CN101412620A - Method for preparing porous alumina ceramic supporting body with sol as additive - Google Patents
Method for preparing porous alumina ceramic supporting body with sol as additive Download PDFInfo
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- CN101412620A CN101412620A CNA2008102322682A CN200810232268A CN101412620A CN 101412620 A CN101412620 A CN 101412620A CN A2008102322682 A CNA2008102322682 A CN A2008102322682A CN 200810232268 A CN200810232268 A CN 200810232268A CN 101412620 A CN101412620 A CN 101412620A
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Abstract
The invention discloses a method for preparing a porous alumina ceramic support body by using a colloidal sol as an addition agent, which comprises the following steps: adopting a low cost method to prepare the colloidal sol; adding the colloidal sol into mixed dry powder on the basis of aluminum oxide aggregate; and performing the processes of pugging, molding, sintering and the like to obtain a multi-channel pipe type or honeycomb type porous alumina ceramic support body. The method uses the colloidal sol as a caking agent, a sintering addition agent, and a performance improver, and makes use of the caking property of the colloidal sol, thus the dosage of organic caking agent can be reduced remarkably to solve the problem of easy cracking of binder removal sintering; and with the fine particles of the colloidal sol as the sintering addition agent, the sintering temperature can be reduced, and the dissolvability of the particles are improved, thus the sintered product does not have glass phase through microscopic analysis. The prior preparation method adopting low melting point glass phase as the sintering addition agent is improved, and the acid resistance, the alkali resistance and the high temperature strength of the porous alumina ceramic support body are improved.
Description
Technical field
The present invention relates to a kind of preparation method of porous alumina ceramic body, particularly a kind ofly prepare porous Al as auxiliary agent with colloidal sol
2O
3The method of ceramic supporting body.
Background technology
Porous material has particular performances with respect to dense material, in eighties of last century, growing field needs porous material, for example filters at molten metal, fields such as the supporter of elevated temperature heat insulation, catalyzed reaction, diesel engine waste gas filtering, High Temperature High Pressure waste gas filtering.
Inorganic ceramic film have polymkeric substance or metal separation film incomparable some advantages: high temperature resistant, can realize sterilization system on line; Chemical stability is good, can antimicrobial degraded.For organic solvent, etchant gas and microbial attack performance satisfactory stability.The physical strength height, high pressure resistant, good wear-resisting, abrasion resistance energy are arranged; Pore size distribution is narrow, and separation performance is good, and infiltration capacity is big and controlled, cleaning and regeneration repeatedly, long service life; Controlled electric property, lower specific inductivity; Lower thermal conductivity reduces thermosteresis.These characteristics can satisfy different actual requirements by the component and the microtexture of control material.The change of void content, pore size distribution, mean pore size and physical strength is the hugest to the influence of material property and Application Areas, simultaneously these performances be subjected to again raw-materially to choose, technogenic influences such as batching, moulding and sintering.Traditional ceramic membrane material, on ceramic matrix, produce the hole, and often to reduce the porosity that firing temperature improves material, and performances such as the porosity of stupalith and physical strength are conflicting all the time, often attend to one thing and lose sight of another on producing and using, particularly the goods of traditional production technique are difficult to satisfy actual performance requriements.
Inorganic ceramic film mainly is made up of porous supporting body and the film that covers thereon, the effect of ceramic film support mainly is the physical strength that increases film, to its requirement is to have bigger aperture and porosity, to increase the fluidic perviousness, reduces the fluid transport resistance.In addition, when ceramic membrane is used in fields such as high-temperature gas removal of impurities, melted metal filterings, also require supporter to have good thermal shock resistance, burst even damage because of violent temperature variation causes material preventing.
Nowadays, the porous alumina material is widely used in preparation of inorganic, and its research focus is to improve ratio defective product, reduces its production cost and improves its military service performance, and support body material plays an important role on the performance of mineral membrane.See with regard to present circumstances, no matter be paper or patent, the preparation porous ceramic support, the viscosity requirement when satisfying extruding all needs to add the organic binder bond of 8-20%, when the binder removal sintering, very easily crack like this, in order to reduce crackle, general by reducing binder removal speed, obviously like this can increase the binder removal sintering time, prolonged the production cycle, effect is not again clearly.
With regard to present situation, the higher preparation cost of ceramic membrane is one of most critical factor that influences the ceramic membrane application, and the preparation cost of ceramic membrane is mainly reflected on the preparation cost of supporter.With regard to homemade 19 passages, 30 millimeters of external diameters, 1000 millimeters of length, 4 millimeters of channel diameters, 1800 yuans, be 2400 yuans and be covered with 0.05 micron inorganic material film price, imported product is wanted more than 4500 yuan of Renminbi.If port number increases to 40 then can be higher, as seen the supporter cost accounts for whole film pipe fitting cost greater than 70%, trace it to its cause is that sintering forms under the 1700 degree high temperature being higher than because the ceramic supporting body overwhelming majority adopts the micron-sized alumina ceramic grain of high purity, yield rate is very low, make the sintering expense increase substantially, and preparation cycle is long or the like, and these factors all cause the preparation cost of ceramic supporting body high.
In addition, though porous ceramic film has unique advantage in sepn process, but in application process, still there are some problems, one is exactly the stability of porous ceramic film microtexture in the sepn process, and the military service performance of product, and provide the acid-alkali-corrosive-resisting performance of the porous supporting body of ceramic membrane intensity directly to determine porous ceramics not re-use stability and the separating effect in the process.Because the restriction of raw material, moulding process often contains SiO in the porous supporting body
2, the molten or alkali-soluble substances of acid such as CaO, MgO, after base substrate burnt till, these more materials will be present in the matrix grain edge with the form of glassy phase.This exist when porous supporting body is used in the soda acid system intensity in time prolongation and the phenomenon that reduces, and then influence the microtexture and the separation performance of ceramic membrane, it does not at high temperature almost have any intensity simultaneously, has limited the military service performance of membrane element widely.Therefore, the Changing Pattern of intensity in corrosive atmosphere and hot environment of research porous ceramic film support, and then the use properties of prediction porous ceramic film are the problems of a significant in the porous ceramic film application process.
Reduce the supporter manufacturing cost and mainly be to improve the sintering activity of ceramic aggregate and reduce sintering temperature, improve yield rate.At present, just how to reduce the sintering temperature of porous alumina ceramic supporting body, generally adopt following two kinds of methods:
1, adds more low-melting glass or oxide compound as sintering aid, as impurity such as silicon oxide, sodium oxide, calcium oxide, form liquid phase at lesser temps, be filled between the particles of aggregates and come promotes oxidn aluminum substrate particle sintering by producing capillary force, therefore with its sintering temperature of this kind feedstock production ceramic supporting body generally below 1600 degree, that have in addition can drop to 1200 the degree about, suitability for industrialized production also all adopts this method; This method is to come acceleration of sintering with the liquid phase that lesser temps produces down, burns till and contains more glassy phase in the product, and ubiquity the not problem of acid-alkali-corrosive-resisting, so sacrificed the performance of supporter to a certain extent.
2, add ultra-fine pottery (nano level) particle in the micron order ceramic powder skeletal grain as sintering aids.It is the focus of present stage research that interpolation ultrafine ceramic powder material comes acceleration of sintering.Ultra-fine grain have very big specific surface and and higher sintering activity, can form cenotype or sosoloid at a lower temperature, acceleration of sintering, thereby can reduce the sintering temperature of porous ceramic support to a certain extent.But directly add superfine ceramic powder and form coacervate easily, this just makes it be can not be evenly dispersed between the aggregate when aggregate mixes, and because intergranular reunion, need under higher temperature, form cenotype or sosoloid, therefore reducing the sintering temperature effect is not clearly, and this has also influenced quality and the cost that adopts the formed ceramic supporting body of this kind method.
Summary of the invention
The objective of the invention is to improve in the preparation of existing porous alumina ceramic supporting body and adopt the method for low melting glass, and then solve the especially problem of acid-proof alkaline and high temperature resistant property reduction of chemically unstable as sintering aid; Overcome the method that adopts the ultra-fine ceramic particle of interpolation and form problems such as reuniting and be difficult for being uniformly dispersed, sintering temperature is higher easily; And utilize sol bonded property, reduce the amount of organic binder bond greatly, thereby solve binder removal sintering problem easy to crack, provide a kind of by add aluminium colloidal sol, titanium colloidal sol, silicon sol as sintering aid and performance improving agent, preparation at a lower temperature has the method for the porous alumina ceramic supporting body of stable chemical performance.
For reaching above purpose, the present invention takes following technical scheme to be achieved:
A kind of colloidal sol prepares the method for porous alumina ceramic supporting body as auxiliary agent, comprises the steps:
(1) with α-Al
2O
3Micro mist is weighed as aggregate, and with α-Al
2O
3The quality of micro mist is the basis, the starch pore-forming material that adds the stearic acid dispersion agent of polyalcohols softening agent, 0.5-4% of cellulosic binder, the 2-8% of 5-10% and 2-6% is dried be mixed even;
(2) with aggregate α-Al
2O
3The quality of micro mist is the basis, and a kind of and water that adds 10-40% silicon sol, aluminium colloidal sol, titanium colloidal sol in doing mixed uniform compound is made pug;
(3) through vacuum pugging, old 24-36 hour, in the conventional vacuum extrusion machine extrusion moulding porous alumina ceramic supporting body blank, and dry;
(4) dried porous alumina ceramic supporting body blank is carried out binder removal and sintering process is made porous alumina ceramic supporting body, sintering temperature 1350-1550 ℃;
In the above-mentioned steps, described cellulosic binder is a Vltra tears; Described polyalcohols softening agent is polyoxyethylene glycol or polyvinyl alcohol; Described stearic acid dispersion agent is a sodium stearate; The median size of described starch pore-forming material is less than aggregate α-Al
2O
3The median size of micro mist.Described silicon sol adopts commercially available finished product Si (OH)
4Colloidal sol, its siliconoxide mass percentage composition is 20%, median size is 15 nanometers; Described aluminium colloidal sol adopts aluminium powder, and nitric acid, ammoniacal liquor are prepared from or adopt aluminium powder, and the aluminum oxide quality percentage concentration that hydrochloric acid, Aluminium chloride hexahydrate are prepared from is 20%, and particle diameter is the Al (OH) of 20-25 nanometers
4Colloidal sol; Described titanium colloidal sol adopts the titanium salt titanium oxide mass percentage concentration that hydrolysis is prepared under pH value 2-4 to be 15%, crystal formation is anatase octahedrite or rutile, median size are the Ti (OH) of 15 nanometers
4Colloidal sol.Described aggregate α-Al
2O
3Micro mist particle diameter between the 20-80 micron.Described binder removal, sintering process, concrete processing parameter is as follows: at the 20-140 degree, heat-up rate be the 3-6 degree/minute; At the 140-600 degree, heat-up rate is 20-40 degree/time; Spend sintering temperature 600, heat-up rate be the 3-6 degree/minute; After sintering temperature, be incubated 1-3 hour; Then with 3-6 degree/minute drop to 800 degree, furnace cooling to 200 degree again, blow-on door air is as cold as sampling about 80 degree.
The present invention utilizes the adhesive property of colloidal sol can reduce the interpolation of organic binder bond even replaces fully, has fundamentally solved the cracking problem of goods in binder removal, has both improved yield rate, has shortened the production cycle again.Colloidal sol of the present invention in addition combines functions such as binding agent, sintering aids and performance improving agent, selects a certain amount of colloidal sol addition for use, suitably adds a spot of organic binder bond, and net effect is best.
The present invention adopts with aluminium, silicon, titanium colloidal sol as sintering aid.For aluminium colloidal sol, behind the sintering in the product composition all be aluminum oxide, no glassy phase, resistance to acids and bases are very high, hot strength is also very high; For high-purity titanium colloidal sol, high temperature is the titanium oxide or the titanium aluminium polycrystalline phase of acid-alkali-corrosive-resisting mutually, simultaneously since add-on seldom, nearly all solid solutions are advanced in the matrix, so acid-alkali-corrosive-resisting performance and hot strength are also very high; For silicon sol, though the silicon oxide acid-proof alkaline not as titanium oxide, also is that performance is also higher because matrix is advanced in the few solid solution of add-on.
The present invention adopts colloidal sol, when having the suspension effect, also has the performance that some suspension can't satisfy.Colloidal sol particle diameter ratio suspension is littler, and specific surface can be bigger, can form liquid phase at a lower temperature during sintering, and the effect of acceleration of sintering can be better; Though the colloidal sol particle diameter is little, has thermodynamic phase, kinetics has stable tendency, in case be prepared into, collosol stability can be better than suspension; In addition, colloidal sol can be used as binding agent and adds in the aggregate, and suspension can't satisfy this point.
Description of drawings
Fig. 1 is the process flow sheet of the inventive method.
Fig. 2 is binder removal of the present invention, sintering temperature control curve.
Fig. 3 is that the base substrate of embodiment 1 is at dried SEM micro-image.Clearly demonstrate colloidal sol in the image and evenly be wrapped in matrix, and do not have agglomeration.
To be colloidal sol prepare the SEM Photomicrograph of the different embodiment sintered compacies of porous alumina supporter as auxiliary agent to Fig. 4, and aluminium colloidal sol embodiment 1, the second behavior interpolation titanium colloidal sol embodiment 2 is added in first behavior, and the third line is for adding silicon sol embodiment 3; 100 times of the first row positions, second classifies 1000 times as, and the 3rd classifies 3000 times as.Pictorial display sintering situation is good, low power pictorial display even air hole distribution, and the high power basic display does not have glassy phase.
Embodiment
As shown in Figure 1, powder (is comprised α-Al
2O
3Micro mist, binding agent, pore-forming material, softening agent and dispersion agent) driedly be mixed evenly, add colloidal sol and water and make pug, make porous alumina ceramic supporting body through pugging, old, extrusion molding, drying, binder removal sintering process.
α-Al
2O
3Micro mist is a micron order, and particle diameter is between the 20-80 micron, and as the ceramic powder aggregate, particle diameter is that the titanium oxide or the zirconium white of 10-100 micron also can use the inventive method to prepare porous ceramic support, is that concrete prescription need be done suitable change.Binding agent is a cellulose family, preferentially selects Vltra tears (HPMC) for use, and the mass percent that its add-on accounts for the aluminum oxide aggregate is 5-10%; Softening agent is a polyalcohols, preferentially selects polyoxyethylene glycol or polyvinyl alcohol for use, and the mass percent that its add-on accounts for the aluminum oxide aggregate is 2-8%; Dispersion agent is a stearic acid, preferentially selects sodium stearate for use, and the mass percent that its add-on accounts for the aluminum oxide aggregate is 0.5-4%; Pore-forming material generally adopts starch and carbon dust, because starch has certain viscosity, the role that in as ceramic additive, also can play the part of a part of binding agent, the total amount of organic additive is reduced, and then reduced the possibility that the binder removal process cracks, help the reduction of erection time, improve ratio defective product etc.The starch kind is a lot, there are some researches show as pore-forming material, and its molecule median size should be less than the median size of aluminum oxide aggregate.If the particle diameter of pore-forming material is greater than the particle diameter of aluminum oxide aggregate, bimodal phenomenon can appear when in the end surveying the pore size distribution of product, total median size is not the size decision by pore-forming material, but by aluminum oxide and pore-forming material particle packing characteristics determined, so in order to reduce the bimodal phenomenon in the pore size distribution, shorten pore size distribution range, preferably select the median size of the median size of pore-forming material less than the aluminum oxide aggregate.Mung bean shallow lake particle diameter is that 4～28 μ m, conventional corn starch 5～26 μ m are, sweet potato starch is that 5～31 μ m yam starchs are 15～100 μ m.Can select different starch as pore-forming material according to the size of different aluminum oxide aggregates in the production.The present invention is directed to particle diameter α-Al between the 20-80 micron
2O
3Micro mist is selected conventional corn starch for use.
The mass percent that the colloidal sol add-on accounts for aluminum oxide powder is 10%-40%, and silicon sol is more cheap in the colloidal sol, directly buys to get final product, and nano silicon oxide quality percentage composition is 20%, and median size is 15 nanometers; But aluminium colloidal sol and titanium colloidal sol are more expensive, and for reducing cost, the present invention adopts the preparation method of lower cost, and concrete grammar is as follows:
One, the preparation method of aluminium colloidal sol:
The aluminium Sol A: raw material is Aluminium chloride hexahydrate AlCl
36H
2O, aluminium powder, hydrochloric acid.With AlCl
36H
2O and mixed in hydrochloric acid add aluminium powder then gradually in above-mentioned mixed liquid, keep 70-80 ° of C of temperature, stir 6 hours in magnetic stirrer, obtain transparent colloidal liquid, i.e. Al (OH)
4Colloidal sol, aluminum oxide quality percentage concentration is 20%, particle diameter is 20-25 nanometers.Each reactant ratio is that the mol ratio of hydrochloric acid and water is 0.21, and the pH value in the reaction process is 3-5, can cooperate hydrochloric acid and ammoniacal liquor to regulate.Aluminium powder and Aluminium chloride hexahydrate mol ratio are 1.76.
The aluminium sol B: raw material is an aluminium powder, nitric acid, ammoniacal liquor.The preparation of aluminium treatment solution adds the 8g/L fine aluminium in the salpeter solution of people 1mol/L, magnetic agitation 1h in 100 ℃ of water-baths, and cooled and filtered is concentrated into 1/3 of original solution volume with filtrate, and is stand-by as the fine aluminium treatment solution; Slowly join the fine aluminium treatment solution in the ammoniacal liquor, make ammoniacal liquor and fine aluminium treatment solution ratio remain on 75 ℃ for the 1.5:1. temperature, after liquid feeding finishes, the salpeter solution that adds 1mol/L, making salpeter solution and fine aluminium treatment solution ratio is 0.5:1, continuation finally obtains transparent gluey Al (OH) at 75 ℃ stirred in water bath 6-12h
4Colloidal sol.Aluminum oxide quality percentage concentration is 20%, and particle diameter is 20-25 nanometers.
Two, the compound method of titanium colloidal sol:
Raw material is a titanium sulfate, hydrochloric acid, NP-10, ammoniacal liquor, nitric acid.Titanium sulfate is added water stir into the salts solution that concentration is 1.0mol/L, press the volumetric molar concentration of 0.02mol/L and add MAP (single Tryfac 5573) as tensio-active agent, be mixed with mixing solutions, stirring heating is 4 hours under magnetic stirrer, control reaction temperature is 75 ℃, pH value 2-4 by dropping ammonia and nitric acid control reaction obtains colloidal liquid, i.e. Ti (OH)
4Colloidal sol.The titanium oxide mass percentage concentration is 15%, and crystal formation is sharp titanium or rutile, and median size is 15 nanometers.
Mixing, pugging technology, siccative is comprised that aluminum oxide aggregate, binding agent, softening agent, lubricant, dispersion agent and pore-forming material do not add ball with planetary ball mill and did mixed 1-3 hour, add an amount of carbon black in the siccative that when experiment, is preparing, do and mix after 2 hours, the black carbon black is evenly dispersed in the white powder, and SEM micro-image (as Fig. 3 embodiment 1) shows that colloidal sol is wrapped on the particles of aggregates uniformly.The layer of substance that the blapharoplast surface is covered can form liquid phase at lesser temps and be dispersed in matrix border uniformly, reduces sintering temperature effectively, makes the product chemical property more even.Batch mixing among the present invention, the high efficiency of pugging technology also are described simultaneously.After in dry blend, adding colloidal sol and an amount of distilled water, synthetic walk, pugging subsequently, directly mediate in mortar owing to pug is less in the laboratory, and suitability for industrialized production needs to practice 3-10 time in vacuum deairing machine.
Old technology, traditional old processing requirement time is longer, generally takes 3-7 days, and the pug that the present invention will perfect mud is put in the encapsulation bag that keeps relative humidity 80-90%, so only needs get final product in 24-36 hour.
Extrusion process adopts the conventional vacuum extrusion machine, extrudes the ceramic supporting body base substrate of different shape and specification.Wherein at the squeezing passage number during greater than 35 tubular type supporter even cellular supporter, the viscosity of pug, humidity requirement are very high, and it is fine to extrude effect by this experimental formula.
Drying process be 60-100 ℃ the degree environment under dry 15-30 hour, remove combination water and water of constitution in the base substrate.
In binder removal, the sintering process, because the used caking agent of the present invention is less, binder removal, sintering carry out in same stove, whole temperature control curve such as Fig. 2.Wherein be provided with special temperature reduction technology in the sintering later stage, the yield rate of supporter is improved very big contribution.Binder removal, sintering process temperature are arranged on the 20-140 degree, heat-up rate be the 3-6 degree/minute; At the 140-600 degree, heat-up rate is 20-40 degree/time; Spend sintering temperature 600, heat-up rate be the 3-6 degree/minute.Be incubated 1-3 hour subsequently.Again with 3-6 degree/minute drop to 800 degree, furnace cooling to 200 degree again, blow-on door air is as cold as sampling about 80 degree.Rate of temperature fall considers from sintering temperature and begins cooling that it is very fast to lower the temperature, and may crack etc.Below 800 degree, actual cooling rate is also slower than the rate of temperature fall of setting, promptly furnace cooling just, below 200 degree, it is very slow lower the temperature, if still cold with stove, need for a long time.Experiment showed, no any crackle behind binder removal, the sintering.
Supporter product correlated performance is measured, and the present invention has designed the simple acid and alkali corrosion performance measurement scheme of using.Raw material is the supporter by three kinds of colloidal sols preparations of interpolation, and etching reagent is nitric acid, the sodium hydroxide of 5mol/L, the water bath with thermostatic control of 5mol/L, deionized water, precise electronic balance.Get each sample of same size, the precise electronic balance claims quality, and constant temperature corroded 24 hours for 90 ℃ in acid, alkali respectively, take out counter sample, use deionized water rinsing, boiled 2 hours with deionized water again, dry under 150 ℃, weigh the calculated mass rate of loss respectively.Formula is: x=(m
0-m
f)/m
0Wherein x is the porous supporting body mass loss rate; m
0, m
fBe respectively the quality of supporter corrosion front and back.
The present invention finds that to burning till product its hot strength of temperature range build-in test of 1000-1200 ℃ intensity is basic consistent with room temperature.
Embodiment 1---and the aluminium Sol A prepares the porous alumina supporter as auxiliary agent:
(1) with 30 microns α-Al
2O
3Micro mist is weighed as aggregate, and with α-Al
2O
3The quality of micro mist is the basis, adds binding agent HPMC6%, softening agent polyoxyethylene glycol (6000) 8%, dispersion agent sodium stearate 2%, pore-forming material W-Gum 4%, does not add ball with planetary ball mill and does mixed 3 hours.
(2) with aggregate α-Al
2O
3The quality of micro mist is the basis, and adding 10% aluminium Sol A and water are made pug in doing mixed uniform compound.
(3) in vacuum deairing machine pugging 5-10 time; The pug of perfecting mud was encapsulated in the encapsulation bag of relative humidity 80-90% old 24 hours.19 passages (28-32 centimetres of external diameters, 3.5-4.0 centimetres of channel diameters, conduit wall aperture 5-15 micron) of long 100 centimetres of extrusion moulding, 50 centimetre of 37 passage (40 centimetres of external diameters, 3.6 centimetres of channel diameters, 10 microns in conduit wall aperture) tubular support and the cellular supporter blank of 20 centimetre of 225 passage (36 centimetres of external diameters, 2 centimetres of channel diameters, 10 microns in conduit wall aperture) are some in the conventional vacuum extrusion machine.
(4) on the zirconium white plate, evenly be covered with 20 microns of one decks, 40 microns α-Al
2O
3Powder, with dried even green body be placed on the zirconium white plate, binder removal burns till in sintering oven.The binder removal sintering temperature is provided with: at the 20-140 degree, heat-up rate be 6 degree/; At the 140-600 degree, heat-up rate was 40 degree/times; Spend to 1550 ℃ of temperature 600, heat-up rate be 6 the degree/minute.Be incubated 2 hours subsequently.Again with 6 degree/minute drop to, 800 degree, furnace cooling to 200 degree again, blow-on door air is as cold as sampling about 80 ℃.
(the room temperature three-point bending strength, 24 hours mass loss rates of sodium hydroxide corrosion of 24 hours mass loss rates of the nitric acid of void content, high temperature (1200 ℃) three-point bending strength, shrinking percentage, 5mol/L corrosion and 5mol/L see attached list 1 to correlated performance
Embodiment 2---and the aluminium sol B prepares the porous alumina supporter as auxiliary agent:
(1) with 20 microns α-Al
2O
3Micro mist is weighed as aggregate, and with α-Al
2O
3The quality of micro mist is the basis, adds binding agent HPMC8%, softening agent polyoxyethylene glycol (6000) 6%, dispersion agent sodium stearate 4%, pore-forming material W-Gum 6%, does not add ball with planetary ball mill and does mixed 2 hours.
(2) with aggregate α-Al
2O
3The quality of micro mist is the basis, and adding 20% aluminium Sol A and water are made pug in doing mixed uniform compound.
(3) in vacuum deairing machine pugging 5-10 time; The pug of perfecting mud was encapsulated in the encapsulation bag of relative humidity 80-90% old 24 hours.19 passages (28-32 centimetres of external diameters, 3.5-4.0 centimetres of channel diameters, conduit wall aperture 5-15 micron) of long 100 centimetres of extrusion moulding, 50 centimetre of 37 passage (40 centimetres of external diameters, 3.6 centimetres of channel diameters, 10 microns in conduit wall aperture) tubular support and the cellular supporter blank of 20 centimetre of 225 passage (36 centimetres of external diameters, 2 centimetres of channel diameters, 10 microns in conduit wall aperture) are some in the conventional vacuum extrusion machine.
(4) on the zirconium white plate, evenly be covered with 20 microns of one decks, 40 microns α-Al
2O
3Powder, with dried even green body be placed on the zirconium white plate, binder removal burns till in sintering oven.The binder removal sintering temperature is provided with: at the 20-140 degree, heat-up rate be 3 degree/; At the 140-600 degree, heat-up rate was 20 degree/times; Spend to 1500 ℃ of temperature 600, heat-up rate be 3 the degree/minute.Be incubated 1 hour subsequently.Again with 4 degree/minute drop to, 800 degree, furnace cooling to 200 degree again, blow-on door air is as cold as sampling about 80 ℃.
(the room temperature three-point bending strength, 24 hours mass loss rates of sodium hydroxide corrosion of 24 hours mass loss rates of the nitric acid of void content, high temperature (1200 ℃) three-point bending strength, shrinking percentage, 5mol/L corrosion and 5mol/L see attached list 1 to correlated performance
Table 1 adds aluminium colloidal sol and prepares porous alumina supporter performance as auxiliary agent
| Sample model (passage) | Aluminium colloidal sol kind | Sintering temperature (℃) | Room temperature three-point bending strength (Mpa) | Void content (%) | High temperature three-point bending strength (Mpa) | Diameter shrinking percentage (%) | 24 hours mass loss rates (%) of nitric acid corrosion of 5mol/L | 24 hours mass loss rates (%) of sodium hydroxide corrosion of 5mol/L |
| 19 | A | 1550 | 57.246 | 45.999 | 56.046 | 9.438 | 0.12 | 0.14 |
| 19 | B | 1550 | 62.648 | 40.862 | 62.589 | 10.268 | 0.11 | 0.15 |
| 37 | A | 1550 | 64.125 | 45.242 | 63.368 | 11.575 | 0.12 | 0.16 |
| 37 | B | 1550 | 60.245 | 48.696 | 59.281 | 11.523 | 0.14 | 0.24 |
| 225 | A | 1550 | 54.125 | 45.242 | 53.368 | 11.775 | 0.12 | 0.16 |
| 225 | B | 1550 | 50.245 | 48.394 | 49.281 | 11.623 | 0.13 | 0.26 |
(1) with 40 microns α-Al
2O
3Micro mist is weighed as aggregate, and with α-Al
2O
3The quality of micro mist is the basis, adds binding agent HPMC5%, softening agent polyoxyethylene glycol (6000) 2%, dispersion agent sodium stearate 1.0%, pore-forming material W-Gum 5%, does not add ball with planetary ball mill and does mixed 2 hours.
(2) with aggregate α-Al
2O
3The quality of micro mist is the basis, and adding 30% self-control titanium colloidal sol and water are made pug in doing mixed uniform compound.
(3) in vacuum deairing machine pugging 5-10 time; The pug of perfecting mud was encapsulated in the encapsulation bag of relative humidity 80-90% old 24 hours.19 passages (28-32 centimetres of external diameters, 3.5-4.0 centimetres of channel diameters, conduit wall aperture 5-15 micron) of long 100 centimetres of extrusion moulding, 50 centimetre of 37 passage (40 centimetres of external diameters, 3.6 centimetres of channel diameters, 10 microns in conduit wall aperture) tubular support and the cellular supporter blank of 20 centimetre of 225 passage (36 centimetres of external diameters, 2 centimetres of channel diameters, 10 microns in conduit wall aperture) are some in the conventional vacuum extrusion machine.
(4) on the zirconium white plate, evenly be covered with 20 microns of one decks, 40 microns α-Al
2O
3Powder, with dried even green body be placed on the zirconium white plate, binder removal burns till in sintering oven.The binder removal sintering temperature is provided with: at the 20-140 degree, heat-up rate be 5 degree/; At the 140-600 degree, heat-up rate was 30 degree/times; Spend to 1450 ℃ of temperature 600, heat-up rate be 5 the degree/minute.Be incubated 3 hours subsequently.Again with 5 degree/minute drop to, 800 degree, furnace cooling to 200 degree again, blow-on door air is as cold as sampling about 80 ℃.
(the room temperature three-point bending strength, 24 hours mass loss rates of sodium hydroxide corrosion of 24 hours mass loss rates of the nitric acid of void content, high temperature (1100 ℃) three-point bending strength, shrinking percentage, 5mol/L corrosion and 5mol/L see attached list 2 to correlated performance
Table 2 adds titanium colloidal sol and prepares porous alumina supporter performance as auxiliary agent
| Sample model (port number) | Sintering temperature (℃) | Room temperature three-point bending strength (Mpa) | Void content (%) | High temperature three-point bending strength (Mpa) | Diameter shrinking percentage (%) | 24 hours mass loss rates (%) of nitric acid corrosion of 5mol/L | 24 hours mass loss rates (%) of sodium hydroxide corrosion of 5mol/L |
| 19 | 1450 | 56.357 | 43.458 | 54.292 | 17.191 | 0.26 | 0.31 |
| 37 | 1450 | 54.357 | 42.458 | 51.292 | 17.191 | 0.24 | 0.29 |
| 225 | 1450 | 49.357 | 43.458 | 45.292 | 17.191 | 0.25 | 0.32 |
Embodiment 4---and silicon sol prepares the porous alumina supporter as auxiliary agent:
(1) with 35 microns α-Al
2O
3Micro mist is weighed as aggregate, and with α-Al
2O
3The quality of micro mist is the basis, adds binding agent HPMC10%, softening agent polyvinyl alcohol 4%, dispersion agent sodium stearate 0.5%, pore-forming material W-Gum 5%, does not add ball with planetary ball mill and does mixed 1 hour.
(2) with aggregate α-Al
2O
3The quality of micro mist is the basis, and adding 40% silicon sol and water are made pug in doing mixed uniform compound.Silicon sol adopts commercially available silicon sol, and its siliconoxide mass percentage composition is 20%, and median size is 15 nanometers.
(3) in vacuum deairing machine pugging 5-10 time; The pug of perfecting mud was encapsulated in the encapsulation bag of relative humidity 80-90% old 24 hours.19 passages (28-32 centimetres of external diameters, 3.5-4.0 centimetres of channel diameters, conduit wall aperture 5-15 micron) of long 100 centimetres of extrusion moulding, 50 centimetre of 37 passage (40 centimetres of external diameters, 3.6 centimetres of channel diameters, 10 microns in conduit wall aperture) tubular support and the cellular supporter blank of 20 centimetre of 225 passage (36 centimetres of external diameters, 2 centimetres of channel diameters, 10 microns in conduit wall aperture) are some in the conventional vacuum extrusion machine.
(4) on the zirconium white plate, evenly be covered with 20 microns of one decks, 40 microns α-Al
2O
3Powder, with dried even green body be placed on the zirconium white plate, binder removal burns till in sintering oven.The binder removal sintering temperature is provided with: at the 20-140 degree, heat-up rate be 3 degree/; At the 140-600 degree, heat-up rate was 30 degree/times; Spend to 1350 ℃ of temperature 600, heat-up rate be 5 the degree/minute.Be incubated 3 hours subsequently.Again with 5 degree/minute drop to, 800 degree, furnace cooling to 200 degree again, blow-on door air is as cold as sampling about 80 ℃.
(the room temperature three-point bending strength, 24 hours mass loss rates of sodium hydroxide corrosion of 24 hours mass loss rates of the nitric acid of void content, high temperature (1000 ℃) three-point bending strength, shrinking percentage, 5mol/L corrosion and 5mol/L see attached list 3 to correlated performance
Table 3 adds silicon sol and prepares porous alumina supporter performance as auxiliary agent
| Sample model (passage) | Sintering temperature (℃) | Room temperature three-point bending strength (Mpa) | Void content (%) | High temperature three-point bending strength (Mpa) | Diameter shrinking percentage (%) | 24 hours mass loss rates (%) of nitric acid corrosion of 5mol/L | 24 hours mass loss rates (%) of sodium hydroxide corrosion of 5mol/L |
| 19 | 1350 | 54.0125 | 59.341 | 53.452 | 7.424 | 0.35 | 0.58 |
| 37 | 1350 | 52.0125 | 57.641 | 52.052 | 7.723 | 0.31 | 0.52 |
| 225 | 1350 | 50.0125 | 55.361 | 50.041 | 7.428 | 0.32 | 0.49 |
Can find out in table 1, table 2, the table 3: the porous alumina supporter according to the present invention's preparation not only satisfies general requirement, and its hot strength and acid-alkali-corrosive-resisting performance are significantly improved, the product of traditional technology preparation can reduce half in intensity more than 1000-1200 ℃, and the acid and alkali corrosion mass loss rate of equal conditions is 3-5%.
Claims (8)
1, a kind of colloidal sol prepares the method for porous alumina ceramic supporting body as auxiliary agent, it is characterized in that, comprises the steps:
(1) with α-Al
2O
3Micro mist is weighed as aggregate, and with α-Al
2O
3The quality of micro mist is the basis, the starch pore-forming material that adds the stearic acid dispersion agent of polyalcohols softening agent, 0.5-4% of cellulosic binder, the 2-8% of 5-10% and 2-6% is dried be mixed even;
(2) with aggregate α-Al
2O
3The quality of micro mist is the basis, and a kind of and water that adds 10-40% silicon sol, aluminium colloidal sol, titanium colloidal sol in doing mixed uniform compound is made pug;
(3) through vacuum pugging, old 24-36 hour, in the conventional vacuum extrusion machine extrusion moulding porous alumina ceramic supporting body blank, and dry;
(4) dried porous alumina ceramic supporting body blank is carried out binder removal and sintering process is made porous alumina ceramic supporting body, sintering temperature 1350-1550 ℃.
2, colloidal sol according to claim 1 prepares the method for porous alumina ceramic supporting body as auxiliary agent, it is characterized in that described cellulosic binder is a Vltra tears; Described polyalcohols softening agent is polyoxyethylene glycol or polyvinyl alcohol; Described stearic acid dispersion agent is a sodium stearate; The median size of described starch pore-forming material is less than aggregate α-Al
2O
3The median size of micro mist.
3, colloidal sol according to claim 1 prepares the method for porous alumina ceramic supporting body as auxiliary agent, it is characterized in that, described silicon sol adopts commercially available finished product Si (OH)
4Colloidal sol, its siliconoxide mass percentage composition is 20%, median size is 15 nanometers; Described aluminium colloidal sol adopts aluminium powder, and nitric acid, ammoniacal liquor are prepared from or adopt aluminium powder, and the aluminum oxide quality percentage concentration that hydrochloric acid, Aluminium chloride hexahydrate are prepared from is 20%, and particle diameter is the Al (OH) of 20-25 nanometers
4Colloidal sol; Described titanium colloidal sol adopts the titanium salt titanium oxide mass percentage concentration that hydrolysis is prepared under pH value 2-4 to be 15%, crystal formation is anatase octahedrite or rutile, median size are the Ti (OH) of 15 nanometers
4Colloidal sol.
4, colloidal sol according to claim 3 prepares the method for porous alumina ceramic supporting body as auxiliary agent, it is characterized in that the preparation method of described aluminium colloidal sol is: AlCl
36H
2O and hydrochloric acid reaction generate Al (OH)
3Precipitation, aluminium powder are as the supplement of aluminium, and the magnetic agitation that process is 70-80 ℃ 6 hours obtains transparent gluey Al (OH)
4Colloidal sol, wherein each reactant ratio is: the mol ratio of hydrochloric acid and water is 0.21, aluminium powder and AlCl
36H
2The mol ratio of O is 1.76; PH value in the reaction process is 3-5.
5, colloidal sol according to claim 3 prepares the method for porous alumina ceramic supporting body as auxiliary agent, it is characterized in that, the preparation method of described aluminium colloidal sol is: the 8g/L fine aluminium is added in the salpeter solution of people lmol/L, magnetic agitation 1h in the water-bath, cooled and filtered, filtrate is concentrated into 1/3 of original solution volume, stand-by as the fine aluminium treatment solution; 1mol/L ammoniacal liquor is heated to 75 ℃, slowly join the fine aluminium treatment solution in the ammoniacal liquor, make ammoniacal liquor and fine aluminium treatment solution ratio remain on 75 ℃ for the 1.5:1. temperature, after liquid feeding finishes, the salpeter solution that adds 1mol/L, making salpeter solution and fine aluminium treatment solution ratio is 0.5:1, continues the stirred in water bath 6-12h at 75 ℃, finally obtains transparent gluey Al (OH)
4Colloidal sol.
6, colloidal sol according to claim 3 prepares the method for porous alumina ceramic supporting body as auxiliary agent, it is characterized in that, the preparation method of described titanium colloidal sol is: titanium sulfate is added water stir into the salts solution that concentration is 1.0mol/L, press the volumetric molar concentration of 0.02mol/L and add MAP as tensio-active agent, be mixed with mixing solutions, stirring heating is 4 hours under magnetic stirrer, control reaction temperature is 75 ℃, pH value 2-4 by dropping ammonia and nitric acid control reaction, obtain colloidal liquid, i.e. Ti (OH)
4Colloidal sol.
7, colloidal sol according to claim 3 prepares the method for porous alumina ceramic supporting body as auxiliary agent, it is characterized in that described aggregate α-Al
2O
3Micro mist particle diameter between the 20-80 micron.
8, colloidal sol according to claim 1 prepares the method for porous alumina ceramic supporting body as auxiliary agent, it is characterized in that, described binder removal, sintering process, concrete processing parameter is as follows: at the 20-140 degree, heat-up rate be the 3-6 degree/minute; At the 140-600 degree, heat-up rate is 20-40 degree/time; Spend sintering temperature 600, heat-up rate be the 3-6 degree/minute; After sintering temperature, be incubated 1-3 hour; Then with 3-6 degree/minute drop to 800 degree, furnace cooling to 200 degree again, blow-on door air is as cold as sampling about 80 degree.
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