CN105467074A - Method for determining solubility of solid in supercritical ammonia, and apparatus used thereby - Google Patents
Method for determining solubility of solid in supercritical ammonia, and apparatus used thereby Download PDFInfo
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Abstract
The invention relates to a method for determining the solubility of a solid in supercritical ammonia, and an apparatus used thereby, and discloses the apparatus for determining the solubility of a supercritical ammonia system. The apparatus is composed of a cyclic balance sampling system and a sample analyzing system; and the cyclic balance sampling system comprises a balancing kettle and a sampling kettle which are two autoclaves, a circulating device, a needle valve and an oil bath pot. The sample analyzing system comprises a valve, a gas flow meter, an ammonia gas absorption bottle (gas collecting bottle) and a corresponding titration device. The invention also discloses the method for determining the solubility of the supercritical ammonia system by using the apparatus. A design idea in the invention is derived from the determination process of the solubility of a solution at normal temperature under normal pressure, that is, a saturated solution is measured, and the solubility of the system keeps unchanged in the operating process. The above static method for determining the solubility of the supercritical ammonia system avoids the disadvantages of valve obstruction and complex operation of present dynamic methods, and allows determination experiment data to be more accurate than data obtained through traditional static methods.
Description
Technical field
The present invention relates to the device that a kind of static method measures solid solubleness in supercritical ammine.It belongs to a kind of supercritical fluids system solubility test technical field.
Background technology
Supercriticality is a kind of state that material that temperature, pressure is all in more than super critical point shows.Supercritical fluid has the viscosity close with gas, the density close with liquid, the coefficient of diffusion between liquids and gases, and the dissolubility being much better than liquid.Therefore, supercritical fluid is adopted to be used widely in extraction process as the supercritical technology of solvent, and to chemical reaction, Water oxidize, crystallization technique, chromatographic technique, liquefaction coal technology, generation technology, one-tenth ore deposit technology, organic pollutant degradation and with being coupled of membrane separation technique, develop with many applications such as to be coupled of Ionic liquids technologies.Especially, in the extraction application of effective ingredients in plant, easily separated with it, nontoxic characteristic, is having huge development in recent years.
Record according to existing supercriticality data in literature, the super critical point of temperature and pressure far above apolar substance of the super critical point of polar material can be found.Therefore, mostly the research for supercritical solution in document is about non-polar material Quality Research such as carbon dioxide.But carbon dioxide is as a kind of apolar substance, and its solubility property is poor, when dissolving the compound of much polarity, suitable entrainer must be added, bring certain inconvenience to the subsequent treatment of product, also result in the increase of production cost simultaneously.Finding the supercritical solvent that the comparatively gentle polarity of a kind of condition is nontoxic, is the comparatively promising developing direction of overcritical research field.
The critical point of ammonia is 11.27MPa, 132.3 DEG C, is that condition is comparatively gentle in polar material.And the toxicity of ammonia itself is lower, nonflammable, has penetrating odor, can allows operating personnel under the condition not using all the other equipment, be easy to perceive the leakage ammonia.According to existing several sections of documents, supercritical ammine solubility property is also very superior, and supercritical ammine can not add entrainer dissolving cellulos, hemicellulose, lignin, salt, theophylline even metal iodide, metal oxide etc.
Supercritical ammine system has comparatively wide prospect in the application of the supercritical extract in future, supercritical reaction technology.Present stage, the quantity of document about the solubility test of supercritical ammine system is less, and the method adopted can be divided into static method and dynamic method two kinds of methods according to the state existing for fluid.
Dynamic method (colleges and universities' chemical engineering journal, 1996,10 (1): 16-21; FluidPhaseEquilibria, 1985,22:175-183) be supercritical fluid is continued through the temperature controlling bed that solute is housed, temperature controlling bed wants long enough, to ensure that the profit reduction and reserving time is comparatively large, allows supercritical fluids system reach capacity state.And then saturated fluid mixture is expand into atmospheric pressure, make supercritical fluid become gaseous state volatilization, and carry out determination and analysis to the solute collected, in whole process, system constantly enters ammonia, constantly dissolves, and makes whole system reach mobile equilibrium.
Static method (" supercritical fluid science and technology ", Sinopec publishing house, 2005:16-22) can be divided into analytic approach and observation method again.Analytic approach component is placed in the autoclave of a fixed volume, places and make system reach static balancing for a long time.For accelerate dissolution, usually adopt the method for stirring or continuous circulation, then take out a small amount of solution sample and carry out data analysis; Observation method is the autoclave a certain amount of solid solute and solvent put into form, raised temperature, simultaneously pressure increase, temperature and pressure when being dissolved completely by form observation solute.
The experimental provision adopted in current document is dynamic method, the shortcoming such as the method exists equipment complexity, operating difficulties (must control mobile equilibrium), blowdown valve easily block.And there is the shortcoming (the autoclave price with form in observation method is higher) of the inaccurate and apparatus expensive of measurement result in static rule described in some overcritical books and periodicals.
At present, the static method of getting saturated solution by constant voltage is not also had to sample and the method that decrease temperature and pressure is separated solute and solvent measures equipment and the method for the solubleness of supercritical fluids system.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method and the equipment therefor that measure solid solubleness in supercritical ammine.The present invention adopts static method to measure the solubleness of supercritical ammine system, overcome some shortcomings of valve blockage in existing dynamic method, complicated operation, and relatively traditional static method can obtain determination experiment data more accurately.
In order to solve the problems of the technologies described above, the invention provides a kind of supercritical ammine system solubility test device, be made up of cyclic balance sampling system and sample analysis system (ammonia Analytical system);
Described cyclic balance sampling system comprises equilibrium still, sampling still, circulating device, the gateway I of equilibrium still is successively by threeway I and be with valvular pipeline I to be connected with circulating device, circulating device is connected by the gateway I of the valvular pipeline II of band with sampling still, the gateway II of sampling still is connected with the gateway II of equilibrium still 1 by the valvular pipeline III of band and threeway II successively, thus forms a circulation system;
Valvular ammonia-feeding pipe is with to be connected with threeway I; Be provided with the gas outlet of valve at the top of equilibrium still, described gas outlet is connected with threeway II;
Equilibrium still, sampling still are all immersed in oil bath pan, and pipeline I, pipeline II, pipeline III are equipped with heating tape;
Described sample analysis system comprises gas meter and gas extractor, described gas extractor comprises at least one gas bottle, the valvular gas collecting pipe of one end connecting band of gas meter, the other end of gas meter is connected by the bore seal of connecting pipe and gas bottle.
Improvement as supercritical ammine system solubility test device of the present invention: described circulating device comprises totally enclosed cylindrical case, arranges the magnetic piston of the inwall movement being close to cylindrical case in cylindrical case; Described circulating device also comprises the magnet matched with magnetic piston.
Further improvement as supercritical ammine system solubility test device of the present invention: described magnetic piston is made up of cylindrical inner case and the iron prop being arranged in cylindrical inner case inner chamber, and the outer wall of iron prop and the inwall of cylindrical inner case form interference fit.
Further improvement as supercritical ammine system solubility test device of the present invention: circulating device in use, (namely magnetic piston often moves once, magnetic piston 31 completes an one way in cylindrical case 3) volume of solution of discharging should be greater than manifold volume (that is, the capacity of pipeline III 25 correspondence) between the gateway II of gateway II to the equilibrium still 1 of sampling still 2.
Further improvement as supercritical ammine system solubility test device of the present invention: arrange funnel in gas bottle, what connecting pipe sealed with the funnel in gas bottle is connected.
Remarks illustrate: the effect of funnel in absorption ammonia process, suck-back phenomenon occurs to prevent.
Further improvement as supercritical ammine system solubility test device of the present invention: be provided with tensimeter and thermopair on equilibrium still; Gas bottle is provided with tensimeter.
Further improvement as supercritical ammine system solubility test device of the present invention:
In the inner chamber of equilibrium still, be provided with extension pipe, the lower port of extension pipe is near the bottom (that is, the spacing of the lower port of extension pipe and the bottom of equilibrium still is 5 ~ 8mm) of equilibrium still, and what the upper port of extension pipe sealed with threeway I is connected.
Present invention also offers the method for the mensuration supercritical ammine system solubleness utilizing said apparatus to carry out, it is characterized in that comprising the following steps:
1), in equilibrium still, the excessive and solid solute to be measured be relatively positioned is placed in advance;
Adopt the method for directly filling with liquefied ammonia, the liquefied ammonia corresponding with condition determination adopting P-R equation estimation to go out by ammonia-feeding pipe disposable input in equilibrium still;
Remarks illustrate: above-mentioned solid solute to be measured is relatively positioned and refers to: only have the solute solids by dissolving could flow in cyclic balance sampling system, and can not do not flowed by undissolved solute solids;
2), by control temperature carry out the intrasystem pressure of controlled circulation balanced sampling and reach desired experiment condition, and temperature and pressure condition all to reach more than the super critical condition of ammonia (i.e. 132.3 DEG C and more than 11.27MPa);
3), by the magnetic piston in attraction circulating device in cylindrical case, make back and forth movement, thus drive the flowing of cyclic balance sampling system internal solvent, accelerate the solution in equilibrium still and the solution equilibria in sampling still;
4), by the closedown of by-pass valve control, from cyclic balance sampling system, sampling still is taken off;
5), use the method for lowering the temperature, reduce the pressure in sampling still, sampling still is connected with sample analysis system, thus makes the ammonia in sampling still be all released in gas bottle, finally carry out the mensuration of the amount of solute and solvent.
Said method can make the ammonia in sampling still become gas-liquid two-phase, thus solvent ammonia and solute solids is separated, and then utilizes sample analysis system to determine the amount of solute and solvent respectively.
Improvement as the method for mensuration supercritical ammine system solubleness of the present invention: acid solution is set in gas bottle, by the mode with HCI; Obtain the amount of the ammonia in sampling still.
Mentality of designing of the present invention is the mensuration process deriving from solubilize degree under normal temperature and pressure, namely takes out saturated solution and measures, and ensures the change that can not produce system solubleness in operation.The principle of the inventive method is as follows: the method heated up by constant volume, system condition is promoted to more than supercriticality, after balance to be dissolved, pass through by-pass valve control, sampling still and equilibrium still are separated, simultaneously in this process can the temperature, pressure of maintenance system constant, thus make the data that record comparatively accurate.For ensureing the accuracy of result, solute must be under this condition can not the solid of melting, and is fixed by solute by certain method (such as adopting asbestos gauge), prevents undissolved solute solids from entering sampling system; Secondly, in order to enable balanced system and sampling system reach dissolution equilibrium in the short period of time, the method for Inner eycle should be adopted to accelerate its dissolution equilibrium.The solubleness of solution is measured under being compared to normal temperature and pressure, supercritical fluids system also has an advantage, be exactly when temperature return is to normal temperature, supercritical fluids system generally can become a liquid-solid two-phase system, solvent in liquid constantly can be volatilized by release gas, thus solute and solvent are separated, to measure metering respectively.
In sum, apparatus of the present invention comprise cyclic balance sampling system, sample analysis system two parts of supercritical ammine.Stable circulation sampling comprises equilibrium still and sampling still two autoclaves, circulating device, needle valve and oil bath pans.Sample analysis system comprises valve, gas meter, ammonia absorption bottle (gas bottle), and corresponding titration apparatus.
The present invention has following technical advantage relative to static method:
1, the present invention adopts the method directly pouring into liquefied ammonia from sample introduction valve (with valvular ammonia-feeding pipe) in equilibrium still, is compared to dynamic method and can saves sampling pump and corresponding operation steps.
2, circulating device is adopted to accelerate the dissolution equilibrium process of system.
3, the experimental data under METHOD FOR CONTINUOUS DETERMINATION different temperatures pressure condition is realized by dismounting replacing valve sampling still.
4, by the method for cooling decompression, the supercritical fluids system in sampling still is become liquid ammonia system, is then connected with sample analysis system, further by liquid ammonia gasification, absorb titration; In sampling still, remaining solid solute adopts and dissolves titration method mensuration.
5, the present invention can solve the shortcoming of the inaccurate and apparatus expensive of the measurement result of static method.
The present invention, relative to dynamic method, has following technical advantage:
1, the present invention is an intermittent operation, can disposablely feed intake, thus the device avoiding the continued operations such as use compression pump to have, make device entirety comparatively simple, easy and simple to handle.
2, in the present invention except just starting warming temperature, only need insulation operation in all the other processes, do not need the temperature of raw material transient heating under experiment condition of normal temperature, the power requirement therefore for firing equipment is not high.
3, the present invention in use, do not relate to the homeostasis process of system.Without the need to controlling sample introduction, sample flow size, make experimental implementation easier, its experimental result recorded is also more accurate.
4, the present invention in use, can not make pressure drop, solute separates out fast, blocking valve or the less place of all the other openings.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 is the schematic diagram of solid of the present invention at supercritical ammine system solubility test device;
Fig. 2 is the structural representation of the magnetic piston 31 in Fig. 1.
Embodiment
With reference to above-mentioned accompanying drawing, the specific embodiment of the present invention is described in detail.In the present invention, pipeline connected is sealing and is connected.
Embodiment 1, Fig. 1 give a kind of solid at supercritical ammine system solubility test device (that is, supercritical ammine system solubility test device), are made up of cyclic balance sampling system and sample analysis system.
Cyclic balance sampling system comprises equilibrium still 1, sampling still 2 and circulating device, and oil bath pan 15 is built with methyl-silicone oil, and equilibrium still 1 and sampling still 2 are all immersed in the methyl-silicone oil being arranged in oil bath pan 15 inner chamber.Equilibrium still 1 is provided with tensimeter 4 and thermopair 5.
Circulating device comprises totally enclosed cylindrical case 3, the magnetic piston 31 that the sidewall that can be close to cylindrical case 3 moves freely is set in cylindrical case 3, described magnetic piston 31 is made up of cylindrical inner case 311 and the iron prop 312 being arranged in cylindrical inner case 311 inner chamber, and the outer wall of iron prop 312 and the inwall of cylindrical inner case 311 form interference fit; Therefore, iron prop 312 can drive cylindrical inner case 311 to do identical movement.
Described circulating device also comprises the magnet 30 matched with magnetic piston 31.
The gateway I of equilibrium still 1 is connected by threeway I 13 and sealing with one end of the cylindrical case 3 in circulating device with the pipeline I 23 of valve 7 successively, the other end of the cylindrical case 3 in circulating device is connected with the gateway I of sampling still 2 by the pipeline II 24 successively with valve 8, valve 9, the gateway II of sampling still 2 successively by being connected with the gateway II of equilibrium still 1 with the pipeline III 25 of valve 11, valve 10 and threeway II 14, thus forms a system circulated.
Ammonia-feeding pipe 22 with valve 6 is connected with threeway I 13; Extension pipe 32 is provided with in the inner chamber of equilibrium still 1, the lower port of extension pipe 32 near the bottom of equilibrium still 1 (namely, the spacing of the lower port of extension pipe 32 and the bottom of equilibrium still 1 is 5mm), being connected through sealing with threeway I 13 behind the gateway I of equilibrium still 1 of the upper port of extension pipe 32 sealing;
Be provided with the gas outlet 26 of valve 12 at the top of equilibrium still 1, described gas outlet 26 is connected with threeway II 14; Pipeline I 23, pipeline II 24, pipeline III 25 are all tied with heating tape.
The above-mentioned set-up mode of extension pipe 32, ammonia-feeding pipe 22 and gas outlet 26 can be guaranteed: in feed liquor ammonia process, (namely liquefied ammonia can add system smoothly, in equilibrium still 1), and after experiment completes, remaining liquefied ammonia can be released from gas outlet 26 (releasing in the form of a vapor).
Sample analysis system comprises gas meter 17 and gas extractor, and this gas extractor comprises 2 gas bottle---gas bottle 19 and the gas bottles 20 that are connected successively, is sealed be connected between gas bottle 19 and gas bottle 20 by connecting pipe 29; The lower port inserting the connecting pipe 29 in gas bottle 20 should be positioned at the middle and lower part of gas bottle 20.
In gas bottle 19, be provided with funnel 21, one end of gas meter 17 connects the gas collecting pipe 27 with valve 16, and what the other end of gas meter 17 was sealed with the funnel 21 in gas bottle 19 by connecting pipe 28 is connected.Gas bottle 19 is provided with tensimeter 18.
In sample analysis system, except valve 16, gas meter 17, tensimeter 18, all the other are all glassware; That is, gas collecting pipe 27, connecting pipe 28, little funnel 21, gas bottle 19, gas bottle 20, connecting pipe 29 etc. are glassware.Tensimeter 18 is the tensimeter of lower range, and its effect is the change of pressure in Measurement process control system, prevents pressure excessive and the gas bottle 19, the cork on gas bottle 20 that cause are rushed out.Funnel 21 is inverted little glass funnel, in absorption ammonia process, suck-back phenomenon occurs for preventing.Remarks explanation, suck-back phenomenon refers to: after ammonia release, because ammonia very easily water-soluble (acid), gaseous pressure in system pipeline is reduced instantaneously, cause absorbing liquid under pressure of the inside of a bottle effect in upstream line and system, cause measure inaccurate.
This sample analysis system is ammonia Analytical system.
During actual use:
Equilibrium still 1 is 200mL high-pressure balancing still, and the volume 20mL of sampling still 2, ammonia-feeding pipe 22, pipeline I 23, pipeline II 24, pipeline III 25 are the 316L stainless-steel tube of external diameter 6mm (internal diameter 4mm).Valve 6 ~ 12 is needle valve.
The structure of circulating device is specific as follows:
The external diameter 14mm of intercepting one section of about 20cm, the stainless steel bassoon (316L stainless-steel tube) of internal diameter 10mm are as cylindrical case 3; Select diameter slightly larger than 8mm, the cast iron post of long about 2cm, as iron prop 312, selects external diameter 10mm, and the stainless steel tubule of internal diameter 8mm is as cylindrical inner case 311; Iron prop 312 is beaten in the inner chamber of cylindrical inner case 311, thus form magnetic force piston 31; Again magnetic force piston 31 is filled in cylindrical case 3, and by two of stainless steel bassoon butt-end packings, thus form totally enclosed cylindrical case 3.Form whole circulating device thus, now, magnetic force piston 31 can be close to stainless steel bassoon--and the inwall of cylindrical case 3 is free to slide.
The magnet 30 matched with magnetic piston 31 adopts your roc strong magnets of 50 × 50 × 50mm iron, guarantees in experimentation, the magnetic piston 31 in circulating device can be attracted comparatively smoothly to move.As magnetic piston 31 dyskinesia, the magnet 30 that magnetic force is stronger or volume is larger can be adopted.
Circulating device in use, (namely magnetic piston 31 often moves once, magnetic piston 31 is in stainless steel bassoon--and complete an one way in cylindrical case 3) volume of solution of discharging should be greater than manifold volume (that is, the capacity of pipeline III 25 correspondence) between the gateway II of gateway II to the equilibrium still 1 of sampling still 2.The each movable volume that can carry of the circulation system (that is, circulating device) through testing front preliminary experiment rough measurement internal diameter 10mm, length 20cm is 14.7cm
3, namely its because of the conevying efficiency that gap causes be 0.936; Internal diameter 4mm, pipeline III 25 cumulative volume that length is about 40cm is about 5.2cm
3, meet the demands.Namely the every circulation primary of magnetic piston 31, can produce 2 × 14.7=29.4cm
3mass exchange.
Remarks illustrate: suppose to meet above-mentioned condition, so magnetic force piston 31 the transported fluid that moves once can not reach sampling still 2 (or from sampling still 2 to equilibrium still 1) from equilibrium still 1, some solution in pipeline III 25 can be caused always to put aside can not carry out mass exchange with the external world in pipeline III 25.Be equivalent to be separated by the liquid put aside in the middle of two stills, mass exchange can only be carried out by diffusion in this segment body system, be unfavorable for system balancing.Therefore, the capacity that must meet pipeline III 25 is less than the volume that magnetic piston 31 is often moved once, makes there is mass exchange between above-mentioned two stills.
Cyclic balance sampling system of the present invention is because be by pipeline, kettle, valves etc. form a closed circulating system, so when building device, that root pipeline finally measured should be comparatively accurate, to ensure that the stress in whole closing pipe line is less when sampling still 1 and equilibrium still 2 imports and exports invariant position.
The supercritical ammine system solubleness of embodiment 2, mensuration ammonium chloride: concrete operation step is as follows:
1, the Peng-Robinson equation of gas state is adopted
wherein, p is pressure, R is ideal gas constant, T is absolute temperature, V is volume, a and b is parameter) estimation, under experimental temperature, pressure condition, be full of the amount of the liquefied ammonia required for whole cyclic balance sampling system, wherein at 25 DEG C, the relative density (water) of saturated liquefied ammonia is 0.603.
2, excessive solute solids (ammonium chloride) asbestos gauge parcel is placed in equilibrium still 1, puts up experimental provision (balanced sampling system) as Fig. 1 and hunt leak to more than 15MPa with nitrogen.
Remarks illustrate: should be able to find after experiment that the solute solids in asbestos gauge has comparatively multiresidue; And asbestos gauge can not hamper mass transter.
3, be connected with valve 12 with vacuum pump, liquid ammonia storage tank is connected with valve 6.
Open valve 7-11, valve-off 6.Open vacuum pump, process is vacuumized to system (cyclic balance sampling system); When vacuum tightness reaches 0.09MPa, valve-off 12, opens valve 6 slightly, thus makes system (cyclic balance sampling system) be full of ammonia; Valve-off 6, again opens valve 12, vacuumizes.Repeat step 3 time rear valve-off 6 and valve 12, unload vacuum pump.
4, liquid ammonia storage tank is inverted, under making outlet be in liquefied ammonia liquid level.Open valve 6, and Open valve 12 slightly, liquefied ammonia is constantly flowed in equilibrium still 1 from storage tank and (flows into the bottom of equilibrium still 1).Claim to weigh the minimizing of liquid ammonia storage tank quality by carrying, when with estimation add liquefied ammonia value close time, valve-off 12, valve-off 6.Unload liquid ammonia storage tank.
5, open oil bath pan 15, make system temperature pressure increase.And note the reading of tensimeter 4, thermopair 5, reach temperature required, the pressure (132 DEG C of experiment, 12.27MPa more than) after, stablize oil bath pan 15 temperature, open the switch on heating tape, regulate temperature, make pipeline (pipeline I 23, pipeline II 24, pipeline III 25) temperature a little more than kettle temperature (within 10 DEG C), thus make system temperature keep constant.
6, after 30 minutes, attract the magnetic piston 31 in circulating device to reciprocate with magnet 30, make the system in system (cyclic balance sampling system) keep flowing.
7, continue after 30 minutes, valve-off 8,9,10,11.Sampling still 2 is unloaded from valve 9,11.
8, sampling still 2 is shifted out oil bath pan 15, the temperature of still 2 to be sampled drops to room temperature.
9, in gas bottle 19,20, add the BAS of 2% (quality %), after checking the impermeability of ammonia Analytical system (sample analysis system), liquid level should not have bottom too small funnel 21 and glass tube 29 (lower port).Valve 9 is connected with valve 16.Open valve 9, slightly open valve 16, make the reading of gas meter 17 at below 10mL per minute.
10, treat ammonia all discharge complete (namely, ammonia in sampling still 2 is all released in gas bottle 19 and gas bottle 20), take off this two gas bottles, collect absorbing liquid, with mixed indicator, (2 part of 0.1% methyl red ethanolic solution and 1 part of 0.1% methylene blue ethanolic solution face the used time and mix, above-mentioned % is quality %, and part refers to parts by volume) as indicator, carry out titration with standard salt acid solution; Thus obtain the amount of the ammonia in sampling still 2.
Open sampling still 2, with solid in suitable dissolution with solvents still, and measure its content (see Kjeldahl's method).
11, solute just to be calculated under experiment condition in the solubleness of supercritical ammine system according to the amount of the ammonia amount that records and solute.
Supercritical ammine system solubility test device of the present invention obtains in the experiment measuring ammonium chloride solubleness in supercritical ammine system: temperature 150 DEG C, under pressure 12MPa, its mole fraction is 0.0298.
Illustrate: also can on pretreatment, first carry out the preliminary experiment of the cycle efficieny measuring circulating device, its method of operating is as follows:
1) sampling still 2 is pulled down, and imported and exported two pipelines connected (that is, pipeline II 24 and pipeline III 25 are corresponding is respectively connected with two-way by valve 9, valve 11) by two-way; Pulled down by equilibrium still 1 kettle, all the other devices connect according to shown in Fig. 1.
2) bottom insert canal (i.e. the bottom of extension pipe 32) on equilibrium still 1 is inserted in liquid soap.
3) by magnetic piston 31 from the right side toward left movement once, measure the diameter lathery that bottom insert canal (extension pipe 32) generates in liquid soap, thus estimate the volume of the fluid that piston movement once can be carried.
Because the viscosity of supercritical fluids system is close with gas, so the conveying adopting air to transport simulation supercritical solution is feasible; And resistance major part comes from pipeline and valve in experimentation, ignoring the resistance of motion produced in sampling still 2, is also feasible.And can find, the movement velocity of magnetic piston 31 is faster, and the volume of air of carrying is larger, therefore in specific experiment process, each circulation should make the movement velocity of magnet fast as far as possible.
In sum, the circulating device in the present invention can meet the requirement of the mass exchange accelerated in operation in equilibrium still 1 and sampling still 2.
In the present invention, if an ebullator that can use under experimental conditions can be found to replace circulating device, device of the present invention and operation steps will be made more simple.Following requirement is had: 1. heatproof 200 DEG C, withstand voltage more than 18MPa for this ebullator; 2. corrosion resistance is strong, does not react, can not be dissolved in supercritical ammine system with ammonia or solute; 3. flow is less, at below 500mL/min.
Confirmatory experiment: adopt the dynamic method (J.Chem.Eng.Data1986 that degree of accuracy generally acknowledged is at present the highest, 31:285-288) detect, ammonium chloride is temperature 150 DEG C, and the solubleness in the supercritical ammine system of pressure 12.0MPa is 0.0293, close with experiment the data obtained.
Comparative example 1,
Make the length of cylindrical case 3 into 5cm by 20cm, all the other are equal to embodiment 1.Now, magnetic piston 31 the discharged liquor capacity that often moves once is 0.5 to the maximum
2× π × 5=3.93cm
3be less than the content volume of pipeline III 25.Experiment finds, almost without solute in sampling still 2.
Comparative example 2,
Make the volume of sampling still 2 into 10mL by 20mL, all the other are equal to embodiment 1.Test, measure ammonium chloride at 150 DEG C, the solubleness in the supercritical ammine of 12.0MPa is 0.0310.
Comparative example 3,
Adopt embodiment 1 equipment therefor, recording temperature is 140 DEG C, and pressure is under the condition of 11.7MPa, and the solubleness of ammonium chloride in supercritical ammine is 0.0267.Higher with temperature, pressure is larger, and the general knowledge that solubleness is higher conforms to.
Finally, note also, the just example of this device in supercritical fluids system solubility test more than enumerated.Obvious the present invention can be applied to ammonium chloride incessantly in this experiment of supercritical ammine system solubility test.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (9)
1. supercritical ammine system solubility test device, is characterized in that: be made up of cyclic balance sampling system and sample analysis system;
Described cyclic balance sampling system comprises equilibrium still (1), sampling still (2), circulating device, the gateway I of equilibrium still (1) is passed through threeway I (13) successively and is with valvular pipeline I (23) to be connected with circulating device, circulating device is connected with the gateway I of sampling still (2) by the valvular pipeline II (24) of band, the gateway II of sampling still (2) is connected with the gateway II of equilibrium still (1) by the valvular pipeline III (25) of band and threeway II (14) successively, thus forms a circulation system;
Valvular ammonia-feeding pipe (22) is with to be connected with threeway I (13); Be provided with the gas outlet (26) of valve at the top of equilibrium still (1), described gas outlet (26) is connected with threeway II (14);
Equilibrium still (1), sampling still (2) are all immersed in oil bath pan (15), and pipeline I (23), pipeline II (24), pipeline III (25) are equipped with heating tape;
Described sample analysis system comprises gas meter (17) and gas extractor, described gas extractor comprises at least one gas bottle, the valvular gas collecting pipe (27) of one end connecting band of gas meter (17), the other end of gas meter (17) is connected by the bore seal of connecting pipe (28) and gas bottle.
2. supercritical ammine system solubility test device device according to claim 1, is characterized in that:
Described circulating device comprises totally enclosed cylindrical case (3), arranges the magnetic piston (31) of the inwall movement being close to cylindrical case (3) in cylindrical case (3);
Described circulating device also comprises the magnet (30) matched with magnetic piston (31).
3. supercritical ammine system solubility test device device according to claim 2, is characterized in that:
Described magnetic piston (31) is made up of cylindrical inner case (311) and the iron prop (312) that is arranged in cylindrical inner case (311) inner chamber, and the outer wall of iron prop (312) and the inwall of cylindrical inner case (311) form interference fit.
4. the supercritical ammine system solubility test device device according to Claims 2 or 3, is characterized in that:
Circulating device in use, often move once the manifold volume between gateway II that the volume of discharged solution should be greater than gateway II to the equilibrium still 1 of sampling still 2 by magnetic piston (31).
5. supercritical ammine system solubility test device device according to claim 4, is characterized in that:
In gas bottle, arrange funnel (21), what connecting pipe (28) sealed with the funnel (21) in gas bottle is connected.
6. supercritical ammine system solubility test device device according to claim 5, is characterized in that:
Equilibrium still (1) is provided with tensimeter and thermopair; Gas bottle is provided with tensimeter.
7. supercritical ammine system solubility test device device according to claim 5, is characterized in that:
Extension pipe (32) is provided with in the inner chamber of equilibrium still (1), the lower port of extension pipe (32) is near the bottom of equilibrium still (1), and what the upper port of extension pipe (32) sealed with threeway I (13) is connected.
8. the method for the mensuration supercritical ammine system solubleness utilizing the arbitrary device of claim 1 ~ 7 to carry out, is characterized in that comprising the following steps:
1), in equilibrium still (1), the excessive and solid solute to be measured be relatively positioned is placed in advance;
Adopt the method for directly filling with liquefied ammonia, the liquefied ammonia corresponding with condition determination adopting P-R equation estimation to go out by ammonia-feeding pipe (22) disposable input in equilibrium still (1);
2), by control temperature carry out the intrasystem pressure of controlled circulation balanced sampling and reach desired experiment condition, and temperature and pressure condition all to reach more than the super critical condition of ammonia;
3), the magnetic piston (31) in circulating device is attracted to make back and forth movement in cylindrical case (3) with magnet (30), thus drive the flowing of cyclic balance sampling system internal solvent, accelerate the solution in equilibrium still (1) and the solution equilibria in sampling still (2);
4), by the closedown of by-pass valve control, from cyclic balance sampling system, sampling still (2) is taken off;
5) method of cooling, is used, reduce the pressure in sampling still (2), sampling still (2) is connected with sample analysis system, thus makes the ammonia in sampling still (2) be all released in gas bottle, finally carry out the mensuration of the amount of solute and solvent.
9. the method for mensuration supercritical ammine system solubleness according to claim 8, is characterized in that: in gas bottle, arrange acid solution, by the mode with HCI; Obtain the amount of the ammonia in sampling still (2).
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