CN108955096A - A kind of method that supercritical carbon dioxide is dry - Google Patents
A kind of method that supercritical carbon dioxide is dry Download PDFInfo
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- CN108955096A CN108955096A CN201810495462.3A CN201810495462A CN108955096A CN 108955096 A CN108955096 A CN 108955096A CN 201810495462 A CN201810495462 A CN 201810495462A CN 108955096 A CN108955096 A CN 108955096A
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- drying
- fluid
- kettle
- supercritical
- drying kettle
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 48
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 45
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 45
- 238000001035 drying Methods 0.000 claims abstract description 138
- 239000012530 fluid Substances 0.000 claims abstract description 95
- 238000000352 supercritical drying Methods 0.000 claims abstract description 47
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 238000005192 partition Methods 0.000 claims description 24
- 238000004891 communication Methods 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 12
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 23
- 239000000463 material Substances 0.000 description 12
- 239000011240 wet gel Substances 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000004964 aerogel Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000005057 refrigeration Methods 0.000 description 7
- 239000003125 aqueous solvent Substances 0.000 description 6
- 230000006641 stabilisation Effects 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 230000036760 body temperature Effects 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910002012 Aerosil® Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000002210 supercritical carbon dioxide drying Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B5/00—Drying solid materials or objects by processes not involving the application of heat
- F26B5/005—Drying solid materials or objects by processes not involving the application of heat by dipping them into or mixing them with a chemical liquid, e.g. organic; chemical, e.g. organic, dewatering aids
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B21/00—Arrangements or duct systems, e.g. in combination with pallet boxes, for supplying and controlling air or gases for drying solid materials or objects
- F26B21/06—Controlling, e.g. regulating, parameters of gas supply
- F26B21/10—Temperature; Pressure
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B21/00—Arrangements or duct systems, e.g. in combination with pallet boxes, for supplying and controlling air or gases for drying solid materials or objects
- F26B21/14—Arrangements or duct systems, e.g. in combination with pallet boxes, for supplying and controlling air or gases for drying solid materials or objects using gases or vapours other than air or steam, e.g. inert gases
Abstract
The present invention relates to a kind of methods that supercritical carbon dioxide is dry.The described method includes: (1) makes 5 DEG C~20 DEG C of the temperature in drying kettle；(2) bottom position and/or medium position for solvent-laden sample to be dried will be wrapped being placed in the short transverse of the drying kettle in the drying kettle；(3) enter supercritical drying in the drying kettle to carry out supercritical drying to the sample to be dried with CO 2 fluid, then the CO 2 fluid comprising the solvent for carrying out supercritical drying generation is discharged.The method of the present invention drying efficiency is high, the integrality of product and the stability of properties of product can be effectively ensured and is suitably applied in the preparation that the porous materials such as aeroge are carried out in large-scale production.
Description
Technical field
The present invention relates to a kind of methods that Supercritical Drying Technology field more particularly to supercritical carbon dioxide are dry.
Background technique
Supercritical Drying Technology (SCD), can simply be defined as will be in solid material or aqueous suspension with supercritical fluid
Liquid (usually water or displacement water after organic solvent) remove process.Due in conventional drying means, gas-liquid surface
The presence of tension cannot get premium quality product so that duct is easy to collapse the material of pore structure in the drying process.Supercritical drying
Dry technology is dried medium to be pressurized to critical condition or more, and gas-liquid interface disappears, and surface tension is almost nil, thus dry
The complete of cellular structure can be preferably protected during dry.
According to the difference of supercritical solvent used in drying process, supercritical drying can be divided into overcritical organic molten
Agent dry (SCOD), supercritical gas dry (SCGD), overcritical mixed solvent are dry (SCMD), supercritical extract-drying
(SCGED) and supercritical spray is dry (SASD).Currently, supercritical gas drying process be will be obtained after solvent is replaced to
Drying sample is placed in full of liquid carbon dioxide (CO2) autoclave in a period of time so that liquid carbon dioxide is sufficiently displaced from
Then solvent in sample adjusts temperature and pressure until more than the critical point of carbon dioxide slowly dropping after being kept for a period of time
Normal pressure is pressed onto obtain dry products.Supercritical gas drying process is practical because operating condition is mild, overcritical
Gas dry technology is the main drying means for preparing aerogel material at present.
But existing supercritical carbon dioxide dry technology is generally only applicable to the overcritical of laboratory and small size autoclave body
Carbon dioxide dries equipment, and to cannot be directly used to heavy caliber, big autoclave body overcritical for small-sized supercritical carbon dioxide dry technology
Carbon dioxide is dry.And with social development, to large scale, special-shaped aerogel material demand it is gradually urgent, it is small-sized overcritical
Drying equipment and technology have been unable to meet actual demand.
A kind of method that CN102491326B discloses the device for supercritical fluid drying and prepares aerogel material,
The device and use device progress supercritical drying of the patent disclosure prepare aeroge and are able to achieve different production scales, different lifes
The preparation of the aerogel material of production mode, the device in the patent can produce different sizes, type face and different types of aeroge
Material；But drying time length is still had using the device and method progress supercritical drying in the patent, drying efficiency needs
Further increase and large-scale production process in product it is possible that the stability of cracking, properties of product to be improved is asked
Topic.
Summary of the invention
The object of the present invention is to provide a kind of drying efficiencies integrality and properties of product high, that product can be effectively ensured
Stability and the method for the supercritical carbon dioxide being suitably applied in large-scale production drying, at least to solve in the prior art
An existing technical problem.
To achieve the goals above, a kind of method dry the present invention provides supercritical carbon dioxide, the method packet
Include following steps:
(1) make 5 DEG C~20 DEG C of temperature in drying kettle；
(2) solvent-laden sample to be dried will be wrapped and is placed in the bottom in the drying kettle in the short transverse of the drying kettle
Portion position and/or medium position；With
(3) enter supercritical drying in the drying kettle to surpass to the sample to be dried with CO 2 fluid
Then critical drying the CO 2 fluid comprising the solvent for carrying out supercritical drying generation is discharged.
Preferably, before carrying out the supercritical drying, the pressure in the drying kettle is adjusted to 10~15MPa.
It preferably, further will be in the drying kettle after the pressure in the drying kettle is adjusted to 10~15MPa
Temperature be adjusted to 35 DEG C~45 DEG C.
Preferably, the supercritical drying is carried out under conditions of pressure is 10~15MPa and temperature is 35 DEG C~45 DEG C
After 10~20min, it will be discharged comprising the CO 2 fluid of the solvent.
Preferably, the supercritical drying CO 2 fluid enter the drying kettle in flow velocity be 1500~
2500L/h。
Preferably, the volume of the drying kettle is 1000~3500L.
Preferably, the bottom position in the drying kettle and/or medium position are equipped with for placing the sample to be dried
Partition；The partition has the fluid through-hole for passing through for the CO 2 fluid, is divided in the drying kettle by partition
The different spaces being divided into are in fluid communication with each other by the fluid through-hole.
Preferably, the method also includes the CO 2 fluid of discharge is carried out separation to isolate described two
The solvent for including in carbon oxide fluid, the step of being then discharged out the CO 2 fluid obtained after separation.
Preferably, the method further includes returning to the CO 2 fluid being discharged after separation to be used as super face
The step of boundary's drying CO 2 fluid.
Preferably, the isolated pressure is 3.5~7.5MPa and/or the isolated temperature is 20~35 DEG C.
The present invention at least has the following beneficial effects: compared with prior art
(1) the method for the present invention first makes 5~20 DEG C of the temperature in drying kettle, then sample to be dried is placed in drying kettle
Bottom position and/or medium position, can dramatically guarantee it is dry after the completion of the obtained integrality and property of product
The stability of energy.
(2) in certain preferred embodiments of the invention, the parameter of supercritical carbon dioxide drying process is controlled
System can greatly improve the dry drying efficiency of supercritical carbon dioxide, shorten drying time.
(3) the method for the present invention is able to achieve the porous materials such as each aerogel-like of large-scale production, is carried out using the method for the present invention
Supercritical drying, drying efficiency is high, separative efficiency is high and CO 2 fluid recovery efficiency is high.
Detailed description of the invention
Fig. 1 is the schematic diagram of device dry for supercritical carbon dioxide in some embodiments of the present invention.
Fig. 2 is the inner section schematic diagram of drying kettle in Fig. 1.
Fig. 3 is the inner section schematic diagram of drying kettle in other embodiments of the invention.
In figure: 1: carbon dioxide storage tank；2: refrigeration machine；3: high-pressure metering pump；4: drying kettle；5: the first separating stills；6: the
Two separating stills；7: filter；8: condenser；9: partition；10: the first preheaters；11: the second preheaters；12: third preheater；
13: the outlet of drying kettle；14: sample to be dried.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this hair
Bright technical solution is clearly and completely described.Obviously, described embodiment is a part of the embodiments of the present invention, and
The embodiment being not all of.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work
Under the premise of every other embodiment obtained, shall fall within the protection scope of the present invention.
The present invention provides a kind of methods that supercritical carbon dioxide is dry, and described method includes following steps:
(1) make (such as 5 DEG C, 8 DEG C, 10 DEG C, 12 DEG C, 15 DEG C, 18 DEG C or 20 of 5 DEG C~20 DEG C of temperature in drying kettle
℃)；
(2) will wrap solvent-laden sample to be dried (such as wet gel) be placed in the short transverse of the drying kettle it is described
Bottom position and/or medium position in drying kettle；With
(3) enter supercritical drying in the drying kettle to surpass to the sample to be dried with CO 2 fluid
Then critical drying the CO 2 fluid comprising the solvent for carrying out supercritical drying generation is discharged.
Illustrate, 5 DEG C~20 DEG C of temperature in drying kettle are made in step (1), that is, make sample to be dried into
The temperature (autoclave body temperature when charging) of drying kettle autoclave body is 5 DEG C~20 DEG C when material；It in the present invention, also will be in the drying kettle
Close bottom position, close medium position in short transverse in the drying kettle are considered bottom position, medium position respectively.
Supercritical Drying Technology in large-scale production process is also absorbed in the ginseng being in supercritical drying process at present
In several research, and to before supercritical drying and other relevant operation is then than more random, therefore can in large-scale production
The phenomenon that product obtained after drying cracks can be will lead to.Present inventors have unexpectedly found that kettle when by guaranteeing reasonable charging
The reasonable placement location of temperature and sample to be dried in drying kettle, can show to avoid what cracking occurred in obtained product
As the integrality of the product obtained after drying and the stability of properties of product can be effectively ensured.
According to some preferred embodiments, before carrying out the supercritical drying, by the pressure in the drying kettle
It is adjusted to 10~15MPa (such as 10,11,12,13,14 or 15MPa).
According to some preferred embodiments, after the pressure in the drying kettle is adjusted to 10~15MPa, into one
Temperature in the drying kettle is adjusted to 35 DEG C~45 DEG C (such as 35 DEG C, 36 DEG C, 37 DEG C, 38 DEG C, 39 DEG C, 40 DEG C, 41 by step
DEG C, 42 DEG C, 43 DEG C, 44 DEG C or 45 DEG C).
According to some preferred embodiments, under conditions of pressure is 10~15MPa and temperature is 35 DEG C~45 DEG C into
Row 10~the 20min of supercritical drying (time of heat-insulation pressure keeping) (such as 10,11,12,13,14,15,16,17,18,19 or
It is preferably 20min) after 15min, will will include the discharge of the CO 2 fluid of the solvent.In the present invention, it is preferred to for that will protect
The time of warm pressure maintaining shorten to 10~20min, compared with the heat-insulation pressure keeping of long period, present invention can ensure that carbon dioxide stream
Body improves drying efficiency to effective dissolution rate of solvent instead to a certain extent.
The present invention has carried out the time of the pressure of supercritical carbon dioxide drying process, temperature and heat-insulation pressure keeping excellent
Change, greatly improves the dry drying efficiency of supercritical carbon dioxide, shortens drying time.
According to some preferred embodiments, the supercritical drying is entered in the drying kettle with CO 2 fluid
Flow velocity be 1500~2500L/h (such as 1500,1600,1700,1800,1900,2000,2100,2200,2300,2400 or
2500L/h).In the present invention, the flow velocity of supercritical drying CO 2 fluid is preferably 1500~2500L/h, and existing
In order to avoid CO 2 fluid consumes excessively in supercritical drying process, generally flow control is compared in 1000L/h or less,
The present invention is optimized by the flow velocity to CO 2 fluid, when can significantly improve drying efficiency and shorten dry
Between, the consumption of CO 2 fluid is largely reduced instead, saves the cost of supercritical drying.
According to some preferred embodiments, the volume of the drying kettle be 1000~3500L (such as 1000,1500,
2000,2500,3000 or 3500L).Drying kettle in the present invention is preferably the big autoclave body of heavy caliber that volume is 1000~3500L,
It is adapted to carry out the porous materials such as each aerogel-like of large-scale production.
Supercritical carbon dioxide drying process according to some specific embodiments, in the present invention are as follows: by a certain amount of warp
The solvent-laden sample to be dried of packet of alcohol displacement is placed in bottom position and/or medium position on drying kettle inner height direction, into
Drying kettle autoclave body temperature is 5~20 DEG C when material；Make supercritical drying CO 2 fluid with the flow velocity of 1500~2500L/h into
Enter in the drying kettle, and the pressure in the drying kettle is adjusted to 10~15MPa, after the pressure in kettle to be dried is stablized,
Temperature in drying kettle is risen to 35 DEG C~45 DEG C, state 15min is kept, CO 2 fluid is allowed sufficiently to dissolve sample to be dried
Solvent in product simultaneously carries out supercritical drying to the sample to be dried；It then include described by carry out supercritical drying generation
The CO 2 fluid of solvent is discharged, until the solvent for including in sample to be dried is almost removed clean.Particularly, Ke Yi
Timing sampling in supercritical drying process, solvent content obtains rate of drying information in test sample.
According to some preferred embodiments, bottom position and/or medium position in the drying kettle are equipped with for putting
The partition of the sample to be dried is set, as shown in Figure 3；The partition has the fluid for passing through for the CO 2 fluid
Through-hole (is not shown) in Fig. 3, is flowed each other by the different spaces that partition is separated by the fluid through-hole in the drying kettle
Body connection.
According to some preferred embodiments, the top position (close to top position) in the drying kettle, which can also be equipped with, to be used
In the partition for placing the solvent-laden sample to be dried of packet, such as shown in Figure 2.It in the present invention, for the convenience of description, can
The partition of the bottom position in drying kettle described in the short transverse that the drying kettle is arranged in is denoted as A partition, will be arranged
The partition of the medium position in the drying kettle be denoted as B partition and by be arranged in the top position in the drying kettle every
Plate is denoted as C partition.
According to some preferred embodiments, the method also includes separating the CO 2 fluid of discharge
To isolate the solvent for including in the CO 2 fluid, it is then discharged out the step of the CO 2 fluid obtained after separation
Suddenly.
According to some preferred embodiments, the carbon dioxide that the method further includes being discharged after separation
Fluid returns to the step of being used as supercritical drying CO 2 fluid.The institute being preferably discharged after separation in the present invention
It states CO 2 fluid and returns and be used as supercritical drying CO 2 fluid, can constantly sent in this way into the drying kettle
Enter supercritical drying CO 2 fluid, the same of supercritical drying constantly is carried out to the sample to be dried in the drying kettle
When, dramatically save total dosage of CO 2 fluid.
According to some preferred embodiments, the isolated pressure be 3.5~7.5MPa (such as 3.5,4,4.5,5,
5.5,6,6.5,7 or 7.5MPa) and/or the isolated temperature be 20~35 DEG C of (such as 20 DEG C, 22 DEG C, 25 DEG C, 28 DEG C, 30
DEG C, 32 DEG C or 35 DEG C).In the present invention, it is preferred to be 3.5~7.5MPa by the isolated pressure control, and/or separation
Temperature control be 20~35 DEG C, can effectively guarantee discharge CO 2 fluid in include solvent separative efficiency and
The recovery efficiency for the CO 2 fluid being discharged after separation.
According to some specific embodiments, the dry method of supercritical carbon dioxide of the present invention passes through for surpassing
The dry device of critical carbon dioxide carries out, and Fig. 1 is dry for supercritical carbon dioxide in some embodiments of the present invention
The schematic diagram of device.The device dry for supercritical carbon dioxide includes: for storing supercritical drying titanium dioxide
The carbon dioxide storage tank 1 of carbon flow body；The refrigeration machine 2 being in fluid communication with the carbon dioxide storage tank；Connect with 2 fluid of refrigeration machine
Logical drying kettle 4；It is provided on the access that the refrigeration machine 2 is in fluid communication with the drying kettle 4 for by carbon dioxide stream
Body is quantitatively sent into the high-pressure metering pump 3 in the drying kettle 4；(first point of two separating stills be in fluid communication with the drying kettle 4
From kettle 5 and the second separating still 6)；The filter 7 being in fluid communication with second separating still 6；It is in fluid communication with the filter 7
Condenser 8；The filter 7 is also directly in fluid communication with the carbon dioxide storage tank 1, and the condenser 8 is also directly and institute
State the fluid communication of carbon dioxide storage tank 1.The inner section Pictorial examples of the drying kettle 4 such as can be as shown in Fig. 2, described dry
Bottom position, medium position and top position in the short transverse of dry kettle 4 in the drying kettle 4 are equipped with for placing the packet
The partition 9 of solvent-laden sample to be dried, the partition 9 have the fluid through-hole for passing through for the CO 2 fluid
(being not shown in Fig. 2), the different spaces being separated by partition 9 in the drying kettle 4 by the fluid through-hole and each other fluid
Connection.First separating still 5 is in fluid communication using concatenated mode in the drying kettle 4 and institute with second separating still 6
It states between filter 7.The device dry for supercritical carbon dioxide further includes being in fluid communication in the high-pressure metering pump 3
The first preheater 10, fluid communication between the drying kettle 4 is between the drying kettle 4 and first separating still 5
Second preheater 11 and the third preheater 12 being in fluid communication between first separating still 5 and second separating still 6.?
In the present invention, carbon dioxide storage tank 1, drying kettle 4 and separating still 5 etc. can be considered pressure vessel, each pressure vessel
Independent pressure control valve can be had, for controlling the pressure size in each pressure vessel；First preheater 10 is used for
The temperature in the drying kettle 4, second preheater 11 and third preheater 12 is controlled to be respectively used to control described first point
From the temperature in kettle 5 and the second separating still 6.
In the present invention, it is believed that circulation path is formd between each pressure vessel, particularly, apparatus of the present invention can
Various control valves (pressure-regulating valve) to be arranged in circulation path, for controlling the stream of fluid such as CO 2 fluid
It is dynamic, thus realize CO 2 fluid by circulation canal constantly to sample to be dried to be dried in the drying kettle 4 into
Row supercritical drying.
Particularly, the endless form in the device dry for supercritical carbon dioxide in circulation path is for example are as follows:
CO 2 fluid first passes through the refrigeration of refrigeration machine 2, makes to obtain after refrigeration machine cooling by the way of low temperature cold feed
Pressurization of the low temperature liquid CO 2 fluid through high-pressure metering pump 3 fluid inlet of bottom out of described drying kettle 4 send to
In drying kettle 4, when the pressure in drying kettle 4 reaches the pressure of setting, such as by opening drying kettle 4 and the first separating still 5
Between and the control valve between the first separating still 5 and the second separating still 6, make CO 2 fluid from the outlet of drying kettle 4
It sequentially enters two separating stills to be separated, when the pressure in two separating stills reaches the separating pressure of setting, opens second
Valve between separating still 6 and filter 7, CO 2 fluid is after the filtering of filter 7, subsequently into condenser 8, dioxy
After change carbon flow body is condensed into liquid carbon dioxide in condenser 8, carbon dioxide storage tank 1 is returned to, to realize carbon dioxide
Circulation of the fluid in circulation path.
After the completion of entire supercritical drying and separation process, various control valves, the heating system of preheater are closed, are put
Residual gas in empty described device opens drying kettle kettle cover, can be obtained dry products.
Particularly, in the cyclic process of circulation canal, for the carbon dioxide stream being decreased back in carbon dioxide storage tank 1
The content for the solvent for including in body avoids the solvent for including in supercritical drying CO 2 fluid to product structure and performance
Influence, can be placed in the first separating still 5 and the second separating still 6 can adsorption solvent material (such as solvent or molecular sieve
Deng).
Hereafter the present invention will be further detailed by way of example, but protection scope of the present invention is unlimited
In these embodiments.
Embodiment 1
It is dry that supercritical carbon dioxide is carried out using device as shown in Figure 1:
On the A partition for the drying kettle that autoclave body temperature is 10 DEG C when 1000L silica wet gel is put into charging, starting is high
Metering pump is pressed, enters supercritical drying CO 2 fluid in drying kettle with the flow velocity of 1500L/h；Control valve makes to do
Pressure in dry kettle is adjusted to 10MPa, after a period of stabilisation to pressure, drying kettle is warming up to 35 DEG C, keeps the state
15min (time of heat-insulation pressure keeping) allows the solvent (alcohol aqueous solvent) for including in CO 2 fluid and silica wet gel to fill
Divide dissolution, then slowly open pressure reducing valve, the fluid-mixing of CO 2 fluid and alcohol aqueous solvent (is wrapped into solvent-laden titanium dioxide
Carbon flow body) slowly to release, it is 1500L/h that whole process, which controls carbon dioxide flow rate,.Entire drying process continues to solvent almost
It is removed clean, closes valve, heating system, gas in emptying device opens drying kettle, obtains aerosil.
The present embodiment aerogel material obtained is tested for the property, including aperture, specific surface area, exterior appearance
Deng；The drying time of the present embodiment is recorded, the results are shown in Table 1.
Test method:
Drying time: to required time when taking out product since sample is put into drying kettle.
Aperture, specific surface area: it is measured on V-Sorb2800P type hole diameter and Determination of Specific Surface Area instrument.
Embodiment 2
It is dry that supercritical carbon dioxide is carried out using device as shown in Figure 1:
On the B partition for the drying kettle that autoclave body temperature is 8 DEG C when 1000L silica wet gel is put into charging, starting is high
Metering pump is pressed, enters supercritical drying CO 2 fluid in drying kettle with the flow velocity of 1500L/h；Control valve makes to do
Pressure in dry kettle is adjusted to 15MPa, after a period of stabilisation to pressure, drying kettle is warming up to 35 DEG C, keeps the state
15min allows the solvent (alcohol aqueous solvent) for including in CO 2 fluid and silica wet gel sufficiently to dissolve, then slowly beats
Pressure valve is reduced, the fluid-mixing (wrapping solvent-laden CO 2 fluid) of CO 2 fluid and alcohol aqueous solvent is slowly released,
It is 1500L/h that whole process, which controls carbon dioxide flow rate,.Entire drying process continues almost to be removed clean to solvent, closes valve
Door, heating system, gas in emptying device open drying kettle, obtain aerosil.
The present embodiment aerogel material obtained is tested for the property using identical test method in embodiment 1,
Including aperture, specific surface area, exterior appearance etc.；The drying time of the present embodiment is recorded, the results are shown in Table 1.
Embodiment 3
It is dry that supercritical carbon dioxide is carried out using device as shown in Figure 1:
On the A partition for the drying kettle that autoclave body temperature is 10 DEG C when 1000L silica wet gel is put into charging, starting is high
Metering pump is pressed, enters supercritical drying CO 2 fluid in drying kettle with the flow velocity of 2000L/h；Control valve makes to do
Pressure in dry kettle is adjusted to 10MPa, after a period of stabilisation to pressure, drying kettle is warming up to 40 DEG C, keeps the state
15min allows the solvent (alcohol aqueous solvent) for including in CO 2 fluid and silica wet gel sufficiently to dissolve, then slowly beats
Pressure valve is reduced, the fluid-mixing (wrapping solvent-laden CO 2 fluid) of CO 2 fluid and alcohol aqueous solvent is slowly released,
It is 2000L/h that whole process, which controls carbon dioxide flow rate,.Entire drying process continues almost to be removed clean to solvent, closes valve
Door, heating system, gas in emptying device open drying kettle, obtain aerosil.
The present embodiment aerogel material obtained is tested for the property using identical test method in embodiment 1,
Including aperture, specific surface area, exterior appearance etc.；The drying time of the present embodiment is recorded, the results are shown in Table 1.
Embodiment 4
Embodiment 4 is substantially the same manner as Example 1, the difference is that: by silica wet gel be placed in the B of drying kettle every
On plate；The flow velocity of CO 2 fluid is 1000L/h.
Embodiment 5
Embodiment 5 is substantially the same manner as Example 1, the difference is that: control valve is adjusted to the pressure in drying kettle
Drying kettle after a period of stabilisation to pressure is warming up to 50 DEG C by 20MPa.
Embodiment 6
Embodiment 6 is substantially the same manner as Example 1, the difference is that: two parts of 500L silica wet gels are put respectively
In on the A partition of drying kettle and on B partition.
Embodiment 7
Embodiment 7 is substantially the same manner as Example 1, the difference is that: the time of heat-insulation pressure keeping is 2h.
Comparative example 1
Comparative example 1 is substantially the same manner as Example 1, the difference is that: the temperature of autoclave body is 30 DEG C when charging.
Comparative example 2
Comparative example 2 is substantially the same manner as Example 1, the difference is that: by silica wet gel be placed in the C of drying kettle every
On plate.
Comparative example 3
Comparative example 3 is substantially the same manner as Example 1, the difference is that: the temperature of autoclave body is 30 DEG C when charging；Regulating valve
Door, makes the pressure in drying kettle be adjusted to 20MPa, after a period of stabilisation to pressure, drying kettle is warming up to 50 DEG C；Titanium dioxide
The flow velocity of carbon flow body is 1000L/h.
Comparative example 4
Comparative example 4 is substantially the same manner as Example 1, the difference is that: by silica wet gel be placed in the C of drying kettle every
On plate；Control valve makes the pressure in drying kettle be adjusted to 20MPa, and after a period of stabilisation to pressure, drying kettle is warming up to
50℃；The flow velocity of CO 2 fluid is 1000L/h.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of dry method of supercritical carbon dioxide, which is characterized in that described method includes following steps:
(1) make 5 DEG C~20 DEG C of temperature in drying kettle；
(2) solvent-laden sample to be dried will be wrapped and is placed in the bottom position in the drying kettle in the short transverse of the drying kettle
It sets and/or medium position；With
(3) enter supercritical drying with CO 2 fluid overcritical to carry out to the sample to be dried in the drying kettle
It is dry, then the CO 2 fluid comprising the solvent for carrying out supercritical drying generation is discharged.
2. according to the method described in claim 1, it is characterized by:
Before carrying out the supercritical drying, the pressure in the drying kettle is adjusted to 10~15MPa.
3. according to the method described in claim 2, it is characterized by:
After the pressure in the drying kettle is adjusted to 10~15MPa, further the temperature in the drying kettle is adjusted
It is 35 DEG C~45 DEG C.
4. according to the method described in claim 3, it is characterized by:
Carried out under conditions of pressure is 10~15MPa and temperature is 35 DEG C~45 DEG C the 10~20min of supercritical drying it
Afterwards, it will be discharged comprising the CO 2 fluid of the solvent.
5. according to method described in right 1, it is characterised in that:
The flow velocity that the supercritical drying CO 2 fluid enters in the drying kettle is 1500~2500L/h.
6. according to the method described in claim 1, it is characterized by:
The volume of the drying kettle is 1000~3500L.
7. according to the method described in claim 1, it is characterized by:
Bottom position and/or medium position in the drying kettle are equipped with the partition for placing the sample to be dried；
The partition has the fluid through-hole for passing through for the CO 2 fluid, is separated into the drying kettle by partition
Different spaces be in fluid communication with each other by the fluid through-hole.
8. method according to any one of claims 1 to 7, it is characterised in that:
The method also includes the CO 2 fluid of discharge is carried out separation to isolate the CO 2 fluid
In include solvent, the step of being then discharged out the CO 2 fluid obtained after separation.
9. according to the method described in claim 8, it is characterized by:
The method further includes returning to the CO 2 fluid being discharged after separation to be used as supercritical drying with two
The step of carbon oxide fluid.
10. according to the method described in claim 8, it is characterized by:
The isolated pressure is 3.5~7.5MPa and/or the isolated temperature is 20~35 DEG C.
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