plane, and the geometry of the compressive plane is circle；Mould the 3rd
Part pressure-bearing part has a pressure-bearing surface；The compressive plane of mould the second part crimping section and the part crimping section of mould the 3rd
The axis direction of cylindrical cavity that can be included from the part of mould first of compressive plane be put into.
Above-mentioned method for preparing catalyst, by above-mentioned raw materials and integral catalyzer mould, its preparation method bag
Containing following steps：
Step one, prepare molding precursor；
Step 2, filling inclusion enclave；
Step 3, to inclusion enclave apply pressure；
Step 4, the roasting of the program of formed blocks.
The specific method of aforementioned four step is as follows：
Step one, prepare molding precursor；Specific method is as follows：
Take aluminum precursor, iron precursor, the first additive, second additive of certain mass；Rubbing containing ferro element wherein in iron precursor
The ratio between molal quantity containing aluminium element is 0.003 ~ 0.12 in that number and aluminum precursor；The quality of the first additive is aluminum precursor quality
0.01 ~ 0.1 times；The quality of the second additive is 0 ~ 0.2 times of aluminum precursor quality；Four kinds of materials uniformly mix, and obtain mixed powder
End；Acid solution is then poured slowly into mixed-powder, dough is formed, the quality of wherein acid solution is aluminum precursor quality
0.5 ~ 1.3 times；Kneading is carried out to dough by hand or banded extruder so that aluminum precursor 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 drop on moulded pottery not yet put in a kiln to bake；By above-mentioned mixed
The moulded pottery not yet put in a kiln to bake that compound kneading is obtained referred to as molding precursor.
Step 2, filling inclusion enclave；Specific method is as follows：
Molding precursor described in the step of taking certain mass one, its quality is in the range of 2 ~ 400g；Take the supportive of certain mass
Material, its quality is 0.01 ~ 0.6 times of molding precursor quality；Molding precursor is filled into entirety together with supportive material
In the cylindrical cavity that formula shaping of catalyst the first part of mould is included；Filling rear support material is formed precursor parcel；
Inclusion enclave is formed after molding precursor parcel supportive material；By mould the second part crimping section and the part press section of mould the 3rd
The both sides of the cylindrical cavity for being included from the part of mould first respectively are divided to load；Load inclusion enclave material requested and place mould
The order of the second part or the part of mould the 3rd is not limited；Compressive plane, the part of mould the 3rd when mould the second part crimping section
The compressive plane of crimping section is collectively forming an airtight cavity with the cylindrical empty cavity wall that the part of mould first is included, and will
Above-mentioned inclusion enclave is enclosed in the airtight cavity, completes to load step.
Step 3, to molding precursor apply pressure；Specific method is as follows：
The integral catalyzer mould combination that inclusion enclave will be assembled is placed on a hydraulic press, mould the second part pressure-bearing
Partial pressure-bearing surface, the pressure-bearing surface of the part pressure-bearing part of mould the 3rd are contacted with the applying press member of hydraulic press so that hydraulic pressure
Machine pressure applied can act on above-mentioned two pressure-bearing surface；The pressure size of applying is in the range of 0.1 ~ 5 MPa；Apply
Pressure time is in the range of 20 s ~ 4 h；The molding precursor after being pressurized then is taken out from mould and obtains formed blocks.
Step 4, the roasting of the program of formed blocks；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 85% 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 stage, the
Two temperature control stages and the 3rd temperature control stage；First temperature control stage had an initial temperature, and its value is 20 ~ 150oIn the range of C
Certain value, with a final temperature, its value is 300 ~ 750oCertain value in the range of C；First temperature control stage is from starting
Temperature is to final temperature average ramp rate 0.5 ~ 8oIn the range of C/min；The total time of the first temperature controlling stages exists
In the range of 30 min ~ 12 h；Second temperature control stage had an initial temperature, and its value is 300 ~ 750oCertain in the range of C
Individual value, with a final temperature, its value is also 300 ~ 750oCertain value in the range of C；Second temperature control stage is warm from starting
Final temperature average ramp rate is spent -2 ~ 2oIn the range of C/min；The total time in the second temperature control stage is in 1 ~ 6 h
In the range of；3rd temperature control stage had an initial temperature, and its value is 300 ~ 750oCertain value in the range of C, with one
Final temperature, its value is 20 ~ 150oCertain value in the range of C；3rd temperature control stage is average from initial temperature to final temperature
Rate of temperature change is -8 ~ -0.5oIn the range of C/min；The total time in the 3rd temperature control stage is in the range of 2 ~ 24 h.
Complete after step 4, formed blocks are converted into the enhanced integral alumina of final products, i.e. high-specific surface area
Supported ferric catalyst；Preparation process is completed.
By the sign to above-mentioned final products, the enhanced monoblock type of the product of above-mentioned preparation method, i.e. high-specific surface area
Alumina load iron catalyst, is also provided simultaneously with following product feature：
（1）The quality of single catalyst block is up to 1 ~ 100 g；
（2）The overall specific surface area of catalyst is 150 ~ 550 m2/g；
（3）Ferro element mass content in single catalyst block is up to 0.3 ~ 15 %；
（4）The X-ray diffraction peak of catalyst only wraps salic SPECTROSCOPIC CHARACTERIZATION, and is free of the SPECTROSCOPIC CHARACTERIZATION on iron component.
It is above-mentioned（2）（3）（4）Feature, not comprising supportive material result contribution；This is because these characterization results are
The sampling of catalyst sample is characterized, and supportive material is avoided during sign.
Because the X-ray diffraction peak SPECTROSCOPIC CHARACTERIZATION of aluminum oxide is known to those skilled in the art, therefore the present invention need not be given.
It is above-mentioned（3）、（4）2 points of comprehensive explanations, while with considerable iron component load capacity, iron component has on microcosmic
There is decentralization very high.It is noted that the characterization test method of the present invention and non-protected product, but the protection present invention is obtained
The due feature of product.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.
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 85% 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.
" 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 enhanced integral alumina supported ferric catalyst, raw material are cheap, and running cost is low, fit
Together in large-scale production；Enhanced integral alumina loads siderophore and ordinary unit alumina supported catalyst phase
Than its mechanical strength is greatly improved so that later stage service life is longer.
（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.
（3）Compared with the existing monoblock type ground of most of utilizations then coats catalytic component, one-shot forming reduces work
Skill number of steps.
（4）Existing most of integral catalyzer specific surface areas are relatively low（Often it is less than<20 m2/g）, and enhancing of the invention
The specific surface area of type integral alumina supported ferric catalyst may be up to 550 m2/g.Due to supportive material proportion compared with
It is small, smaller is influenceed on total body surface area.Product also has substantial amounts of nanoscale Jie view hole road, and size makes between 7 ~ 20 nm
It has good catalysis, adsorption applications prospect.
Brief description of the drawings
The integral catalyzer mould schematic diagram of accompanying drawing 1.；1 is the part of mould first；2 is the part of mould second；3 are
The part of mould the 3rd；4 is the cylindrical cavity that the part of mould first is included；5 be the part of mould first institute comprising cylindrical empty
The geometrical axis in chamber 4, the axis only to facilitate understand and draw, and non-actual existence；6 is mould the second part press section
Point；7 is mould the second part pressure-bearing part；8 is the compressive plane of mould the second part crimping section；9 is that the part of mould second holds
The pressure-bearing surface of laminate section；10 is the part crimping section of mould the 3rd；11 is the part pressure-bearing part of mould the 3rd；12 is mould the 3rd
The compressive plane of part crimping section；13 is the pressure-bearing surface of the part pressure-bearing part of mould the 3rd；14 representatives are enclosed within the first part institute
Comprising cylindrical cavity 4 inside molding precursor；8th, 9,12,13 4 directions of arrow are also represented when mould is integrally subject to outer
After power extruding, the Impact direction of mould is illustrated.
Specific embodiment
Embodiment one,
A kind of enhanced integral alumina supported ferric catalyst of high-specific surface area, comprising enhanced integral alumina load iron
Method for preparing catalyst and enhanced integral alumina supported ferric catalyst product feature；Wherein preparation method uses following former
Material：
Aluminum precursor：Aluminium hydroxide；
Iron precursor：Ferrocene；
First additive：The mixture of sesbania powder and sodium hydroxyethlcellulose, the two mass ratio is 4.5 to 1；
Second additive：Carbon black of the granularity less than 60 mesh；
Acid solution：PH value is 0.5 nitric acid and oxalic acid mixed aqueous solution, and wherein the ratio between nitric acid and oxalic acid material mole is 1 ratio
1；
Supportive material：Stainless steel strip, length is for about 2.5 cm；The cm of its sectional area about 0.032。
Method for preparing catalyst described in the present embodiment, uses integral catalyzer mould；The mould works
When as shown in Figure 1；The mould includes the first part of mould 1, the second part of mould 2 and the part 3 of mould the 3rd；Mould
One part includes a cylindrical cavity 4；The second part of mould 2 includes the second part of mould crimping section 6 and mould the 2nd 0
Part pressure-bearing part 7；The geometry of the second part of mould crimping section 6 is cylinder, and it has a compressive plane 8, the extruding
The geometry in face 8 is circle；Mould the second part pressure-bearing part 7 has a pressure-bearing surface 9；The part 3 of mould the 3rd includes mould
Have the 3rd part crimping section 10 and the part pressure-bearing part 11 of mould the 3rd；The geometry of the part crimping section 10 of mould the 3rd
It is cylinder, it has a compressive plane 12, and the geometry of the compressive plane 12 is circle；The part pressure-bearing part 11 of mould the 3rd
With a pressure-bearing surface 13；The compressive plane 8 of mould the second part crimping section and the compressive plane of the part crimping section of mould the 3rd
The axis direction of 12 cylindrical cavities that 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, circle
A height of 35 mm of cylindricality.
Method for preparing catalyst described in the present embodiment, by above-mentioned raw materials and integral catalyzer mould, its
Preparation method is comprised the steps of：
Step one, prepare molding precursor；
Step 2, filling inclusion enclave；
Step 3, to inclusion enclave apply pressure；
Step 4, the roasting of the program of formed blocks.
The specific method of aforementioned four step is as follows：
Step one, prepare molding precursor；Specific method is as follows：
Take aluminum precursor, iron precursor, the first additive, second additive of certain mass；Wherein aluminum precursor quality is 78 g, before iron
The ratio between molal quantity containing aluminium element is 0.044 in molal quantity and aluminum precursor containing ferro element in body, in conversion cost implementation
Iron precursor（Ferrocene）Quality be 8.2 g；The quality of wherein the first additive is 0.04 times of aluminum precursor quality, the second addition
The quality of thing is 0.08 times of aluminum precursor quality；Four kinds of materials uniformly mix, and obtain mixed-powder；Then acid solution is slowly fallen
Enter mixed-powder, form dough, the quality of wherein acid solution is 0.88 times of aluminum precursor quality；Hand is first passed through, after
Kneading is carried out to dough using banded extruder so that aluminum precursor therein, the first additive, the second additive, acid are molten
Liquid further uniformly mixes, and forms a moulded pottery not yet put in a kiln to bake for appearance uniform, does not have obvious drop on moulded pottery not yet put in a kiln to bake；By said mixture kneading
The moulded pottery not yet put in a kiln to bake for obtaining referred to as molding precursor.
Step 2, filling inclusion enclave；Specific method is as follows：
Molding precursor described in the step of taking certain mass one, its quality is 35.2 g；Take the supportive material of certain mass, its matter
Amount is 3.8 g, is 0.108 times of molding precursor quality；Molding precursor is filled into monoblock type together with supportive material to urge
Agent mould（Accompanying drawing 1）In the cylindrical cavity 4 that first part 1 is included（As marked shown in 14）；Filling rear support
Material is formed precursor parcel；Inclusion enclave is formed after molding precursor parcel supportive material；By the second part of mould crimping section 6
The both sides of the cylindrical cavity 4 included from the part of mould first respectively with the part crimping section 10 of mould the 3rd load；Load
Inclusion enclave material requested is not limited with the order for placing the part of mould second or the part of mould the 3rd；When mould the second part press section
In the cylindrical cavity 4 that compressive plane 8, the compressive plane 12 of the part crimping section of mould the 3rd and the part of mould first for dividing are included
Wall is collectively forming an airtight cavity, and above-mentioned inclusion enclave is enclosed in the airtight cavity（As shown at 14）, complete to load step.
Step 3, to inclusion enclave apply pressure；Specific method is as follows：
The integral catalyzer mould combination that inclusion enclave will be assembled is placed on a hydraulic press, mould the second part pressure-bearing
Partial pressure-bearing surface 9, the pressure-bearing surface 13 of the part pressure-bearing part of mould the 3rd are contacted with the applying press member of hydraulic press so that liquid
Press pressure applied can act on above-mentioned two pressure-bearing surface；The pressure size of applying is 1.4 MPa；Apply pressure time
It is 20 min；The molding precursor after being pressurized then is taken out from mould and obtains formed blocks.
Step 4, the roasting of the program of formed blocks；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 about 71% before drying；The present embodiment is using the drying side dried naturally in atmosphere
Method；Formed blocks are placed in a Muffle furnace with temperature programmed control function afterwards carry out heating roasting；The atmosphere of roasting is
Air；Temperature and time relation in program roasting includes three temperature controlling stages, is referred to as the first temperature control stage, second
Temperature control stage and the 3rd temperature control stage；First temperature control stage had an initial temperature, and its value is 50oC, with a termination
Temperature, its value is 650oC；First temperature control stage was 2.0 from initial temperature to final temperature average ramp rateoC/min；
The total time in the first temperature control stage is 5.0 h；Second temperature control stage had an initial temperature, and its value is 650oC, with one
Individual final temperature, its value is also 650oC；Second temperature control stage was 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 control stage had an initial temperature, and its value is 650oC, with a final temperature, its value is 30oC, the 3rd temperature control stage is from initial temperature to final temperature average ramp rate
For -0.7oC/min；The total time in the 3rd temperature control stage is 14 h.
Complete after step 4, formed blocks are converted into the enhanced integral alumina of final products, i.e. high-specific surface area
Supported ferric catalyst；Preparation process is completed.
By the sign to above-mentioned final products, the enhanced monoblock type of the product of above-mentioned preparation method, i.e. high-specific surface area
Alumina load iron catalyst, is also provided simultaneously with following product feature：
（1）The quality of single catalyst block is 12.4 g；
（2）The specific surface area of catalyst is 192 m2/g；
（3）Ferro element mass content in single catalyst block is up to 4.8 %；
（4）The X-ray diffraction peak of catalyst only wraps salic SPECTROSCOPIC CHARACTERIZATION, and is free of the SPECTROSCOPIC CHARACTERIZATION on iron component.
It is above-mentioned（2）（3）（4）Feature, not comprising supportive material result contribution.
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 the enhanced integral alumina supported ferric catalyst of high-specific surface area is foregoing low temperature
Nitrogen adsorption-desorption isotherm method；Tested by same sign, while it has also been found that, enhanced integral alumina load iron is urged
Agent also has a large amount of nanoscale Jie view hole roads, and its most probable bore dia is about 13 nm.
Embodiment two,
The present embodiment is a comparative example, in order to verify that supportive material increases for the mechanical strength of integral catalyzer
Pretend use.Specific practice is distinguished and is with embodiment one：
Step 2, filling inclusion enclave；Supportive material is not used；It is identical with embodiment one that other load process；Now inclusion enclave
In only molding precursor, and be free of supportive material.
Resulting product is referred to as " integral alumina supported ferric catalyst " after completion step 4（Labeled as product
A）.By the product " enhanced integral alumina supported ferric catalyst " of embodiment one（Labeled as product B）With the product A of this example
Mechanical strength comparing is carried out, process is as follows：
By above-mentioned two product（Sheet cylinder）It is individually placed in approximately the same plane, then with a rigid board for ruler shape
Body is positioned on two products, and product is located at the lower section that ruler two breaks.Ruler top to be placed on a rigid block movement certain high afterwards
Degree, allows its free-falling to clash into ruler middle part so that the impulsive force that rigid block movement falls is acted on two products by ruler.
The height of rigid block movement is improved constantly, until at least one product occurs to crush.
Test result finds that product A ruptures prior to product B, and the mechanical strength for illustrating product B is higher than product A；Namely
Say, embodiments of the invention one have reached the enhanced effect of mechanical strength of monolithic substrate product.
Embodiment three,
Other are with embodiment one, difference：
Iron precursor：Ferric nitrate；
First additive：Sesbania powder；
Second additive：Ethanol；
Step one, prepare molding precursor；Wherein in iron precursor in molal quantity and aluminum precursor containing ferro element containing aluminium element mole
The ratio between number is 0.022, converts into ferric nitrate（Do not calculate the crystallization water）Quality be 5.3 g；
Step 2, filling inclusion enclave；Molding precursor described in the step of taking certain mass one, its quality is 35.6 g；Take certain matter
The supportive material of amount, its quality is 2.8 g, is 0.078 times of molding precursor quality；
Step 4, the roasting of the program of formed blocks；The atmosphere being wherein calcined is purity oxygen；Wherein the first temperature control stage has one
Initial temperature, its value is 40oC, with a final temperature, its value is 350oC；First temperature control stage is from initial temperature to end
Only temperature-averaging rate of temperature change is 2.1oC/min；The total time in the first temperature control stage is 2.5 h；Second temperature control stage had
One initial temperature, its value is 350oC, with a final temperature, its value is 700oC；Second temperature control stage is from initial temperature
It is 1 to final temperature average ramp rateoC/min；It is 5.8 h that second temperature controls the total time in stage；3rd temperature control rank
Section has an initial temperature, and its value is 700oC, with a final temperature, its value is 30oC, the 3rd temperature control stage is from
Beginning temperature to final temperature average ramp rate be -0.55oC/min；The total time in the 3rd temperature control stage is 20.3 h.
Complete after step 4, formed blocks are converted into the enhanced integral alumina of final products, i.e. high-specific surface area
Supported ferric catalyst；Preparation process is completed.
By the sign to above-mentioned final products, the enhanced monoblock type of the product of above-mentioned preparation method, i.e. high-specific surface area
Alumina load iron catalyst, is also provided simultaneously with following product feature：
（1）The quality of single catalyst block is 11.9 g；
（2）The specific surface area of catalyst is 233 m2/g；
（3）Ferro element mass content in single catalyst block is up to 2.2 %；
（4）The X-ray diffraction peak of catalyst only wraps salic SPECTROSCOPIC CHARACTERIZATION, and is free of the SPECTROSCOPIC CHARACTERIZATION on iron component.
Example IV,
Other are with embodiment one, difference：
Supportive material：Diameter is about the aluminum alloy sheet of 30 mm, and monolithic quality is about 1.1 g.
Using integral catalyzer mould, the cylindrical bottom of wherein cylindrical cavity 4 is a diameter of 100 mm
Circle, a height of 35 mm of cylinder.
Step 2, filling inclusion enclave；Molding precursor described in the step of taking certain mass one, its quality is 56.6 g；Take one
Determine the supportive material of quality, its quality is 4.4 g, be 0.078 times of molding precursor quality；
Step 3, to molding precursor apply pressure；The pressure size for wherein applying is 1.4 MPa；Applying pressure time is 2 h.
Complete after step 4, formed blocks are converted into the enhanced integral alumina of final products, i.e. high-specific surface area
Supported ferric catalyst；Preparation process is completed.
By the sign to above-mentioned final products, the enhanced monoblock type of the product of above-mentioned preparation method, i.e. high-specific surface area
Alumina load iron catalyst, is also provided simultaneously with following product feature：
（1）The quality of single catalyst block is 20.5 g；
（2）The specific surface area of catalyst is 206 m2/g；
（3）Ferro element mass content in single catalyst block is up to 4.6 %；
（4）The X-ray diffraction peak of catalyst only wraps salic SPECTROSCOPIC CHARACTERIZATION, and is free of the SPECTROSCOPIC CHARACTERIZATION on iron component.
Claims (6)
1. the enhanced integral alumina supported ferric catalyst of a kind of high-specific surface area, comprising method for preparing catalyst and catalyst
Product feature, it is characterised in that wherein method for preparing catalyst uses the following raw material：
Aluminum precursor：One kind of aluminium hydroxide, boehmite, or above-mentioned substance arbitrary proportion mixture；
Iron precursor：Be frerrous chloride, iron chloride, ferrous nitrate, ferric nitrate, ferrous sulfate, ferric sulfate, ferrous acetate, ferric acetate,
Ferrous carbonate, ferric carbonate, ferrous oxalate, ferric oxalate, ferric acetyl acetonade, ferrocene, methyl ferrocene, ethyl dicyclopentadienyl iron, second two
One kind in amine tetraacethyl-iron complex, or above-mentioned substance arbitrary proportion mixture；
First additive：It is sesbania powder, sesbania gum, guar gum, cation guar gum, sodium alginate, carboxymethylcellulose calcium, carboxylic second
One kind in base cellulose, sodium carboxymethylcellulose, sodium hydroxyethlcellulose, galactomannans, or above-mentioned substance is any
The mixture of ratio；
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；
Supportive material：One kind in wire, bonding jumper, sheet metal, wire netting or carbon fiber, or the above-mentioned type material
It is applied in combination with arbitrary proportion；The material of wherein metal be one kind in iron, stainless steel, copper, chromium, nickel, zinc, aluminium, titanium, manganese or
Alloy material based on above-mentioned material；Metal material species can be one kind of above-mentioned material, or various with arbitrary proportion group
Conjunction is used；For wire, bonding jumper or carbon fiber, its stretched length is not less than 1 cm；For sheet metal or wire netting
For, its circumference projected area is not less than 0.1 cm2；
Above-mentioned method for preparing catalyst, uses integral catalyzer mould；The mould includes the part of mould first, mould
Have the second part and the part of mould the 3rd；The part of mould first includes a cylindrical cavity；The part of mould second includes mould
Second part crimping section and mould the second part pressure-bearing part；The geometry of mould the second part crimping section is cylinder
Body, it has a compressive plane, and the geometry of the compressive plane is circle；Mould the second part pressure-bearing part has a pressure-bearing
Face；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 part of mould the 3rd is squeezed
The geometry of laminate section is cylinder, and it has a compressive plane, and the geometry of the compressive plane is circle；Mould the 3rd 0
Part pressure-bearing part has a pressure-bearing surface；The compressive plane of mould the second part crimping section and the part crimping section of mould the 3rd
The axis direction of the cylindrical cavity that compressive plane can be included from the part of mould first is put into；
Above-mentioned method for preparing catalyst, by above-mentioned raw materials and integral catalyzer mould, its preparation method include with
Lower step：
Step one, prepare molding precursor；
Step 2, filling inclusion enclave；
Step 3, to inclusion enclave apply pressure；
Step 4, the roasting of the program of formed blocks.
2. the enhanced integral alumina supported ferric catalyst of high-specific surface area according to claim 1, its feature exists
One specific method is as follows the step of, its preparation method：Take aluminum precursor, iron precursor, the first additive, second of certain mass
Additive；Wherein in iron precursor in molal quantity and aluminum precursor containing ferro element the ratio between molal quantity containing aluminium element for 0.003 ~
0.12；The quality of the first additive is 0.01 ~ 0.1 times of aluminum precursor quality；The quality of the second additive is the 0 of aluminum precursor quality
~ 0.2 times；Four kinds of materials uniformly mix, and obtain mixed-powder；Acid solution is then poured slowly into mixed-powder, dough is formed
The quality of mixture, wherein acid solution is 0.5 ~ 1.3 times of aluminum precursor quality；Dough is mixed by hand or banded extruder
Thing carries out kneading so that aluminum precursor therein, the first additive, the second additive, acid solution further uniformly mix, and forms one
Individual moulded pottery not yet put in a kiln to bake, does not have obvious drop on moulded pottery not yet put in a kiln to bake；The moulded pottery not yet put in a kiln to bake referred to as molding precursor obtained by said mixture kneading.
3. the enhanced integral alumina supported ferric catalyst of high-specific surface area according to claim 1, its feature exists
Two specific method is as follows the step of, its preparation method：Molding precursor described in the step of taking certain mass one, its quality is 2
In the range of ~ 400g；The supportive material of certain mass is taken, its quality is 0.01 ~ 0.6 times of molding precursor quality；Will shaping
Precursor is filled into the cylindrical cavity that the part of integral catalyzer mould first is included together with supportive material；Dress
Fill out rear support material and be formed precursor parcel；Inclusion enclave is formed after molding precursor parcel supportive material；By mould the 2nd 0
The both sides dress of the cylindrical cavity that part crimping section is included from the part of mould first respectively with the part crimping section of mould the 3rd
Enter；Load inclusion enclave material requested and do not limited with the order for placing the part of mould second or the part of mould the 3rd；When mould the 2nd 0
The cylindrical empty that the compressive plane of part crimping section, the compressive plane of the part crimping section of mould the 3rd and the part of mould first are included
Cavity wall is collectively forming an airtight cavity, and above-mentioned inclusion enclave is enclosed in the airtight cavity, completes to load step.
4. the enhanced integral alumina supported ferric catalyst of high-specific surface area according to claim 1, its feature exists
Three specific method is as follows the step of, its preparation method：The integral catalyzer mould combination of inclusion enclave will be assembled
Be placed on a hydraulic press, the pressure-bearing surface of mould the second part pressure-bearing part, the pressure-bearing surface of the part pressure-bearing part of mould the 3rd with
The applying press member contact of hydraulic press so that hydraulic press pressure applied can act on above-mentioned two pressure-bearing surface；Apply
Pressure size in the range of 0.1 ~ 5 MPa；Applying pressure time is in the range of 20 s ~ 4 h；Then from mould
Take out the molding precursor after being pressurized and obtain formed blocks.
5. the enhanced integral alumina supported ferric catalyst of high-specific surface area according to claim 1, its feature exists
Four specific method is as follows the step of, its preparation method：Operation is dried to formed blocks described in step 3, part is waved
Hair property moisture leaves formed blocks with other materials, until the dried quality of formed blocks is less than 85% before drying；Dry
Operation including but not limited to drying in atmosphere, drying in baking oven or Muffle furnace, dry in vacuum drying chamber, do in drier
Dry, blowing drying, daylight is dried, infrared lamp dry, centrifuge is dried etc. operates, or any combination of aforesaid operations is operated；It
Formed blocks are placed in a heater with temperature programmed control function are afterwards calcined；The atmosphere of roasting is air, or pure
Oxygen, or any mixed gas of the oxygenous ratio more than 20%；Temperature and time relation in program roasting includes three temperature
In the control stage, it is referred to as the first temperature control stage, the second temperature control stage and the 3rd temperature control stage；First temperature control stage had one
Initial temperature, its value is 20 ~ 150oCertain value in the range of C, with a final temperature, its value is 300 ~ 750oC models
Enclose certain interior value；First temperature control stage is from initial temperature to final temperature average ramp rate 0.5 ~ 8oC/min models
In enclosing；The total time of the first temperature controlling stages is in the range of 30 min ~ 12 h；Second temperature control stage had a starting temperature
Degree, its value is 300 ~ 750oCertain value in the range of C, with a final temperature, its value is also 300 ~ 750oC scopes
Certain interior value；Second temperature control stage is from initial temperature to final temperature average ramp rate -2 ~ 2oC/min scopes
It is interior；The total time in the second temperature control stage is in the range of 1 ~ 6 h；3rd temperature control stage had an initial temperature, and its value is 300
~ 750 oCertain value in the range of C, with a final temperature, its value is 20 ~ 150oCertain value in the range of C；3rd temperature
The control stage is from initial temperature to final temperature average ramp rate -8 ~ -0.5oIn the range of C/min；3rd temperature control stage
Total time in the range of 2 ~ 24 h；
Complete after step 4, formed blocks are converted into the enhanced integral alumina load of final products, i.e. high-specific surface area
Iron catalyst；Preparation process is completed.
6. the enhanced integral alumina supported ferric catalyst of high-specific surface area and its system according to claim 1-5
Preparation Method, it is characterised in that the enhanced integral alumina load iron catalysis of the product of above-mentioned preparation method, i.e. high-specific surface area
Agent, is also provided simultaneously with following product feature：The quality of single catalyst block is up to 1 ~ 100 g；The totality of catalyst compares table
Area is 150 ~ 550 m2/g；Ferro element mass content in single catalyst block is up to 0.3 ~ 15 %；Catalyst
X-ray diffraction peak only wraps salic SPECTROSCOPIC CHARACTERIZATION, and is free of the SPECTROSCOPIC CHARACTERIZATION on iron component.
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