CN110193382A - The method for preparing the adjustable reticulated ceramics catalyst carrier of porosity using concave convex rod - Google Patents
The method for preparing the adjustable reticulated ceramics catalyst carrier of porosity using concave convex rod Download PDFInfo
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- CN110193382A CN110193382A CN201910378859.9A CN201910378859A CN110193382A CN 110193382 A CN110193382 A CN 110193382A CN 201910378859 A CN201910378859 A CN 201910378859A CN 110193382 A CN110193382 A CN 110193382A
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- catalyst carrier
- porosity
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- convex rod
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 239000000919 ceramic Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000004094 surface-active agent Substances 0.000 claims abstract description 32
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 22
- 230000004913 activation Effects 0.000 claims abstract description 21
- 229960000892 attapulgite Drugs 0.000 claims abstract description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims abstract description 13
- 229940001007 aluminium phosphate Drugs 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000011268 mixed slurry Substances 0.000 claims abstract description 12
- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 6
- 238000000465 moulding Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- -1 polyoxyethylene Polymers 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 229920000428 triblock copolymer Polymers 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 230000031709 bromination Effects 0.000 claims 1
- 238000005893 bromination reaction Methods 0.000 claims 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 238000005245 sintering Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 239000012876 carrier material Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 12
- 239000011148 porous material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- 230000003321 amplification Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000010908 plant waste Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001992 poloxamer 407 Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical class [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000008685 targeting Effects 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/182—Phosphorus; Compounds thereof with silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/657—Pore diameter larger than 1000 nm
-
- 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
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of methods for preparing the adjustable reticulated ceramics catalyst carrier of porosity using concave convex rod, by solid content be 40% the attapulgite of hydrochloric acid activation, the surfactant solution that mass concentration is 5 ~ 20%, aluminium phosphate sol that mass concentration is 15% through mechanical stirring to after uniformly, fumed silica microballoon is added, it mixes to get mixed slurry；Then, the mixed slurry is poured into curing molding in mold, at room temperature naturally dry, most afterwards after drying, calcining up to the adjustable reticulated ceramics catalyst carrier of porosity.Present invention process is simple, and operation is easily controllable, is not necessarily to double sintering, can prepare catalyst carrier material porous, that shrinking percentage is low and high-intensitive.
Description
Technical field
The present invention relates to catalyst carrier preparation technical fields, more particularly to prepare the adjustable net of porosity using concave convex rod
The method of eye ceramic catalyst carrier.
Background technique
Attapulgite, also known as palygorskite are a kind of aqueous zeopan clay minerals of chain layer structure, have uniqueness
Crystal structure and physicochemical property, there is crystal lattice in its structure, help to contain variable amount of Na in crystal+、Ca2+、Fe3+、
Al3+, crystal is in needle-shaped, fibrous or fiber set shape.Attapulgite has unique dispersion, high temperature resistant, salt resistance alkali etc. good
Colloidal nature and higher adsorption bleaching ability.There is pole in multiple fields such as environmental protection, chemical industry, light industry, agricultural, building materials
It is widely applied.In addition, Mg contained in structural unit2+、A13+Ion is easy to by other metal ion exchangeds.Layer knot
Structural hydroxyl group in structure can form Bronst acid site, and the Al of exposure3+Ion then forms Lewis acid site, therefore, recessed
Soil has certain acidity；Meanwhile attapulgite clay has certain adsorption capacity to organic matter, also has big specific surface
Long-pending, considerable micropore and thermal stability, therefore be the excellent of the potential catalyst of many heterogeneous catalytic reactions and many catalyst
Good carrier.
By attapulgite after peracid treatment, Surface L ewis acid increases, be conducive to abundant duct, high-specific surface area and
The porous mineral of strong characterization of adsorption can realize the targeting enrichment of water and pollutants in air；Have in the attapulgite that carrier introduces
Properties that expansion is uniformly, good thermal shock stability, hardness is big, chemical stability is good etc., and silica is good with wearability, chemically
The properties such as energy stabilization, fusing point height, can also increase the intensity of catalyst carrier.For this purpose, using this two kinds of mineral as main mine phase
Material is stablized as catalyst carrier, performance.To make to form suitable stomata in carrier, pore former (table is added in the carrier
Face activating agent), surfactant is introduced in catalyst carrier, active component can be made to be dispersed.
Porous ceramics is a kind of through high temperature firing, in vivo with the hole for largely communicating with each other and also connecting with material surface
The ceramic material of road structure.Porous ceramics is in filtering and cleaning technique, smart filtering technique, catalyst carrier, diaphragm material and reduction
The fields such as noise are widely used.And screen like and porous ceramic be it is a kind of with three-dimensional netted skeleton structure high porosity (75 ~
95%) porous ceramics, in addition to low-density possessed by porous ceramics, anticorrosive, good heat-proof quality, high temperature resistant and making
With the service life it is long the advantages that except, it also has the characteristics such as the cellular structure of high permeability, high-specific surface area and complexity, these characteristics
Make it in industries such as chemical industry, environmental protection, may be used as high temperature gas cleaning device, metallic filter, and processing chemical plant waste and
The catalyst carrier etc. of vehicle exhaust.
Zhu Jianliang (application number CN201710731090.2) etc. is by aluminium oxide, silicon carbide, kaolin, dolomite and sesbania
Carrier green body is made in powder and the pug of water after mixing；By carrier green body at 250 ~ 270 DEG C it is dry after, then carrier green body existed
1200 ~ 1300 DEG C of degeneration at high temperature, which is handled, is made catalyst carrier.There are drying and dehydratings and carrier green body to move back for the preparation method
Fiery treatment temperature is too high, and the disadvantages of surfactant carrys out its multi-component feedstock of aid dispersion is not added.
Who precious (application number CN201710152348.6) et al. is with Al2O3Powder, SiO2Powder, La (NO3)3, carbon fiber,
Dispersing agent and cornstarch are raw material, by La (NO3)3Load to Al2O3Powder, SiO2Powder, cornstarch, dispersing agent and
The porous aluminosilicate molecular sieve surface formed after carbon fiber sintering, forms La2O3Modified porous aluminosilicate molecular sieve catalytic
Agent carrier.Due to introducing in the preparation method, there are combustion-supporting property La (NO3)3Explosive material.In addition, the substance has storage to underground water
, there is the disadvantages of property harmful to environment in product effect.
Zhang Jingde (application number CN201611112555.0) et al. using kaolin, talcum powder, alumina powder as matrix material,
After adding a certain amount of monomer, crosslinking agent, initiator, after being made into ceramic slurry with sol-gal process, pours into mold and solidify
Molding.Then drying forms green compact.It is sintered to obtain porous cordierite ceramics catalyst carrier in high temperature sintering furnace.Due to
It needs to introduce monomer, crosslinking agent and initiator in the preparation method, therefore experiment condition is harsher.In addition, in raw material
Be matrix material with alumina powder, thus it is high there are sintering temperature the disadvantages of.
Tan Demin (application number CN201510539835.9) et al. aluminum oxide, titanium dioxide and pore creating material are matrix
After being mixed uniformly, the stirring of a certain concentration nitric acid is added in material；Then dry by mixture extrusion molding, it is placed in 500 ~
600 DEG C roast 2 ~ 5 hours, and cooled to room temperature obtains precursor carrier；Silicate solutions are sprayed on resulting vehicle precursor, are placed in
300 ~ 400 DEG C roast 2 ~ 4 hours, and cooled to room temperature obtains catalyst carrier.It needs to carry out twice in the preparation method
High temperature sintering, therefore that there are experimental procedures is cumbersome, the disadvantages of being unfavorable for heavy industrialization.
Wei Wei (application number CN201511024759.4) et al. is with low-quality bauxite, starch, dextrin, polyvinyl alcohol or carboxylic first
One of base cellulose is a variety of for additive and lauryl sodium sulfate, methyl anyl alcohol, cellulose derivative, poly- third
One of acrylamide, guar gum or fatty acid polyethylene glycol ester or it is a variety of be dispersing agent, after mixing be added pelletizer make
Grain is warming up to 1200 ~ 1400 DEG C after haydite calcining and obtains micropore ceramics catalyst carrier.It needs in the preparation method to low-quality
Bauxite activates at high temperature, complex steps.Furthermore this method can only prepare the ceramic catalyst carrier of pore type.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of utilization concave convex rods low in cost, easily industrialized to prepare hole
The method of the adjustable reticulated ceramics catalyst carrier of porosity.
To solve the above problems, of the present invention prepare the adjustable reticulated ceramics catalyst load of porosity using concave convex rod
The method of body, it is characterised in that: by solid content be 40% the attapulgite of hydrochloric acid activation, mass concentration be 5 ~ 20% surface it is living
Property agent solution, mass concentration be 15% aluminium phosphate sol through mechanical stirring to uniformly after, be added fumed silica microballoon, mix
It is even to get mixed slurry；Then, the mixed slurry is poured into curing molding in mold, at room temperature naturally dry, finally
Up to the adjustable reticulated ceramics catalyst carrier of porosity after drying, calcining；The attapulgite of the hydrochloric acid activation, the table
Face activator solution, the aluminium phosphate sol mass ratio be 1:0.5 ~ 2:1 ~ 5；The attapulgite of the hydrochloric acid activation with it is described
The mass ratio of fumed silica microballoon is 1:0.1 ~ 0.5.
The attapulgite of the hydrochloric acid activation refer to by the natural concave convex rod of 5 g with 50 mL concentration be 4mol/L hydrochloric acid it is molten
Liquid in 70 DEG C of activation 3h, and with deionized water washed to neutrality to get solid content be 40% hydrochloric acid activation concave convex rod
Stone.
The surfactant solution refers to is uniformly mixed surfactant with deionized water by the mass ratio of 1:5 ~ 19,
The surfactant solution for being 5 ~ 20% up to mass concentration；The surfactant refers to cetyl trimethylammonium bromide, ten
One in dialkyl benzene sulfonic acids sodium and polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer (PluronicF127)
Kind.
The aluminium phosphate sol refers to the Al (OH) of 1mol3It is added in the phosphoric acid solution of 3.5mol, is stirred at 95 DEG C
It mixes until in colourless transparent solution to obtain the final product.
The condition of the drying refers to prior to 80 DEG C dry 2 ~ 5h, then be warming up to 120 DEG C dehydration and drying 12 ~ for 24 hours.
The condition of the calcining refers to using rotary tube furnace, in N2Under protection, heated up with the heating rate of 5 DEG C/min
To 300 DEG C, 1h is kept the temperature, then be warming up to 850 DEG C with the heating rate of 5 DEG C/min.
Compared with the prior art, the present invention has the following advantages:
1, present invention adds fumed silica microballoons, due to SiO2Wearability is good, stable chemical performance, fusing point are high, therefore,
Enhance the intensity of catalyst carrier in practical applications.
2, the present invention introduces different types of surfactant, not only contributes in catalyst carrier preparation process
Enhance concave convex rod and SiO2The dispersibility of micron ball, and suitable screen like and porous ceramic is easily formed in calcination process, that is, it fills
When the pore former for forming meshed porous ceramic catalyst carrier.
3, it for raw material is because of it is good with unique dispersion, high temperature resistant, salt resistance alkali etc. that the present invention, which select concave convex rod,
Colloidal nature and higher adsorption capacity, and there is certain plasticity and cohesive force.Meanwhile concave convex rod is by HCl treatment
Afterwards, Surface L ewis acid site increases, and is conducive to the screen like and porous ceramic catalysis that synthesis can be stabilized in acid condition
Agent carrier.
4, present invention addition aluminium phosphate sol makes it when high-temperature calcination forms meshed porous ceramic catalyst carrier, has
Conducive to the shrinking percentage for reducing catalyst carrier.
5, the present invention can effectively be controlled screen like and porous ceramic and be urged by the concentration of surfactant in control volume phase solution
The porosity of agent carrier and aperture.
6, the present invention utilizes cheap raw material, is not necessarily to double sintering, can prepare that porous, shrinking percentage is low and high-intensitive
Catalyst carrier material.
7, present invention process is simple, operates easily controllable.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 is that the present invention is adjustable using a kind of porosity that cetyl trimethylammonium bromide is surfactant preparation
The amplification SEM photograph of reticulated ceramics catalyst carrier.Wherein: A: × 80；B: × 300.
Fig. 2 is that the present invention is made pottery using the adjustable mesh of a kind of porosity that Pluronic F127 is surfactant preparation
The amplification SEM photograph of porcelain catalyst carrier.Wherein: A: × 140；B: × 280.
Fig. 3 is that the present invention utilizes the adjustable mesh of a kind of porosity that neopelex is prepared by surfactant
The amplification SEM photograph of ceramic catalyst carrier.Wherein: A: × 120；B: × 240.
Specific embodiment
The method that embodiment 1 prepares the adjustable reticulated ceramics catalyst carrier of porosity using concave convex rod, this method are
Refer to: by 8 g solid contents be 40% the attapulgite of hydrochloric acid activation, 4 g mass concentrations be 5% surfactant solution, 8 g matter
Measure concentration be 15% aluminium phosphate sol through mechanical stirring to uniformly after, be added 0.8 g fumed silica microballoon, mix to get
Mixed slurry；Then, mixed slurry is poured into curing molding in mold, at room temperature after natural drying, prior to 80 DEG C dry 2
H, then 120 DEG C of 12 h of dehydration and drying are warming up to, form green compact；Last green compact use rotary tube furnace, in N2Under protection, with 5
DEG C/heating rate of min is warming up to 300 DEG C, heat preservation 1h removes its surfactant, then is heated up with the heating rate of 5 DEG C/min
It is calcined to 850 DEG C to get the adjustable reticulated ceramics catalyst carrier of porosity.
Wherein: the attapulgite of hydrochloric acid activation refer to by the natural concave convex rod of 5 g with 50 mL concentration be 4mol/L hydrochloric acid it is molten
Liquid is washed in 70 DEG C of activation 3h, and with deionized water to the attapulgite of the neutral hydrochloric acid activation for being 40% up to solid content.
Surfactant solution, which refers to, mixes 5 g surfactant cetyl trimethylammonium bromides and 95 g deionized waters
Close the surfactant solution for being uniformly 5% to get mass concentration.
Aluminium phosphate sol refers to the Al (OH) of 1mol3Be added in the phosphoric acid solution of 3.5mol, stirred at 95 DEG C to
Until in colourless transparent solution to obtain the final product.
Resulting catalyst carrier is tested through SEM, it can be found that compact area is the support construction of open pores, while
It is the guarantee that porous ceramics has some strength and integrality.In addition, there is also burnings except having larger-size stomata in material
Remain on gas in material after knot and forms micropore, the possible reason is gas is introduced when preparing green body, it still can be residual after sintering
Formation micropore (referring to Fig. 1) in material is stayed, porosity is 47.8 %, and aperture is 80 microns.
Resulting catalyst carrier is tested through dimensional measurement and pressure testing machine, and linear shrinkage is 1.28 %, intensity
For 38.2 MPa.
The method that embodiment 2 prepares the adjustable reticulated ceramics catalyst carrier of porosity using concave convex rod, this method are
Refer to: by 8 g solid contents be 40% the attapulgite of hydrochloric acid activation, 16 g mass concentrations be 20% surfactant solution, 40
G mass concentration be 15% aluminium phosphate sol through mechanical stirring to uniformly after, be added 4 g fumed silica microballoons, mix, i.e.,
Obtain mixed slurry；Then, mixed slurry is poured into curing molding in mold, it is at room temperature after natural drying, dry prior to 80 DEG C
Dry 5 h, then it is warming up to 120 DEG C of dehydration and drying for 24 hours, form green compact；Last green compact use rotary tube furnace, in N2Under protection,
300 DEG C are warming up to the heating rate of 5 DEG C/min, heat preservation 1h removes its surfactant, then with the heating rate liter of 5 DEG C/min
Temperature is calcined to get the adjustable reticulated ceramics catalyst carrier of porosity to 850 DEG C.
Wherein: the attapulgite of hydrochloric acid activation, aluminium phosphate sol are the same as embodiment 1.
Surfactant solution, which refers to, mixes 20 g surfactant sodium dodecyl base benzene sulfonic acid sodium salts with 80 g deionized waters
The surfactant solution for being uniformly 20% to get mass concentration.
Resulting catalyst carrier is tested through SEM, it can be found that compact area is the support construction of open pores, while
It is the guarantee that porous ceramics has some strength and integrality.In addition, there is also burnings except having larger-size stomata in material
Remain on gas in material after knot and forms micropore, the possible reason is gas is introduced when preparing green body, it still can be residual after sintering
Formation micropore (referring to Fig. 3) in material is stayed, porosity is 67.7 %, and aperture is 100 microns.
Resulting catalyst carrier is tested through dimensional measurement and pressure testing machine, and linear shrinkage is 2.12 %, intensity
For 25.7 MPa.
The method that embodiment 3 prepares the adjustable reticulated ceramics catalyst carrier of porosity using concave convex rod, this method are
Refer to: by 8 g solid contents be 40% the attapulgite of hydrochloric acid activation, 8 g mass concentrations be 15% surfactant solution, 24 g
Mass concentration be 15% aluminium phosphate sol through mechanical stirring to uniformly after, be added 2.4 g fumed silica microballoons, mix, i.e.,
Obtain mixed slurry；Then, mixed slurry is poured into curing molding in mold, it is at room temperature after natural drying, dry prior to 80 DEG C
Dry 3 h, then 120 DEG C of dehydration and drying 18h are warming up to, form green compact；Last green compact use rotary tube furnace, in N2Under protection,
300 DEG C are warming up to the heating rate of 5 DEG C/min, heat preservation 1h removes its surfactant, then with the heating rate liter of 5 DEG C/min
Temperature is calcined to get the adjustable reticulated ceramics catalyst carrier of porosity to 850 DEG C.
Wherein: the attapulgite of hydrochloric acid activation, aluminium phosphate sol are the same as embodiment 1.
Surfactant solution, which refers to, is uniformly mixed 15 g surfactant PluronicF127 with 85 g deionized waters,
The surfactant solution for being 15% up to mass concentration.
Resulting catalyst carrier is tested through SEM, it can be found that compact area is the support construction of open pores, while
It is the guarantee that porous ceramics has some strength and integrality.In addition, there is also burnings except having larger-size stomata in material
Remain on gas in material after knot and forms micropore, the possible reason is gas is introduced when preparing green body, it still can be residual after sintering
Formation micropore (referring to fig. 2) in material is stayed, porosity is 67.2 %, and aperture is 120 microns.
Resulting catalyst carrier is tested through dimensional measurement and pressure testing machine, and linear shrinkage is 4.64 %, intensity
For 18.6 MPa.
Claims (6)
1. the method for preparing the adjustable reticulated ceramics catalyst carrier of porosity using concave convex rod, it is characterised in that: by solid content
For the attapulgite of 40% hydrochloric acid activation, mass concentration be 5 ~ 20% surfactant solution, the phosphoric acid that mass concentration is 15%
Aluminum sol through mechanical stirring to uniformly after, be added fumed silica microballoon, mix to get mixed slurry；It then, will be described mixed
Slurry cast curing molding into mold is closed, at room temperature naturally dry, it is most adjustable up to porosity after drying, calcining afterwards
Reticulated ceramics catalyst carrier；The attapulgite of the hydrochloric acid activation, the surfactant solution, the aluminium phosphate sol
Mass ratio is 1:0.5 ~ 2:1 ~ 5；The mass ratio of the attapulgite of the hydrochloric acid activation and the fumed silica microballoon is 1:
0.1~0.5。
2. the method for preparing the adjustable reticulated ceramics catalyst carrier of porosity using concave convex rod as described in claim 1,
Be characterized in that: the attapulgite of the hydrochloric acid activation refer to by the natural concave convex rod of 5 g with 50 mL concentration be 4mol/L hydrochloric acid it is molten
Liquid in 70 DEG C of activation 3h, and with deionized water washed to neutrality to get solid content be 40% hydrochloric acid activation concave convex rod
Stone.
3. the method for preparing the adjustable reticulated ceramics catalyst carrier of porosity using concave convex rod as described in claim 1,
Be characterized in that: the surfactant solution refers to is mixed surfactant with deionized water by the mass ratio of 1:5 ~ 19
The even surfactant solution for being 5 ~ 20% to get mass concentration；The surfactant refers to cetyl trimethyl bromination
One of ammonium, neopelex and polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer.
4. the method for preparing the adjustable reticulated ceramics catalyst carrier of porosity using concave convex rod as described in claim 1,
Be characterized in that: the aluminium phosphate sol refers to the Al (OH) of 1mol3It is added in the phosphoric acid solution of 3.5mol, is stirred at 95 DEG C
It mixes until in colourless transparent solution to obtain the final product.
5. the method for preparing the adjustable reticulated ceramics catalyst carrier of porosity using concave convex rod as described in claim 1,
Be characterized in that: the condition of the drying refers to prior to 80 DEG C dry 2 ~ 5h, then be warming up to 120 DEG C dehydration and drying 12 ~ for 24 hours.
6. the method for preparing the adjustable reticulated ceramics catalyst carrier of porosity using concave convex rod as described in claim 1,
Be characterized in that: the condition of the calcining refers to using rotary tube furnace, in N2Under protection, with the heating rate liter of 5 DEG C/min
Temperature keeps the temperature 1h to 300 DEG C, then is warming up to 850 DEG C with the heating rate of 5 DEG C/min.
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