CN102491326A - Device for drying supercritical fluid and method for preparing aerogel material - Google Patents
Device for drying supercritical fluid and method for preparing aerogel material Download PDFInfo
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Abstract
The invention provides a device for drying supercritical carbon dioxide. The device comprises a circulating carbon dioxide storage tank, a pressurizing pump, one or more drying kettles, one or more separating kettles, a reclaiming tank, a compressor pump and a condenser. The invention also provides a method for preparing an aerogel materials by using the device. The device disclosed by the invention has the advantages of high solvent separation efficiency, high drying speed, recyclable carbon dioxide and the like; furthermore, the device and the method disclosed by the invention can be used for preparing various aerogel materials in small scale or producing the same in large scale.
Description
Technical field
The present invention relates to be used for the apparatus and method of functional materials preparation, specifically, the present invention relates to a kind of supercritical co drying installation and adopt said device to make the method for aerogel material.
Background technology
Gas gel is known as " solid cigarette " again, is present the lightest known solid material.The lightweight that it is made up of nanometer colloid particle or high-polymer molecular, porousness condensed state solid material, its particle size belongs to the category of nano material between 1 to 100nm.Gas gel has unique open continuous poriferous random structure and three-dimensional network, has extremely low density, high-specific surface area and high porosity.Demonstrate peculiar property at aspects such as mechanics, acoustics, calorifics, optics, have extensively and great application prospect in various fields such as space flight, military affairs, communication, medical, building materials, electronics, metallurgy.
Aerogel material is applied in a lot of fields.As: patent CN1295496 has invented a kind of pure aluminium silicate-magnesium of IX or has fluoridized the Magnesium Silicate q-agent gas gel, and they are very suitable for the body that supports as 3-10 family metal complex catalyst, thereby is used for reactions such as olefinic polymerization, shortening; Patent CN1810356 discloses a kind of preparation highlight catalytic active gas gel TiO
2Method.This method makes alcogel through the mode of sol-gel, after aging, supercritical drying, calcination process, obtains the meticulous adjustable nanocrystalline gas gel TiO of microstructure character such as grain size, pore structure and crystal formation
2Block or powder.This invents obtained TiO
2Gas gel has than commercial P-25 photocatalyst up to nearly photocatalytic activity more than three times in WWT Application Areass such as nitrobenzene degradations; CN101376501 has reported a kind of preparation method of silica aerogel, and this film has low optical index and high hardness, can be used as light anti-reflection film material efficiently.CN101051566 has reported the preparation method of a kind of electrical condenser with carbon gas gel electrode material; This method is a reactant with Resorcinol and formaldehyde; Obtain charcoal-aero gel through collosol and gel-drying-Pintsch process, this material is a kind of high performance capacitor electrode material.In addition; Gas gel has important use in heat insulation field; Patent CN101041770, CN101913835A, CN1546312 etc. have all reported the preparation method of aerogel heat-insulating material; Related gas gel all adopts the sol-gel method preparation, and through fiber composite aerogel material mechanical property and use properties is improved, and in heat insulation field very big application prospect is arranged.
The supercritical fluid drying technology is to utilize supercutical fluid that the strong dissolving power of solute, high diffustivity are transferred to solute in the supercutical fluid, can solute separated out through decompression then.Supercritical fluid drying has many good characteristics, as: wide adaptability, efficient height, separation are simply; Surface tension is zero, can arrive deep hole that conventional solvent can't arrive etc.In various supercritical fluid drying technology, the application of supercritical co dry technology is the most extensive.It is main because supercritical co is nontoxic, do not burn, cheaply be easy to get, have moderate critical temperature and emergent pressure (31.06 ℃, 7.38MPa), environmental friendliness.
Many patent reports have been arranged and utilized supercritical drying to prepare the aerogel material technology, reported the SO that has photocatalysis performance with the preparation of Supercritical Ethanol desiccating method like CN1562478A
4 2-/ TiO
2Aerogel powder, CN1569737A have been reported with the preparation of Supercritical Ethanol desiccating method does not have the zinc-aluminium composite oxides aerogel powder of reuniting or reuniting less and having photoelectric properties.But, the temperature required and hypertonia of using in these two pieces of patents of Supercritical Ethanol has big dangerous.CN101863479A has reported and has a kind ofly carried out supercritical drying with high-pressure liquid medium (carbonic acid gas, alkane, alkene etc.) and prepare SiO
2The method of gas gel, this method raw material is easy to get, and technology is simple, but this method does not reclaim drying medium, and this is not suitable for scale operation.CN1139390A has reported a kind of method of using supercutical fluid to prepare aerogel particle and containing the antiperspirant of aerogel particle; This patent is described a cover ability high efficiency separation product in detail, is reclaimed the system of drying medium; But, this system is only applicable to the sample that raw material is pulpous state or flow-like.
This patent has been described a kind of dry method that prepare aerogel material of supercritical co that can realize different industrial scales (several milliliters to several kilolitres), the different mode of production (continuously or intermittent type), this method drying efficiency and carbon dioxide recovery efficient height, can produce the aerogel material of different size, profile, dissimilar (powder, block, fiber composite types etc.).
Summary of the invention
The present invention realizes through following technical scheme:
1. one kind is used for supercritical co exsiccant device, and wherein, said device comprises:
The circulate carbon dioxide storage tank;
The force (forcing) pump that is connected with the circulate carbon dioxide storage tank;
One or more the dry still that is connected with said circulate carbon dioxide storage tank fluid via said force (forcing) pump;
The one or more separating stills that are connected with said dry still fluid;
The withdrawing can that is connected with said separating still fluid;
The compression pump that is connected with said withdrawing can fluid; With
Via the condensing surface that said compression pump is connected with said withdrawing can fluid, said condensing surface also is connected with said circulate carbon dioxide storage tank fluid.
2, like technical scheme 1 described device, wherein, the quantity of said separating still is more than two, and adopts placed in-line mode fluid to be connected between said dry still and the said withdrawing can.
3, like technical scheme 1 or 2 described devices, wherein, the quantity of said dry still is more than two, and adopts parallel connection and/or placed in-line mode fluid to be connected between said circulate carbon dioxide storage tank and the said separating still.
4, like technical scheme 1 to 3 each described device, wherein, said dry still also directly is connected with said withdrawing can fluid.
5, like technical scheme 1 to 4 each described device, wherein, said separating still also directly is connected with said condensing surface fluid.
6. like technical scheme 1 to 5 each described device, wherein, said dry still, separating still and/or circulate carbon dioxide storage tank have temperature regulating device.
7, like technical scheme 1 to 6 each described device, wherein, the temperature of said dry still and/or separating still is controlled as 0 to 100 ℃, and the temperature of circulate carbon dioxide storage tank is controlled as 0 to 40 ℃.
8, like technical scheme 1 to 5 each described device, wherein, said device also comprises feed carbon dioxide storage tank and injection pump, and said feed carbon dioxide storage tank is connected with said circulate carbon dioxide storage tank fluid via said injection pump.
9, a kind of method of making gas gel, said method adopt carries out the supercritical co drying like technical scheme 1 to 8 each described device to wet gel.
Adopt technical scheme of the present invention, a kind of supercritical co exsiccant device that is used for can be provided, the material that adopts this device to make has the aerogel material of nano-scale pore structure, and industrial scale is adjustable, can realize continuous production.In addition, the present invention has the efficient height, carbonic acid gas can recycle, and can be used for the advantages such as block materials of large-scale industrial production aerogel powder material, various size, scale.
Description of drawings
To combine following accompanying drawing that the present invention is at length explained, in the accompanying drawings:
Fig. 1 be according to certain embodiments of the present invention be used for supercritical co exsiccant schematic representation of apparatus, comprising a dry still, a separating still.
Fig. 2 be according to certain embodiments of the present invention be used for supercritical co exsiccant schematic representation of apparatus, comprising two dry stills and with a separating still.
Fig. 3 be according to certain embodiments of the present invention be used for supercritical co exsiccant schematic representation of apparatus, comprising two dry stills and, two separating stills.
Fig. 4 be according to certain embodiments of the present invention be used for supercritical co exsiccant schematic representation of apparatus, comprising two dry stills and three separating stills, one of them separating still is equipped with solvent absorbent.
Embodiment
Describe illustrative embodiments of the present invention with reference to the accompanying drawings in detail.
Fig. 1 is the synoptic diagram that is used for supercritical co exsiccant device (hereinafter referred apparatus of the present invention) according to certain embodiments of the present invention; As shown in Figure 1; In embodiments more of the present invention; Apparatus of the present invention comprise circulate carbon dioxide storage tank 2, the force (forcing) pump B2 that is connected with circulate carbon dioxide storage tank 2; The dry still G1 that is connected with said circulate carbon dioxide storage tank 2 fluids via said force (forcing) pump B2; The separating still F1 that is connected with said dry still G1 fluid; The withdrawing can 3 that is connected with said separating still F1 fluid; The compression pump B3 that is connected with said withdrawing can fluid; With the condensing surface 4 that is connected with said withdrawing can 3 fluids via said compression pump B3, said condensing surface 4 also is connected with said circulate carbon dioxide storage tank 2 fluids.
In embodiments more of the present invention, apparatus of the present invention also comprise feed carbon dioxide storage tank 1 and injection pump B1, and said feed carbon dioxide storage tank 1 is connected with said circulate carbon dioxide storage tank 2 fluids through said injection pump B1.
According to preferred implementations more of the present invention, said dry still G1 further is connected with said withdrawing can 3.Like this, under the situation that the drying end needs, can the carbonic acid gas among the said dry still G1 be directly released in the withdrawing can, after reclaim through the pressurized carbon dioxide pump B3 that contracts.
According to certain embodiments of the present invention, said separating still F1 also directly is connected with said condensing surface 4 fluids.
According to certain embodiments of the present invention, said dry still G1, separating still F1 and/or circulate carbon dioxide storage tank 2 have temperature regulating device, so that control temperature wherein.
According to certain embodiments of the present invention, the temperature of said dry still G1 and/or separating still F1 is controlled as 0 to 100 ℃, and the temperature of circulate carbon dioxide storage tank 2 is controlled as 0 to 40 ℃.
Apparatus of the present invention can be provided with various valves in the circulation path, high pressure control valve for example, and in order to flowing of controlling flow style such as dioxide gas, these valves can be high-pressure valves, manual valve etc.For example optional is 1) between said force (forcing) pump 2 and said dry still G1, be provided with valve Y1; And/or 2) between said dry still G1 and said separating still F1, be provided with valve Y2; And/or 3) between said separating still F1 and said withdrawing can 3, be provided with valve Y4; And/or 5) between separating still F1 and condensing surface 4, valve Y5 is set.Thereby can control for example flowing of CO 2 fluid through valve Y1, Y2, Y3 and/or Y4.
In addition, all pressurized vessels (for example feed carbon dioxide storage tank 1, circulate carbon dioxide storage tank 2, dry still G1, separating still F1 and condensing surface 4 etc.) all can have independently exhaust-valve (not shown).All pressurized vessels all can have tensimeter, thermometer, and these instrument can show kettle temperature inside and pressure.Feed carbon dioxide storage tank, circulate carbon dioxide storage tank can also have carbonic acid gas volume table, and these volume tables can show the volume of Liquid carbon dioxide in the tank body.Inlet at dry still G1 all can be equipped with a mass flowmeter, and this under meter can show the flow of liquid carbon dioxide amount that gets into each dry still.
In addition, supercritical temperature, pressure need be set according to the difference of solvent total amount to be dried in the system, and basis of design is the phase diagram of multicomponent systems such as this solvent and carbonic acid gas.This phase diagram can or be carried out quantitative test through small-sized supercritical drying device according to document and obtained.For improving rate of drying, can adopt the pressure higher to produce than supercritical pressure.
In addition, each pressurized vessel and pump etc. can have the various safety attachments that meet design requirement.Dry still in apparatus of the present invention, separating still and/or circulate carbon dioxide storage tank can have independently temperature function.For realizing gas recycle process, comprise that the flow of each pump of injection pump, force (forcing) pump and compression pump is provided with each other with mating or sets according to concrete needs.
The present invention does not have special demonstration to the volume of each pressurized vessel, and for example the volume of circulate carbon dioxide gas reservoir 2 can be 2 to 3 times of volume of dry still G1; The volume of feed carbon dioxide storage tank 1 can be 2 to 3 times of volume of circulate carbon dioxide storage tank 2.
The present invention does not have special requirement to the pressure in the circulate carbon dioxide storage tank 2, temperature, and wherein pressure for example can be for 5 to 8MPa, and temperature is 0 to 40 ℃, is preferably 10 to 20 ℃, further is preferably 10 ℃.If temperature is too high, then need fully heating, if temperature is low excessively, then need in the downstream pressure container, heat.
The present invention has no particular limits the pressure and temperature among the dry still G1, and for example, pressure can be for 10 to 30MPa, and temperature is 50 to 60 ℃.
In addition, the present invention also has no particular limits the pressure and temperature of separating still F1, is that pressure is low more generally speaking, and separated from solvent is abundant more more soon.But be preferably 5 to 8Mpa, further be preferably 5 to 6MPa.Pressure is excessive, separate insufficient because carbonic acid gas is high to the solubleness of solvent when pressure is high.Pressure is too small, and the pressure difference between separating still and the dry still is excessive, then requires the separating still with excessive bulk.Temperature is preferably 20 to 40 ℃.
In addition, the pressure of condensing surface 4 of the present invention generally keeps basically identical with the pressure in the circulate carbon dioxide storage tank 2, and temperature for example can be controlled at 0 to 10 ℃ scope.
Adopt apparatus of the present invention to carry out the supercritical co exsiccant below in conjunction with preferred implementation explanations more of the present invention and use flow process, this flow process mainly comprises the steps:
(1) prepare before dry: in circulate carbon dioxide storage tank 2, inject Liquid carbon dioxide through injection pump B1 (seeing the empty frame part Fig. 1 for example) from feed carbon dioxide storage tank 1, the volume of the liquid carbon dioxide in circulate carbon dioxide storage tank 2 reaches for example 2 times of dry still TV for use; In embodiments more of the present invention, can there be said feed carbon dioxide storage tank 1 and injection pump B1 yet, but direct injecting carbon dioxide in the circulate carbon dioxide storage tank.
(2) in dry still G1, put into sample to be dried (for example wet gel): the temperature of the kettle of dry still G1 is controlled at for example 0 to 50 ℃, then sample to be dried is put into the kettle of dry still G1 (see figure 1);
(3) for example through open valve Y1; From circulate carbon dioxide storage tank 2, pass through force (forcing) pump B2 injecting carbon dioxide gas in the kettle of dry still G1; Carbonic acid gas for example can make dioxide gas heated earlier through having heating water jacket's pipeline (not shown) before getting into dry still G1.Gas temperature is controlled at for example 0 to 50 ℃;
(4) dioxide gas circulation, this round-robin mode has:
Recycle design 1: when the pressure in the dry still G1 reaches the supercritical pressure of setting,, make dioxide gas get into separating still F1 for example through opening the valve Y2 between dry still G1 and the separating still F1.When the pressure in the separating still F1 reaches setting pressure; Open the pressure regulator valve Y5 (this moment, valve Y3 and Y4 still closed) between separating still F1 and the condensing surface 4; Dioxide gas is condensed into liquid carbon dioxide in condensing surface 4 after; Get back to circulate carbon dioxide storage tank 2, thereby realize the circulation of dioxide gas between dry still G1, separating still F1, condensing surface 4 and circulate carbon dioxide storage tank 2.In this mode, the pressure in dry still G1, the separating still F1 is for example controlled through the flow of control pump B2 and the opening degree of each valve, and the pressure in the circulate carbon dioxide storage tank 2 is mainly by the interior gas temperature decision of for example this jar.Wherein, it is identical with the interior gaseous tension of circulate carbon dioxide storage tank 2 that the pressure Schwellenwert that can realize in the separating still F1 can be arranged to;
Recycle design 2: when dry still G1 internal pressure reaches the supercritical pressure of setting, for example through opening the valve Y2 between dry still G1 and the separating still F1; When separating still F1 internal pressure reaches setting pressure, for example through opening the valve Y4 (this moment, valve Y3 and Y5 closed) between separating still F1 and the withdrawing can 3.Dioxide gas in the entering withdrawing can 3 is compressed pump B3 and compresses back entering condensing surface 4 again; Gas is condensed into liquid carbon dioxide in condensing surface after; Get back in the circulate carbon dioxide storage tank 2, thereby realize the circulation of dioxide gas between dry still G1, separating still F1, withdrawing can 3, condensing surface 4 and circulate carbon dioxide storage tank 2.In this mode, separating still F1 internal pressure Schwellenwert can be reduced to normal atmosphere;
In Recycle design 2, through the operation force (forcing) pump, in dry still G1, inject through compressed carbon dioxide gas, the solvent that is dried out is separated in separating still.In separating still, can not separate solvent (for example no longer oozing solvent) again, can think that then the gas gel drying process accomplishes;
(5) after solvent seasoning process was accomplished, force (forcing) pump B2 was out of service.Begin to carry out the removal process of dioxide gas in the dry still G1.This process at first is for example to pass through shut-off valve Y1, Y3 and Y4, and the dioxide gas through pressurization in open valve Y2 and the Y5, dry still G1 comes back to circulate carbon dioxide storage tank 2 through separating still F1 and condensing surface 4 automatically.Up to dry still G1 internal pressure and circulate carbon dioxide storage tank F1 pressure quite after; For example through shut-off valve Y2, Y4, Y5; Open pump B3, valve Y3, dioxide gas begins to continue through withdrawing can 3, compression pump B3, condensing surface 4 and circulate carbon dioxide storage tank 2 removal process of residual carbon dioxide in the dry still G1 of realization in the dry still G1.This process will last till that dry still G1 internal pressure reaches till the minimum working pressure of the compression pump that withdrawing can connects, and subsequently, residual carbon dioxide can for example directly get final product through the exhaust-valve emptying in the dry still G1.When dry still G1 internal pressure is normal pressure, can opens dry still G1 and take out the sample that is dried.
More than described the embodiment that has only a dry still and a separating still, these embodiments are used to realize step drying process, and sample for example to be dried carries out drying in batches.
But; The present invention is to the not special restriction of the quantity of dry still and separating still; Can increase and decrease the quantity of dry still and/or separating still according to actual needs, thereby realize the for example lifting of throughput or the improvement of supercritical fluid drying, thereby improve the performance of prepared aerogel material.When for example comprising plural dry still, can realize the serialization production process.
Fig. 2 be according to certain embodiments of the present invention be used for supercritical co exsiccant schematic representation of apparatus, comprising two dry stills and a separating still.Fig. 3 be according to certain embodiments of the present invention be used for supercritical co exsiccant schematic representation of apparatus, comprising two dry stills and two separating stills.Fig. 4 be according to certain embodiments of the present invention be used for supercritical co exsiccant schematic representation of apparatus, comprising two dry stills and three separating stills, one of them separating still is equipped with solvent absorbent.
As shown in Figure 2, comprising two dry still G1, G2 and separating still F1.Two dry still G1, G2 can adopt parallel connection and/or placed in-line mode fluid to be connected between said circulate carbon dioxide storage tank and the said separating still.In addition, preferably flow to through valve control fluidic.
Under the situation that adopts the series system fluid to connect, can be for example the valve of import and export through controlling a plurality of dry stills realize carbonic acid gas separately through one of them dry still, then successively through other dry still.Under the situation that adopts the parallel way fluid to connect, can make gas get into dry still G1, G2 respectively.Under the situation that adopts parallel connection and series system, promptly on the basis of above parallel way, further the direct fluid of each dry still is connected.As shown in Figure 2, if for example shut-off valve Y6, Y7, Y8 and Y9, open valve Y10 can realize that then air-flow is only separately through dry still G2.Likewise, can realize in a similar fashion that also fluid is only separately through dry still G1.If valve-off Y7, Open valve Y6, Y10 can realize that then air-flow is in parallel through dry still G1, G2.If valve-off Y8, Y9, Y10 can realize that then air-flow successively passes through dry still G1, G2 with placed in-line mode.Therefore, through controlling the opening and closing of these valves, can realize the drying process of continous way.For example, in dry still G1, put into sample to be dried earlier, the control air-flow only passes through G1 earlier, and sample carries out exsiccant simultaneously in to G1, can in dry still G2, put into sample to be dried.When the sample in the still G1 to be dried can not separate solvent again, the air-flow with pump B2 injected dry still G2 at once, begins sample in the G2 is carried out drying.And can begin the dioxide gas in the dry still G1 is reclaimed this moment.After waiting to accomplish the interior dioxide gas recovery of dry still G1 and taking out the interior sample of G1, in dry still G1, put into other sample to be dried at once again.But implement device continuity production process like this.
In working cycle, get back to the content (need in the gel remove material) of solvent in the carbonic acid gas in the circulate carbon dioxide storage tank 2 for reduction, avoid these materials to product structure and Effect on Performance, can take following method:
(1) quantity (shown in Fig. 3 and 4) of increase separating still, these separating stills preferably adopt placed in-line mode fluid to be connected between said dry still and the said withdrawing can.Can realize the Recycle design of " dry still (can be a plurality of dry stills), a plurality of separating still, condensing surface, circulate carbon dioxide storage tank " in this way, and the Recycle design of " dry still (can be a plurality of dry stills), a plurality of separating still, withdrawing can, condensing surface and circulate carbon dioxide storage tank ".
(2) along the direction of air-flow, place in the end one or more separating stills can adsorption solvent material, such as molecular sieve etc., and regularly these materials are changed or activation (as shown in Figure 4), apparatus of the present invention comprise the separating still FX1 that solvent absorbent is housed.In the drying process, this still is last or a plurality of separating still of air-flow process, the little solvent that can adsorb the remnants that all the other separating stills are not separated in the gas circuit of the upper reaches.After treating that the solvent absorbent absorption is saturated,, cut off the gas circuit of this still,, can change or activation the solvent absorbent in this still subsequently then with this gas reactor emptying through valve control.Comprise in a plurality of modes that solvent absorbent is housed in apparatus of the present invention; Adopt a plurality of sorbent materials that are equipped with (are for example adsorbed the material that ethanol is insoluble to carbonic acid gas simultaneously again easily; As the separating still of molecular sieve (aperture 0.4nm) in parallel fluid be connected between upper reaches separating still and the withdrawing can; Let the air-flow separating still that solvent absorbent is housed of only flowing through at every turn; Treat wherein solvent absorbent absorb saturated after, air-flow is switched to the separating still that another is equipped with solvent absorbent, realize using by turns of these a plurality of separating stills thus;
(3) separating pressure of reduction separating still.In embodiments more of the present invention, adopt the Recycle design of " dry still (can be a plurality of dry stills), separating still (can be a plurality of dry stills), withdrawing can, condensing surface, the circulate carbon dioxide storage tank " of CO 2 fluid to realize this target more easily.In this mode; Through one be installed on the withdrawing can send for compression pump B 3 to start or the shutdown signal pressure unit controls the startup of compression pump B3 or cuts out that (this pressure unit has the pressure low limit set-up function; When detecting the withdrawing can internal pressure and be lower than this pressure low limit set(ting)value; Pressure unit sends shutdown signal and gives compression pump B3, and compression pump B3 quits work; When detecting the withdrawing can internal pressure and be higher than this pressure low limit set(ting)value; Pressure unit sends the work initiating signal and gives compression pump B3; Compression pump B3 starts working), can be with withdrawing can pressure-controlling to a normal atmosphere size, therefore; The separating still top hole pressure value that is attached thereto also can be reduced to the normal atmosphere size, thereby realizes that through for example controlling separating still outlet valve size it is near withdrawing can internal pressure value that the still internal pressure of separating still is reduced to minimum.
The present invention also provides the method for preparing aerogel material, and said method adopts aforesaid apparatus of the present invention to carry out the supercritical carbon dioxide fluid drying.
Adopt aforesaid method, can prepare does not have fibre-reinforced gas gel, and its particle size can be less than 100nm; With the aperture less than 100nm; Volume density is 0.01g/cm
3To 1g/cm
3
Place the preparation and the treating processes of wet gel to be dried, can carry out with reference to the description in the patent documentations such as CN101698584A, CN101698591A, CN 101955350A.
Certainly, adopt method of the present invention, also can prepare aerogel powder material, block materials or fiber reinforcement type aerogel material.
Compare with other disclosed aerogel material preparation method, the present invention for example has following advantage: the present invention's aerogel material that can be mass-produced, throughput can reach more than 1 cubic metre/batch; Under the situation that adopts a plurality of dry stills, then can realize serialization production; Under the situation that adopts a plurality of separating stills, can dryly get more thorough; Under the situation that adopts withdrawing can, can improve the separation efficiency of solvent in rate of drying and the separating still, thereby improve performance of products; The present invention can produce the broad variety aerogel material, comprises different compositions, form, profile, size etc.; The prepared aerogel material density of the present invention, microtexture etc. are more controlled; Has very large application potential in fields such as chemical, high performance materials.
Embodiment
Hereinafter mode by way of example is described further the present invention.Yet these embodiment just are illustrated with regard to embodiment of the present invention, and protection scope of the present invention should not be construed as and only limits to these embodiment.In addition, the chemical reagent that embodiment adopted is available from Beijing chemical reagents corporation, and inorganic fibers is available from Shandong Luyang share co.,ltd.
The preparation of embodiment 1 aerogel powder material
The supercritical co exsiccant device that is used for that adopts in the present embodiment comprises parts as shown in table 1, and the parameter of each parts is as shown in table 1.
Table 1
Annotate:
The adjust flow of " * " compression pump under 1MPa is 5000m
3/ h.
"-" expression is not provided with or does not record.
" # " includes the inner aperture of 200Kg is the molecular sieve of 0.4nm.
In addition, exist under the situation of a plurality of dry stills, adopt parallel connection or placed in-line mode to connect; Exist under the situation of a plurality of separating stills, separating still all adopts placed in-line mode to connect.
In the preparation container, add the ethanolic soln (40 volume %) of tetraethoxy, add entry then, dripping hydrochloric acid (1M) and ammoniacal liquor (1M) successively under stirring condition again, gelation reaction begins.Wherein, the mol ratio of material is: tetraethoxy: water: hydrochloric acid: ammoniacal liquor=100: 400: 1: 1.Mixing continued stirred 5 minutes.
At room temperature, gel continued aging 1 day.Take out wet gel afterwards, put into absolute ethyl alcohol and carry out solvent exchange.Every ethanol that changed one time at a distance from 48 hours, water-content is lower than till 1% in using karl Fischer moisture titration apparatus mensuration ethanol.The wet gel of accomplishing solvent exchange is put into carries out the supercritical carbon dioxide fluid drying in the dry still.
Drying process is following: the wet gel of 500L is put into dry still, and injecting carbon dioxide in dry still at room temperature is incubated 2 hours; Temperature is warming up to design temperature, will takes dry still out of as the ethanol of assist medium with the carbon dioxide flow of 1000L/h again and separate, to the last a separating still no longer oozes till the ethanol, and sepn process is accomplished.After sepn process is accomplished; Blowdown rate with 2MPa/h is reduced to the pressure in the dry still suitable with the circulate carbon dioxide tank inner pressure earlier; After the carbonic acid gas in the dry still be discharged into the tail gas storage tank with the blowdown rate of 2MPa/h reclaim, reach 0.7MPa up to pressure, after with the residual carbon dioxide emptying in the dry still; Till dry still internal pressure reaches normal pressure, obtain silicon dioxide powder powder material.
The aerogel powder that this method makes can be used as the raw material of insulating brick, the carrier of catalyzer etc.
By being the wet gel of 1000L, and calculate alcoholic acid separation efficiency and time of drying with the dry total amount of upper type.
Except the condition shown in the table 2, adopt and carry out embodiment 2 to 5 and 11 with embodiment 1 identical mode.
Embodiment 6: the preparation of fibre-reinforced aerogel matrix material
In the preparation container, add the ethanolic soln (40 volume %) of tetraethoxy, add entry then, dropping ammonia (1M) and ammonium fluoride aqueous solution (0.1M) successively under stirring condition again, gelation reaction begins.Wherein, the mol ratio of material ratio is: tetraethoxy: ammoniacal liquor: Neutral ammonium fluoride=100: 400: 1: 1.Mixing continued stirred 5 minutes.
Use prepared sol impregnation volume density to be 0.1g/cm
3Glass fiber blanket.Dipping method is: earlier glass fiber blanket is put into mold cavity, above-mentioned colloidal sol is slowly being added in the die cavity, make glass fiber blanket absorb colloidal sol.After glass fiber blanket soaks into colloidal sol, closed die.After at room temperature carrying out gel, promptly obtain glass fiber blanket enhanced silica wet gel.
At room temperature, gel continued aging 1 day.Take mould afterwards apart, take out wet gel, put into absolute ethyl alcohol and carry out solvent exchange.Every ethanol that changed one time at a distance from 48 hours, water-content is lower than till 1% in using karl Fischer moisture titration apparatus mensuration ethanol.The fiber reinforcement wet gel of accomplishing solvent exchange is put in the ethanol solution of the hexamethyldisilazane that contains 5% (volume content), and room temperature left standstill 24 hours; Once more wet gel is taken out afterwards, be placed on solvent exchange twice in the absolute ethyl alcohol, each 48 hours.Begin to carry out supercritical drying then.
Drying process is following: the wet gel of 500L is put into dry still, and injecting carbon dioxide in dry still at room temperature is incubated 2 hours; Temperature with dry still rises to design temperature afterwards, will take dry still out of as the ethanol of assist medium with the carbon dioxide flow of 1000L/h again and separate; After sepn process is accomplished; Blowdown rate with 2MPa/h is reduced to the pressure in the dry still suitable with the circulate carbon dioxide tank inner pressure earlier; After the carbonic acid gas in the dry still be discharged into the tail gas storage tank with the blowdown rate of 2MPa/h reclaim, reach 0.7MPa up to pressure, after with the residual carbon dioxide emptying in the dry still; Till dry still internal pressure reaches normal pressure, can obtain glass fiber blanket enhanced aerogel composite.
It is a kind of lagging material of efficient and light weight that the made glass fiber blanket of this method strengthens aerogel composite.By being the wet gel of 1000L, and calculate alcoholic acid separation efficiency and time of drying with the dry total amount of upper type.
Embodiment 7 to 10
Except the condition shown in the table 2, adopt and carry out embodiment 7 to 10 with embodiment 6 identical modes.
Measuring method
Specific surface area: on V-Sorb2800P type specific surface determinator, measure.
Room temperature thermal conductivity: on TPS2500 Hot Disk type specific surface determinator, survey.
The ethanol separation efficiency: wet gel heavily is m before dry
1, behind the supercritical drying, obtaining gas gel weight is m
2, isolating ethanol weight is m
3, ethanol separation efficiency=m
3/ (m
1-m
2) * 100%, separation efficiency are high more, explain that the separating still separating effect is good more, and the amount of alcohol that is brought in the circulate carbon dioxide storage tank is few more.
Time of drying: put into dry still from sample and begin required time when sample takes out.
The concrete illustrative embodiments of above reference describes and shows the present invention in detail.But the present invention be not limited to said with shown in illustrative embodiments.Under the situation that does not break away from the spirit and scope of the present invention, those skilled in the art can carry out various modifications and change to the present invention, and these modifications and change all fall in the scope of accompanying claims.
Claims (9)
1. one kind is used for supercritical co exsiccant device, and wherein, said device comprises:
The circulate carbon dioxide storage tank;
The force (forcing) pump that is connected with the circulate carbon dioxide storage tank;
One or more the dry still that is connected with said circulate carbon dioxide storage tank fluid via said force (forcing) pump;
The one or more separating stills that are connected with said dry still fluid;
The withdrawing can that is connected with said separating still fluid;
The compression pump that is connected with said withdrawing can fluid; With
Via the condensing surface that said compression pump is connected with said withdrawing can fluid, said condensing surface also is connected with said circulate carbon dioxide storage tank fluid.
2. device as claimed in claim 1, wherein, the quantity of said separating still is more than two, and adopts placed in-line mode fluid to be connected between said dry still and the said withdrawing can.
3. according to claim 1 or claim 2 device, wherein, the quantity of said dry still is more than two, and adopts parallel connection and/or placed in-line mode fluid to be connected between said circulate carbon dioxide storage tank and the said separating still.
4. like each described device of claim 1 to 3, wherein, said dry still also directly is connected with said withdrawing can fluid.
5. like each described device of claim 1 to 4, wherein, said separating still also directly is connected with said condensing surface fluid.
6. like each described device of claim 1 to 5, wherein, said dry still, separating still and/or circulate carbon dioxide storage tank have temperature regulating device.
7. like each described device of claim 1 to 6, wherein, the temperature of said dry still and/or separating still is controlled as 0 to 100 ℃, and the temperature of circulate carbon dioxide storage tank is controlled as 0 to 40 ℃.
8. like each described device of claim 1 to 5, wherein, said device also comprises feed carbon dioxide storage tank and injection pump, and said feed carbon dioxide storage tank is connected with said circulate carbon dioxide storage tank fluid via said injection pump.
9. method of making gas gel, said method adopt each described device of claim 1 to 8 that wet gel is carried out the supercritical co drying.
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Application publication date: 20120613 Assignee: China Aerospace Science and engineering flying Technology Research Institute Assignor: Aerospace Research Istitute of Special Material and Process Technology Contract record no.: 2015990000504 Denomination of invention: Device for drying supercritical fluid and method for preparing aerogel material Granted publication date: 20140625 License type: Exclusive License Record date: 20150625 |
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