CN102471158A - Porous ceramic material having a macroporosity controlled by layering pore-forming agents - Google Patents
Porous ceramic material having a macroporosity controlled by layering pore-forming agents Download PDFInfo
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- CN102471158A CN102471158A CN201080034581.0A CN201080034581A CN102471158A CN 102471158 A CN102471158 A CN 102471158A CN 201080034581 A CN201080034581 A CN 201080034581A CN 102471158 A CN102471158 A CN 102471158A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/18—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mixtures of the silica-lime type
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28085—Pore diameter being more than 50 nm, i.e. macropores
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28095—Shape or type of pores, voids, channels, ducts
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0051—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity
- C04B38/0064—Multimodal pore size distribution
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C11/00—Use of gas-solvents or gas-sorbents in vessels
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C11/00—Use of gas-solvents or gas-sorbents in vessels
- F17C11/002—Use of gas-solvents or gas-sorbents in vessels for acetylene
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00948—Uses not provided for elsewhere in C04B2111/00 for the fabrication of containers
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Abstract
The invention relates to a porous ceramic material, including: a microstructure including a material with a crystalline xonotlite and/or tobermorite structure, said material being crystallized in the form of needles connected to each other so as to provide therebetween a pore diameter D95 that is greater than or equal to 0.4 [mu]m and less than 5 [mu]m, and a mean pore diameter D50 that is greater than or equal to 0.4 [mu]m and less than 1.5 [mu]m, preferably 0.4 to l [mu]m; and a macrostructure consisting of a continuous and/or discontinuous layering of macropores.
Description
Theme of the present invention is novel porous stupalith, makes the method for this type material, contains the container of this type material and the purposes that this container is used for store fluid (for example gas and/or liquid).
Known in various uses, the use held the pressurizing vessel that is dissolved in the gas (for example acetylene) in the solvent (for example acetone or DMF), is particularly useful for combining to weld with oxygen cylinder, soldering and heating operation.
These containers are lined with the solid packing that is used to stablize the gas that they hold usually, and they are thermodynamic instability under the effect of pressure and/or temperature variation, therefore in its storage, transportation and/or transport process, is prone to decompose.
These materials must have sufficient porosity, with the absorption and the release of the gas that promotes to hold in the container.They also must be not flammable, and these gases are inertia and have good mechanical strength.These materials are made up of the calcareous pottery of porous silicon usually; It is for example obtained by unslaked lime or milk of lime and the uniform mixture of silicon-dioxide (especially silica powder form) in water described in document WO-A-93/16011, WO-A-98/29682 and EP-A-262031; To form thickener, to stand hydro-thermal synthetic for this thickener then.Particularly; Under partial vacuum, this thickener is introduced the container of wanting lining; Under certain pressure and temperature, said container is pressed heat operation then, in stove, cure then, to remove the Ca that consists of that anhydrates and form crystalline structure fully with tobermorite and xonotlite type
xSi
yO
zWH
2The integrated solid material of O wherein maybe remaining quartz.Can various additives be added in these mixtures of prior art,, and avoid being formed on observed structural inhomogeneity and shrinkage phenomenon in the porous insert process of setting thus with the dispersion of improvement lime and silicon-dioxide.In fact the gained filler must have even porosity and not have dead zone (bubble possibly accumulate in the dead zone and have explosion hazard).
Document EP-A-264550 also points out, contain by weight at least 50% or at least 65% or even the porous insert of at least 75% crystallization phases (with respect to the weight of Calucium Silicate powder) can satisfy compressive strength and hydro-thermal synthetic with stoving temperature under these two requirements of anti-contracility.
Although it is satisfactory that known porous insert is seen usually from the angle of their physical strength, the fact is that still filling, recovery, discharge and filtration time are still long.
This be because; According to operational conditions (gas vol that holds in use temperature, working flow rate, the bottle etc.), these known materials are not in the required time whole process of some purposes (especially welding), to extract the gas that they hold with the maximum gas recovery (ratio that is equivalent to available gas vol and the initial gas vol that stores) continuously with high flow rate.Now; For 1 liter, preferred 3 to 10 liters minimum water volume; When hope can be as far as on-test 50% or the peak flow rate of higher gas volume (gas volume is meant gas vol that this moment exists and the ratio that is loaded into the gas vol in the container at first) satisfy continuous 200 liters/hour flow velocity 15 minutes and 400 liters/hour 4 minutes; This container has 0.2 to 0.7, preferred 0.35 to 0.5 diameter/length ratio.
This deficiency is especially owing to the high pressure drop that is caused by microstructure.This microstructure is by the microporosity formation that (this material void distribution in this case) forms of piling up through silico-calcium matter spicule, and said silico-calcium matter spicule is mainly formed by other phase (foshagite, riversideite etc.) of xonotlite and/or tobermorite and/or CSH type.Term " CHS " is understood that to be meant lime/water/silica ratio.Free space between the spicule forms 60 to 95% percentage of open area that do not wait thus.In document EP 1887275 and EP 1886982, this microstructure has been described especially.High pressure drop is owing to very little pore size (0.1 micron to 1 micron) and their very narrow volume void distribution (accurate single mode type).Pore size is understood that to be meant by what the spicule that mainly is xonotlite caused and on average piles up.
Therefore, a problem of appearance provides ceramic porous material, and wherein pressure drop is limited to improve gas and/or the liquid diffusion in this porous material.This for example can reclaim the liquid or the gas content of storage quickly and still keep gratifying SF.
A solution of the present invention is a ceramic porous material, and it comprises:
-microstructure, this microstructure comprise the material with interconnective spicule form crystalline xonotlite and/or tobermorite crystalline structure, are equal to or greater than 0.4 micron but less than 5 micron pore size D thereby between them, provide
95Be equal to or greater than 0.4 micron but less than 1.5 microns, preferred 0.4 to 1 micron mean pore size D
50With
-the nacrostructure that forms by the continuous and/or discontinuous stacked body of macropore.
Term " macropore " is meant that diameter is 10 to 2000 microns a hole.The shape of these macropores can be sphere, ellipse, rod etc.
Term " microstructure " is meant the microtexture of material.
Term " nacrostructure " is meant the structure of material.In this article, no matter this structure is that to interconnect also be the big well format of non-interconnection, can both be formed for making the continuous or discrete preferred path of fluid at this microstructure internal diffusion.
The diagram of Fig. 1 on the left is used for the acicular thing microstructure of the ceramic porous article of gas and/or fluid storage, diagram microstructure on the right-nacrostructure combination (constituting at this stacked body by " rod " hole).
Aperture D
95Be equivalent to following diameter: the hole of 95 volume % has the diameter less than 5 microns.
Mean pore size D
50Be equivalent to following diameter: the hole of 50 volume % has the diameter less than 1.5 microns.
Xonotlite is the formula Ca with the repeating unit that is made up of three tetrahedrons
6Si
6O
17(OH)
2Calucium Silicate powder.In addition, tobermorite also is a Calucium Silicate powder, has formula Ca
5Si
6(O, OH)
185H
2O is with the crystallization of orthorhombic form.
Water as the situation of solvent under with about 1 CaO/SiO
2Mol ratio is by CaO and SiO
2The most generally acknowledged mechanism that precursor forms xonotlite is following:
CaO/SiO
2/ H
2O → Ca (OH)
2/ SiO
2/ H
2O → CSH gel → tobermorite → xonotlite
Preferably, intermediate phase accounts for 0 to 10% of the crystallization phases weight that exists in this porous material altogether, and more preferably 0 to 5%.
Preferably, lime carbonate and silicon-dioxide account for separately these final crystallization phases gross weights less than 3%.
Use this structure of porous material enable of the stacked body form of intermeshing spicule to have and be used for stablizing gas dissolved and/or the used required character of solvent of liquid; And can limit its decomposition in the unlimited micro-space through said gas and/or liquid are limited to; Guarantee the security and the conformance with standard test of container thus, for example ISO 3807-1 standard.
Preferably, interconnection or non-interconnection macropore have the diameter greater than 10 microns.
The macrovoid of ceramic porous article piles up owing to pore former, and the continuity of this network or discontinuity are owing to the interconnection of said pore former, and the volume content and the shape of said pore former depended in this interconnection.The advantage of this technology is that it can be according to the pore former that is used for this manufacturing (or mixture of pore former), and promptly its raw material is stuck with paste content and the geometrical shape thereof in (preparation), changes the nacrostructure of porous insert.
The shape and size of hole directly depend on initial pore former.Term " initial pore former " is meant natural carbon compound (starch, yam starch etc.) or synthetic carbon cpd (PMMA, PS etc.).This continuous and/or discontinuous stacked body depends on the initial content of pore former in the raw material preparation.Common sense be, if this content less than 35 volume % of solid material volume, this interconnection mainly is discontinuous.Be higher than this value, nacrostructure is considered to successive.
According to circumstances, porous material can have one or more following characteristics:
-nacrostructure is formed by 10 microns to 10 millimeters of diameters, preferred 10 microns to 2 millimeters macropore;
-macropore has the geometrical shape of the combination of the sphere of being selected from, sheet shape, cylindrical, cubes or these shapes;
-said spicule has 2 to 10 microns, preferred 2 to 5 microns length, 0.010 to 0.25 micron width and less than 0.25 micron thickness; With
-said material contains the crystallization phases of at least 70 weight %, preferred at least 90 weight %.
In addition, this porous material also can comprise fiber, and this fiber is selected from the carbon back synthon; Special those as describing among the document US-A-3454362, alkali resistant glass fibre, those especially as describing among the document EP-A-262031; And their mixture, this is enumerated and is not limit.These fibers especially are used as strongthener to improve the shock strength of porous material, the cracking problem in the time of also avoiding this structure of drying.These fibers can use like this or use in the back, surface of handling them.
Ceramic porous material also can comprise dispersion agent or tackiness agent in its manufacturing processed (thickener formation); For example derivatived cellulose, particularly CMC 99.5, hydroxypropylcellulose or Type 3U, polyethers; Polyoxyethylene glycol for example; The synthesis of clay of smectite type, advantageously have an amorphous silica of 150 to 300 meters squared per gram specific surface areas, and their mixture, this is enumerated and is not limit.
Ceramic porous material also can contain the calcareous compound of initial silicon, for example wollastonite (CaSiO
3), it serves as nucleator (planting brilliant operation) so that the faster nucleation of tobermorite and/or xonotlite crystal.The content of nucleator is that 0.1 to 5 weight % of all solids precursor does not wait.
This ceramic porous material also can in its method of manufacture (thickener formation), contain phosphoric acid (less than the thickener TV that contains lime, silicon-dioxide and water 1%).
Preferably, porous material contains fiber, particularly carbon and/or glass and/or cellulosic fibre.Fibre weight is advantageously less than 55 weight % of all solids precursor used in the method for making porous material.It is preferably 3 to 20 weight %.
Preferably, porous material of the present invention has the 15kg/cm of being equal to or greater than
2, i.e. 1.5MPa is more preferably greater than 25kg/m
2, i.e. the compressive strength of 2.5MPa.Can measure compressive strength as follows: from porous material, get 100 * 100 square metres cubes, and when leaning against this material on the horizontal metal plate, on this cubical upper surface, apply force of compression.This power is equivalent to following pressure: be higher than this pressure, said material begins cracking.
In this article, in order to realize above-mentioned certain ceramics porous material, another theme of the present invention is a method of making porous material of the present invention, comprises the steps:
A) preparation is based on the step of the pasty mixture of quicklime, silicon-dioxide and excessive water.This mixture can also contain spun glass, organic cpds, nucleator and phosphoric acid;
B) introducing in the mixture of in step a), processing can be in the step of the mixture of 150 to 600 ℃ at least a pore former of temperature pyrolysated;
C) being raw material, in the step of the pore former stacked body ambient water thermal synthesis porous material of step b) from step a) and the mixture that comprises the pore former of step b);
D) drying is available from the step of the porous material of step c); With
E) through remove the step of pore former at the temperature combustion that is lower than 600 ℃.
Fig. 2 has shown each step of method of manufacture of the present invention.
Certainly, it should be understood that this method can comprise that these possibly be preparation, centre or additional step except that the step those mentioned above.
According to circumstances, method of manufacture of the present invention can have one or more following characteristics:
-step d) and e) merge;
-said pore former is a polymeric;
-said pore former is based on PVC, polymethylmethacrylate, PS, urethane, Vilaterm, plant (starch, yam starch, coconut etc.) fiber, thomel or these mixture of ingredients.Particularly, said pore former must be polymer-based carbon, carbon back or natural.
Pore former can have different forms: bead, fiber, tubercle, flap.
Select the size of pore former according to the required macroporosity that will obtain.Usually, it is 10 microns to 2 millimeters.
Second step (step b)) is the mixture that is preferably polymeric and/or natural carbon pore former introduced and comprises in the raw mix of silico-calcium matter precursor (lime, silicon-dioxide).Term " pore former " is meant and has controlled shape the combination of the junior unit of (spherical, fiber, etc.) and controlled size.It is many these unitary stacked bodies, and stacked body forms nacrostructure, and this nacrostructure will be used as anti-body to obtain macroporosity.
After incorporating the mixture of pore former into; Carry out third step (step c)); Its hydro-thermal that is that the lime-silica mixture (going into pore former to wherein having drawn) to step a) imposes under the temperature between about 170 ℃ to 300 ℃, preferred 180 to 220 ℃ is synthesized; According to the volume of a container of wanting lining, hydro-thermal is synthetic carried out 10 hours to 70 hours, for example the container with the volume of water that equals 6 liters was about 40 hours.
The 4th step (step d)) of this method or the function of drying step are not only and are removed residuary water, also make treated material have the crystalline of being mainly structure.This conventional electric furnace or the steam stove (can be used for the identical or different of hydro-thermal synthetic operation) of operating under atmospheric pressure carries out.
The 5th step (step e)) of this method is to remove pore former through burning.This removes and causes forming hole, and it helps liquid state or gaseous fluid at this microstructure internal diffusion.For this reason, porous material is heated to the temperature of ability burn off carbon pore-forming composition.This temperature must keep below 600 ℃, so that do not destroy initial microstructures.Step e) can combine with drying step.Remove after the pore former mixture, in this ceramic porous material, obtain the corresponding continuous and/or discontinuous stacked body of shape with initial pore former.Therefore, according to the present invention, macroporosity combines with microporosity, is formed by two types holes (being micropore and macropore).
Fig. 3 on the left shows the full figure of porous material of the present invention, shows the enlarged view of identical porous material on the right.Can find out the nacrostructure that forms by the interconnection macropore that is of a size of 0.1 to 0.2 millimeter in the figure.
Fig. 4 has shown four Photomicrographs, very accurately shows the interconnection macropore.Photomicrograph is to use Zeiss Ultra 55FE-SEM (field emission scanning electron microscope) to obtain through EM.
Fig. 4 on the left has shown two Photomicrographs (is full figure, and another is an enlarged view), shows the porous material (promptly not having interconnected pores) according to prior art; Show two Photomicrographs (is full figure, and another is an enlarged view) on the right, showed porous material of the present invention (promptly containing the interconnection macropore).
In some zone of cavity, possibly observe the passage aisle (being of a size of the 5-10 micron) that outgas that the burning by pore former in the drying step process causes forms.These passages help total perviousness of this material.Fig. 5 diagram these outgas passages.
Theme of the present invention also is the container that contains aforesaid porous material, and this container can hold and conveyance fluid.
This container is can be on its outer wall heat insulation and can hold and delivering cryogenic fluid.
This container comprises the metal shell that contains above-mentioned porous material usually.This metal shell can be made up of metallic substance, and steel for example for example meets the P265NB normalization carbon steel of NF EN 10120 standards, and its thickness can bear the withstand voltage pressure of at least 60 crust (6MPa)---hold the rules normal values of acetylene under these conditions.This container also is generally round shape, and has enclosed appts and pressure-regulator usually.This container preferably have 0.2 to 0.7, more preferably 0.35 to 0.5 diameter/length than and 1 liter minimum water volume.Usually, this container is the doleiform formula.
The fluid that is stored in the packaging structure of the present invention can be gas or liquid.
As gas; Can mention following these: the compression scrubbed gas or the gaseous mixture of gas or liquid form; For example hydrogen, hydrocarbon gas (alkane, alkynes and alkene), nitrogen and acetylene; With the gas that is dissolved in the solvent, for example be dissolved in acetylene and acetylene/ethene or acetylene/ethylene/propylene mixture in the solvent (for example acetone or N DMF).
As liquid, can mention especially following these: Organometallic precursor, for example Ga and In precursor particularly are used in the electronic unit; And soup.Also can mention all alcohol or alcohol mixture.
Especially, container of the present invention holds the acetylene that is dissolved in DMF or the acetone.
According to another possibility, this container is can be on its outer wall heat insulation and can hold and delivering cryogenic fluid, for example hydrogen, helium, oxygen or any other liquefied gas.
At last; Ceramic porous material of the present invention can reduce the effect (long filling, recovery and efflux time) that is caused by pressure drop; Because the structure of being arranged (nacrostructure) can make gas and solvent arrive porous insert sooner and fully equably, still keep microstructure simultaneously according to prior art.
For example, under the situation of the acetylene cylinder in being dissolved in acetone or DMF, the high pressure drop limited flow rate of existing porous material (no microchannel).This has following consequence:
-in filling process, prolonged the filling time: every bottle is average about 6 hours; With
-in discharge process, the restriction gas flow rate and the gas vol that can from bottle, reclaim: as far as 6 litre flasks, flow velocity be limited to 400 liters/hour about 40 minutes, recyclable gas vol be to export about 50% at every turn.
Ceramic porous material of the present invention with controlled macroporosity can alleviate these negative effects, still keeps gratifying SF simultaneously.
Claims (14)
1. ceramic porous material comprises:
-microstructure, this microstructure comprise the material with interconnective spicule form crystalline xonotlite and/or tobermorite crystalline structure, are equal to or greater than 0.4 micron but less than 5 micron pore size D thereby between them, provide
95Be equal to or greater than 0.4 micron but less than 1.5 microns, preferred 0.4 to 1 micron mean pore size D
50With
-the nacrostructure that forms by the continuous and/or discontinuous stacked body of macropore.
2. the porous material described in claim 1 is characterized in that said nacrostructure is formed by 10 microns to 10 millimeters of diameters, preferred 10 microns to 2 millimeters macropore.
3. the porous material described in claim 1 or 2 is characterized in that said macropore has the geometrical shape of the combination of the sphere of being selected from, sheet shape, cylindrical, cubes or these shapes.
4. the porous material described in one of claim 1 to 3, it is characterized in that said spicule have 2 to 10 microns, preferred 2 to 5 microns length, 0.010 to 0.25 micron width and less than 0.25 micron thickness.
5. the porous material described in one of claim 1 to 4 is characterized in that said material contains the crystallization phases of at least 70 weight %, preferred at least 90 weight %.
6. make method, it is characterized in that comprising following step like the ceramic porous material of claim 1 to 5 described in each:
A) preparation is based on the step of the pasty mixture of quicklime, silicon-dioxide and excessive water;
B) introducing in the mixture of in step a), processing can be in the step of the mixture of 150 to 600 ℃ at least a pore former of temperature pyrolysated;
C) be raw material from step a) and the mixture that comprises the pore former of step b), in the step of the pore former stacked body ambient water thermal synthesis porous material of step b);
D) drying is available from the step of the porous material of step c); With
E) through remove the step of pore former at the temperature combustion that is lower than 600 ℃.
7. the method for manufacture described in claim 6 is characterized in that step d) and e) merge.
8. the method described in claim 6 or 7 is characterized in that said pore former is a polymeric.
9. the method described in claim 6 or 7 is characterized in that said pore former is based on PVC, polymethylmethacrylate, PS, urethane, Vilaterm, vegetable fibre, thomel or these mixture of ingredients.
10. contain the container just like the porous material of claim 1 to 5 described in each, said container has the bottle shape that can hold with delivering liquid and/or gaseous fluid.
11. the container described in claim 10 is characterized in that it is equipped with the acetylene that is dissolved in solvent, particularly DMF or the acetone.
12. the container described in claim 10 is characterized in that it is heat insulation and can hold and delivering cryogenic fluid on its outer wall.
13. the container described in claim 10 or 11 or the purposes of the porous material described in one of claim 1 to 4 are used for storing acetylene.
14. the purposes of container described in claim 10 or the ceramic porous material described in one of claim 1 to 5 is used to store organic liquid.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0955510 | 2009-08-05 | ||
| FR0955510A FR2948884B1 (en) | 2009-08-05 | 2009-08-05 | POROUS CERAMIC MATERIAL HAVING POROGENIC STACK CONTROLLED MACROPOROSITY |
| PCT/FR2010/051506 WO2011015751A1 (en) | 2009-08-05 | 2010-07-19 | Porous ceramic material having a macroporosity controlled by layering pore-forming agents |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102471158A true CN102471158A (en) | 2012-05-23 |
Family
ID=42138953
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201080034581.0A Pending CN102471158A (en) | 2009-08-05 | 2010-07-19 | Porous ceramic material having a macroporosity controlled by layering pore-forming agents |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP2462077A1 (en) |
| CN (1) | CN102471158A (en) |
| BR (1) | BR112012007894A2 (en) |
| CA (1) | CA2767774A1 (en) |
| FR (1) | FR2948884B1 (en) |
| IN (1) | IN2012DN00925A (en) |
| MX (1) | MX2012001499A (en) |
| RU (1) | RU2012108078A (en) |
| WO (1) | WO2011015751A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104529523A (en) * | 2014-12-12 | 2015-04-22 | 盐城工学院 | Method for preparing oriented porous silicon nitride ceramics based on carbon fiber serving as pore forming agent |
| CN103322635B (en) * | 2012-10-12 | 2016-02-24 | 中国科学院广州能源研究所 | Accumulation type porous ceramic grain wets curtain |
| CN109719297A (en) * | 2019-01-31 | 2019-05-07 | 广东科技学院 | A kind of porous metal composite material and preparation method thereof |
| CN115626833A (en) * | 2015-02-27 | 2023-01-20 | 通用电气公司 | Ceramic matrix composite structures with controlled microstructure prepared with Chemical Vapor Infiltration (CVI) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2969186B1 (en) * | 2010-12-15 | 2014-01-10 | Saint Gobain Rech | PROCESS FOR PREPARING INSULATING MATERIAL |
| FR2977889B1 (en) | 2011-07-13 | 2014-01-10 | Saint Gobain Isover | HIGH PERFORMANCE THERMAL INSULATION MATERIALS |
| FR2977888B1 (en) | 2011-07-13 | 2014-01-10 | Saint Gobain Isover | THERMAL INSULATION MATERIALS HIGH PERFORMANCE. |
| FR2987620B1 (en) | 2012-03-05 | 2016-01-01 | Air Liquide | CONSTRUCTION BRICK COMPRISING A POROUS MATERIAL WHOSE MICROSTRUCTURE IS CONTROLLED BY ADDING A GERMINATING AGENT DURING ITS PROCESS OF PREPARATION |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1093084A (en) | 1965-03-16 | 1967-11-29 | Union Carbide Corp | Manufactured graphite yarn |
| JPS6021846A (en) * | 1983-07-12 | 1985-02-04 | 株式会社大阪パツキング製造所 | Lightweight calcium silicate formed body |
| FR2604102B1 (en) | 1986-09-18 | 1988-11-10 | Air Liquide | HIGH POROSITY SILICOCALCARY MASS FOR GAS STORAGE, AND MANUFACTURING METHOD |
| US4765458A (en) | 1986-10-14 | 1988-08-23 | Ni Industries, Inc. | Asbestos free hardened monolithic filler mass |
| JPH0631172B2 (en) * | 1986-10-15 | 1994-04-27 | 株式会社ノダ | Extruded product and manufacturing method thereof |
| IT1254430B (en) | 1992-02-11 | 1995-09-25 | Siad | "ASBESTOS FREE" POROUS MASS FOR ACETYLENE CYLINDERS. |
| YU48898B (en) | 1996-12-26 | 2002-10-18 | "Tehnogas"D.D. | Porous mass asbestos free intended for filling of cylinders for acetylene storaging and a method of production a porous mass |
| FR2792850B1 (en) * | 1999-04-29 | 2001-07-13 | Air Liquide | HIGH MACROPOROSITY ADSORBENT FOR USE IN A GAS ADSORPTION PROCESS, IN PARTICULAR A PSA PROCESS |
| FR2904240B1 (en) * | 2006-07-26 | 2008-12-05 | Air Liquide | TRAPPING STRUCTURE FOR GAS CONTAINER WITH CRYSTALLIZED MATERIAL IN THE FORM OF NEEDLES |
| FR2904239B1 (en) * | 2006-07-26 | 2008-12-05 | Air Liquide | CRYSTALLINE PHASE STRAPPING STRUCTURE OF GAS CONTAINERS |
-
2009
- 2009-08-05 FR FR0955510A patent/FR2948884B1/en not_active Expired - Fee Related
-
2010
- 2010-07-19 BR BR112012007894A patent/BR112012007894A2/en not_active Application Discontinuation
- 2010-07-19 WO PCT/FR2010/051506 patent/WO2011015751A1/en active Application Filing
- 2010-07-19 EP EP10752037A patent/EP2462077A1/en not_active Withdrawn
- 2010-07-19 CA CA2767774A patent/CA2767774A1/en not_active Abandoned
- 2010-07-19 CN CN201080034581.0A patent/CN102471158A/en active Pending
- 2010-07-19 MX MX2012001499A patent/MX2012001499A/en unknown
- 2010-07-19 IN IN925DEN2012 patent/IN2012DN00925A/en unknown
- 2010-07-19 RU RU2012108078/03A patent/RU2012108078A/en unknown
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103322635B (en) * | 2012-10-12 | 2016-02-24 | 中国科学院广州能源研究所 | Accumulation type porous ceramic grain wets curtain |
| CN104529523A (en) * | 2014-12-12 | 2015-04-22 | 盐城工学院 | Method for preparing oriented porous silicon nitride ceramics based on carbon fiber serving as pore forming agent |
| CN115626833A (en) * | 2015-02-27 | 2023-01-20 | 通用电气公司 | Ceramic matrix composite structures with controlled microstructure prepared with Chemical Vapor Infiltration (CVI) |
| CN109719297A (en) * | 2019-01-31 | 2019-05-07 | 广东科技学院 | A kind of porous metal composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| MX2012001499A (en) | 2012-10-15 |
| IN2012DN00925A (en) | 2015-04-03 |
| EP2462077A1 (en) | 2012-06-13 |
| BR112012007894A2 (en) | 2016-03-22 |
| FR2948884B1 (en) | 2012-06-01 |
| CA2767774A1 (en) | 2011-02-10 |
| RU2012108078A (en) | 2013-09-10 |
| FR2948884A1 (en) | 2011-02-11 |
| WO2011015751A1 (en) | 2011-02-10 |
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Application publication date: 20120523 |