• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Equipment for the determination of the isobaric equilibrium vapor-liquid-solid and vapor-liquid-liquid-solid. The invention consists of a device for determining the balance when there are solids present. The equipment includes a boiler that houses an ultrasonic probe that facilitates the reduction of the particle size of the solid, a separation chamber attached to the boiler that is connected to a condenser to carry out steam condensation and stable recirculation, and a flask mixer. Additionally, the diameter of the duct connecting the boiler and the mixing flask has been increased to be sufficient to allow the circulation of solids without obstruction and a recirculation device formed by a recirculation duct with an external electrical resistance has been incorporated. controlled to keep the mixture at bubble temperature. Likewise, valves for cleaning and sampling have been installed in the equipment. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2715502A1
    申请号:ES201830582
    申请日:2018-06-14
    公开日:2019-06-04
    发明作者:Yagües Vicente Gomis；Steegman Juan Carlos Asensi；Ferrandiz Maria Dolores Saquete；Escamilla Alicia Font；Cano Jorge Garcia；Blasco Alejandro Gomis
    申请人:Universidad de Alicante；
    IPC主号:
    专利说明:

    [0001] EQUIPMENT FOR THE DETERMINATION OF THE ISOBARIC BALANCE VAPOR-LIQUID-
    [0002]
    [0003]
    [0004]
    [0005] FIELD OF THE INVENTION
    [0006] The present invention relates to a device that allows the determination of thermo-dynamic equilibrium vapor-liquid-solid and vapor-liquid-liquid-solid isobaric in systems with solid phase and a phase or two liquid phases. The knowledge of this balance is fundamental for the design of equipment in industrial chemical processes such as extractive salt distillation or solvent regeneration.
    [0007]
    [0008] STATE OF THE PREVIOUS TECHNIQUE
    [0009] In an investigation carried out by the Working Party on Thermodynamic and Transport properties of the European Federation of Chemical Engineering, EFCE (GM Kontogeorgis et al., Ind. Eng. Chem. Res., 49 (22), (2010), 11131-11141) on the requirements that the industry needed in the field of thermodynamics, it became clear the imperative need to have accurate, reliable and thermodynamically consistent experimental equilibrium data of different mixtures of compounds, to be able to perform design calculations in processes of separation by distillation.
    [0010]
    [0011] Among these, the systems of solvent mixtures with electrolytes is one of the fields where this lack of data is notorious. Obtaining data for these systems is not simple due to the presence of solids (the electrolyte), together with the existence of two liquid phases that may be present. Both circumstances cause that the speed of transfer of matter between all the present phases is slow and delays and makes difficult to reach the balance vapor-liquid-solid and vapor-liquid-liquid-solid that it is desired to determine.
    [0012]
    [0013] The determination of the isobaric equilibrium between phases requires equipment that allows to accurately measure, for a set pressure, the boiling temperature of the mixture and separate the present phases to later measure their composition. According to the number of present phases (vapor-liquid, vapor-liquid-liquid, vapor-liquid-solid or vapor-liquid-liquid-solid) the equipment to be used varies.
    [0014]
    [0015] For the simplest determination of isobaric equilibrium, such as the vapor-liquid equilibrium in homogeneous systems with a single liquid phase present besides the vapor phase, there are different methods that allow to obtain the boiling temperature of the liquid, separating it from the vapor in equilibrium with him and determine the composition of both phases. The best known are:
    [0016]
    [0017] - Distillation method: the oldest but rarely used nowadays since it usually produces errors in the measured temperature and in the composition of both phases due to the rectification of the mixture that is produced in the upper part of the distiller.
    [0018] - Dynamic method with single-phase recirculation (Othmer method): it largely minimizes previous systematic errors but does not completely eliminate them. - Dynamic method with two recirculations (Guillespie method): one recirculation for the homogeneous liquid phase and another for the vapor phase. It is the most used method with which precise data of the vapor-liquid isobaric equilibrium is obtained.
    [0019]
    [0020] However, when what is desired to be determined is the vapor-liquid-liquid isobaric balance, the application of the Guillespie method would not be possible since the recirculation of the mixture formed by two liquid phases can only be carried out if there is a good dispersion of the two liquid phases. This can be achieved using ultrasound that promotes this dispersion. To solve this problem, the patent ES2187220 B2 was developed and is being marketed through a license to a company. However, this equipment can not be applied directly to the determination of the isobaric equilibrium vapor-liquid-solid and vapor-liquid-liquid-solid because the presence of solids makes it difficult and prevents the recirculation of the liquid phase due to the solid particles that it carries in suspension.
    [0021]
    [0022] The determination of the isobaric equilibrium vapor-liquid-solid and vapor-liquid-liquid-solid to which the present application refers has been tried to be carried out to date using equipment with only the recirculation of the vapor phase (Othmer method). Thus, different authors (Johnson and Furter., Can. J. Chem. Eng., June, (1960) 78-86, Morrison et al., J. Chem. Eng. Data 35 (1990) 395-404 and Ch.-L. et al. J. Chem. Eng. Data, 38 (1993) 306-309) determined data from different systems using Othmer equipment but as recently shown (García-Cano et al., J. Chem. Therm. 116 (2018) 352-362 ) the data obtained were not precise, differed among them and even some were thermodynamically inconsistent. The problem is that with these equipment the balance between phases is not adequately reached.
    [0023]
    [0024] There is thus a need to provide equipment that solves the problems described in the state of the art, that is to say that allows for a fixed pressure to determine with precision the boiling point of a solid-liquid-liquid mixture, to separate all the present phases and obtain their composition.
    [0025]
    [0026] EXPLANATION OF THE INVENTION
    [0027] The present invention solves the problems described above since it relates to a device for the determination of the vapor-liquid-solid and vapor-liquid-liquid-solid isobaric equilibrium.
    [0028]
    [0029] The starting point is a device for the determination of vapor-liquid-liquid balance protected by a patent ES2187220 B2 owned by the Alicante University that was developed by some of the inventors of this same invention. The aforementioned patent protects equipment that allows the determination of vapor-liquid-liquid balance and that uses an ultrasonic probe to carry out the dispersion of the two liquid phases present.
    [0030]
    [0031] Starting from the previous equipment and in view of the problems cited in the state of the art, in order to determine the isobaric balance vapor-liquid-solid and vapor-liquid-liquid-solid, it has been investigated to carry out the adaptation of the equipment mentioned above and generate a technical solution to this problem; solution that although apparently simple, has involved solving different technical problems to finally get a team fully prepared to be marketed.
    [0032] Thus, the present invention refers to an equipment comprising a boiler that carries inside it an electrical resistance coated with a quartz sleeve whose heating power is fixed with an external controller. Said boiler has an ultrasonic probe attached that allows to apply ultrasounds to the mixture. To do this, it has a side tube designed to house the aforementioned probe, located in the lower part of the boiler and with the minimum possible inclination with respect to its imaginary axis, being always less than 45 °.
    [0033]
    [0034] The boiler is connected at the top, through a Cotrell pump, with a separating chamber and at the bottom with a mixing flask through a duct, which joins the boiler and the flask, with an inside diameter sufficient for allow the circulation of solids inside without causing obstructions.
    [0035]
    [0036] The separation chamber is thermally insulated from the outside by a Dewar cup type insulation and contains a thermometer with which the boiling temperature is precisely measured and a pressure gauge that linked to a controller allows the pressure of the system to be adjusted to a value determined.
    [0037]
    [0038] The upper part of said separation chamber is connected to a condenser which carries out the condensation of the steam and the stable recirculation of this phase until reaching the mixing flask (recirculation I) through a recirculation duct I.
    [0039]
    [0040] On the other hand, the lower part of the separation chamber is also connected to the mixing flask (recirculation II) through a recirculation device comprising at least one recirculation duct II with an externally coiled resistance and covered with insulation and an element temperature gauge located between the insulator and the resistance, and which is attached to a controller on which a temperature setpoint signal equal to the bubble temperature of the sample has been established.
    [0041]
    [0042] The two ducts of both recirculations are again attached to the mixing flask. The mixing flask comprises a mixing element for mixing the two streams that reach it and that joins them again to the reboiler.
    [0043]
    [0044] In addition, the equipment includes a series of valves that allow, among other things, the intake of samples and cleaning the sampling ducts.
    [0045]
    [0046] In a particular embodiment, the diameter of the conduit connecting the reboiler to the mixing flask is 1-1.5 cm.
    [0047]
    [0048] In a particular embodiment, the temperature measuring element located in the recirculation conduit II between the resistance and the insulator is a thermocouple.
    [0049]
    [0050] In a particular embodiment, the flask comprises an external magnetic stirrer and a magnet.
    [0051]
    [0052] In a particular embodiment, the flask comprises an external electrical resistance coated with an insulator and a temperature controller.
    [0053]
    [0054] In a particular embodiment, the recirculation conduit II comprises two valves, one for sampling and one for cleaning.
    [0055]
    [0056] During operation, the mixture whose vapor-liquid-liquid-solid or vapor-liquid-solid balance is to be determined is placed inside the equipment occupying the boiler and the mixing flask, the electric resistance heats the solid and liquid mixture to be tested and with the application of ultrasound is achieved on the one hand a very fine dispersion of the liquids present and on the other the decrease in particle size and suspension of the solid phases. In this way, the transfer rates of matter between the different phases are increased and with this, the time to reach equilibrium is greatly reduced.
    [0057]
    [0058] The suspension-dispersion that is in the boiler, together with the steam generated in it by the energy input of the electrical resistance located inside, is raised by the Cottrell pump to a higher area of the equipment where it is separated from the vapor phase , the equilibrium temperature is measured and both the mixture and the vapor are recirculated by gravity through the two recirculations described above.
    [0059]
    [0060] Through the recirculation I, the generated steam is condensed and recirculated to the mixing flask. On the other hand, through the recirculation II, the mixture of liquids and non-evaporated solids is recirculated. As the solubility of the solid usually decreases with temperature, the Cooling of the liquid and solid mixture circulating through the recirculation duct II would produce the precipitation of the solid and the obstruction of the duct. Therefore, recirculation duct II must be heated externally to a temperature controlled and close to the bubble temperature, this being one of the novelties of the proposed equipment to solve one of the problems cited above that would have the equipment that can not handle solids .
    [0061]
    [0062] Then, the two recirculation ducts enter the flask where they are mixed by means of the stirrer placed inside the flask. For the same reasons as to change the solubility of the solid with temperature, the mixing flask must be coated with insulation to prevent heat loss. In some cases in which the amount of solid that can precipitate by the temperature decrease is very large, it must also be heated externally to a controlled temperature and close to the bubble temperature in the same way as recirculation duct II.
    [0063]
    [0064] In addition, the heaters on the recirculation duct II and on the mixing flask allow the dissolution of a large part of the solid that may have precipitated there by cooling the material, starting from the ambient temperature during the start-up process. mix after the completion of an experiment performed previously.
    [0065]
    [0066] Of special importance and also novelty is the design of the valves. For the elimination of the particles remaining in the sample collection tube, the new entrance, located just above the sampling one, is added to the equipment, which allows to add liquid from the outside to dissolve the solids that have been deposited with object to leave it ready for a new sampling. The remaining liquid remains are eliminated by application of vacuum.
    [0067]
    [0068] As mentioned above, this equipment allows stable recirculation at a temperature very close to that of the suspension bubble and the dispersion of the solid and liquid phases and the taking of samples for analysis. These drawbacks are the main problems of the equipment that do not allow to deal with samples with dissolved solids and in suspension, preventing the determination of the isobaric equilibrium vapor-liquid-solid and vapor-liquid-liquid-solid.
    [0069] Regarding the methodology to carry out the measure, it must:
    [0070]
    [0071] ● Introduce the mixture to be determined in the reboiler and in the mixing flask.
    [0072]
    [0073] ● Heat and stir with ultrasound until the sample boils.
    [0074]
    [0075] ● Heat the resistance that covers the recirculation duct II with the controller.
    [0076] ● Heat the resistance around the mixing flask.
    [0077]
    [0078] ● Adjust the liquid level in the boiler and the heating power and the ultrasonic probe until the flow rates of both recirculations are small and stable.
    [0079]
    [0080] ● Wait for the necessary time until reaching the steady state and with that the boiling temperature is stable.
    [0081]
    [0082] ● Take samples of the condensed vapor phases and rest of liquid and solid phases using the valves of the equipment or by means of some online sampling method. The solid-liquid or solid-liquid-liquid mixture should be taken through the valves on thermostatic tubes at the same temperature as the bubble of the sample, let the solid and liquid phases present be separated by gravity and proceed to the capture of samples of each of the present phases.
    [0083]
    [0084] ● Analyze the samples taken.
    [0085]
    [0086] To give continuity to the measurements and to be able to carry out subsequent experiments, the cleaning of the sampling tube described above is necessary. In the equipment that deals only with liquids, this cleaning can be done by applying a vacuum that produces the evaporation of the remains that remain from the sampling of the previous experiment; but in the case of the presence of solids, the vacuum does not eliminate them and an additional entry is necessary right at the beginning of the sampling tube to be able to inject a solvent that dissolves them and eliminates them avoiding the contamination of the samples taken later .
    [0087]
    [0088] BRIEF DESCRIPTION OF THE FIGURES
    [0089] To complement the description made and in order to help a better understanding of the characteristics of the invention, an illustrative and non-limiting drawing is attached as an integral part of said description.
    [0090]
    [0091] Figure 1. Schematic sample of the equipment for determining the equilibrium solid vapor-liquid and vapor-liquid-liquid-solid
    [0092]
    [0093] DETAILED EXHIBITION OF REALIZATION MODES
    [0094] The equipment comprises the boiler 1 internally heated by an electrical resistor 2 covered by a quartz sleeve. The boiler 1 has a side tube arranged in the lower part and with an inclination with respect to its imaginary axis less than 45 °. Said tube contains the ultrasound probe 3 inside it.
    [0095]
    [0096] The boiler 1 is connected at the top with the separation chamber 5 and at the bottom with the mixing flask 7 through the conduit 10 connecting the boiler with the mixing flask. This duct has an inner diameter of 1-1.5 cm.
    [0097]
    [0098] The mixing flask 7 incorporates another external electrical resistance coated with insulation and a temperature controller.
    [0099]
    [0100] The upper part of the separation chamber 5 is connected with a condenser to carry out steam condensation and stable recirculation (recirculation I) to the mixing flask 7.
    [0101]
    [0102] The lower part of the separation chamber is connected to the mixing flask 7 through the recirculation device 15. This recirculation device 15 comprises the conduit 6 which carries the electrical resistance 8 covered with insulation 9 with a thermocouple which is connected to a controller on which a temperature setpoint signal equal to the bubble temperature of the sample has been established.
    [0103]
    [0104] On the other hand, at the end of the circulation duct 6, there is the electrically operated valve 11 which is the one that allows the taking of samples through the outlet 12.
    [0105]
    [0106] The solid-liquid or solid-liquid-liquid mixture whose bubble temperature and composition of the vapor phase in equilibrium is to be determined is placed in the reboiler (also occupying the mixing flask). There, the ultrasounds 3 disperse the liquid phases, decrease the particle size of the solid and put them in suspension while the heat provided by the electrical resistance 2 raises its temperature up to the bubble temperature producing bubbles steam.
    [0107]
    [0108] The inclined arrangement of the ultrasonic probe 3 together with the steam bubbles produced causes the release of the suspension dispersion vapor mixture upwards where it is collected by the Cotrell pump 4 which continues to raise the mixture to the separation chamber 5 where separation occurs. of the vapor of the rest of liquid and solid phases. The thermometer contained in the camera allows to measure the equilibrium temperature.
    [0109]
    [0110] From there, the separated steam is recirculated (recirculation I) back to the reboiler condensing it in the condenser and taking it to the mixing flask 7 through the conduit 14.
    [0111]
    [0112] On the other hand, the mixture with the dispersion of phases and suspension of particles descends by the recirculation device 15. In this way, the mixture descends through the circulation conduit 6 to the mixing flask 7. The controller modifies the electric power supplied to resistance 8 to reach the pre-set temperature on the outside of the duct.
    [0113]
    [0114] For the elimination of the particles that remain in this conduit after taking the sample in order to leave it ready for a new sampling, the entrance 13 is incorporated into the equipment that allows to add liquid from the outside to dissolve the solids that have been deposited . The liquid remains that may remain in the conduit are eliminated by application of vacuum.
    [0115]
    [0116] As an example, the new equipment was used in the determination of two ternary systems whose equilibrium data could not be obtained with other equipment due to the problems mentioned above. Specifically, they tested with the LABODEST® VLLE 602 and had different problems in that in the return conduction of the suspension salt precipitation occurred. Since said precipitation was prior to taking samples, changes in the composition of the circulating liquid occurred and consequently the collected sample did not have the composition corresponding to the equilibrium. As the precipitation continued, it reached a point where the pipe was completely obstructed by the deposition of salt, it stopped recirculating liquid and ultimately the equipment stopped working.
    [0117]
    [0118] Next, in tables 1 and 2, the vapor-liquid-liquid-solid equilibrium data obtained where the compositions of the two liquid phases and the vapor phase (in mole fraction) are specified, as well as the bubble temperature.
    [0119]
    [0120] Table 1. Vapor-liquid-liquid-solid equilibrium data of the water system K2SO4 2-methyl 2-propanol at 101.3 kPa. Compositions in molar fractions.
    [0121]
    [0122]
    [0123]
    [0124]
    [0125] Table 2. Vapor-liquid-liquid-solid equilibrium data of the water system NH4Cl 2-propanol at 101.3 kPa. Compositions in molar fractions.
    [0126]
    [0127]
    权利要求:
    Claims (6)
    [1]
    1. Equipment for the determination of the vapor-liquid-solid and vapor-liquid-liquid-solid isobaric equilibrium comprising at least:
    a boiler that has inside it an ultrasonic probe housed in a tube arranged in the lower part with an inclination always lower than 45 °,
    a separating chamber thermally isolated from the outside, joined to the boiler through a Cotrell pump, which comprises a thermometer and a pressure meter linked to a controller, and which is connected to a condenser to carry out the condensation of the steam and the stable recirculation,
    a mixing flask, attached to the reboiler, comprising a mixing element, characterized by :
    understand a duct that connects the boiler and the mixing flask and has a sufficient inner diameter to allow the circulation of solids inside without causing blockages,
    comprising a recirculation device comprising at least one recirculation duct with an externally coiled resistance coated with insulation and a temperature measuring element located between the insulator and the resistance, and which is attached to a controller on which a signal has been established of temperature setpoint equal to the bubble temperature of the sample,
    understand at least two valves.
    [2]
    2. Equipment for determining the vapor-liquid-solid and vapor-liquid-liquid-solid isobaric equilibrium according to claim 1, wherein the diameter of the duct connecting the reboiler to the mixing flask is 1-1.5 cm.
    [3]
    3. Equipment for the determination of the vapor-liquid-solid and vapor-liquid-liquid-solid isobaric equilibrium according to claim 1, wherein the temperature measuring element located in the recirculation conduit II between the resistance and the insulator is a thermocouple.
    [4]
    4. Equipment for determining the vapor-liquid-solid and vapor-liquid-liquid-solid isobaric equilibrium according to claim 1, wherein the flask comprises an external magnetic stirrer and a magnet.
    [5]
    Equipment for the determination of the vapor-liquid-solid and vapor-liquid-solid-liquid isobaric balance according to claim 1, wherein the flask comprises an external electrical resistance covered with an insulator and a controller temperature.
    [6]
    6. Equipment for determining the vapor-liquid-solid and vapor-liquid-liquid-solid isobaric equilibrium according to claim 1, wherein the recirculation conduit of the recirculation device comprises a valve for sampling and another for cleaning.
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    同族专利:
    公开号 | 公开日
    ES2715502B2|2020-06-10|
    WO2019238986A1|2019-12-19|
    引用文献:
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    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    ES201830582A|ES2715502B2|2018-06-14|2018-06-14|EQUIPMENT FOR THE DETERMINATION OF THE ISOBARIC BALANCE VAPOR-LIQUIDO-SOLIDO AND VAPOR-LIQUIDO-LIQUIDO-SOLIDO|ES201830582A| ES2715502B2|2018-06-14|2018-06-14|EQUIPMENT FOR THE DETERMINATION OF THE ISOBARIC BALANCE VAPOR-LIQUIDO-SOLIDO AND VAPOR-LIQUIDO-LIQUIDO-SOLIDO|
    PCT/ES2019/070354| WO2019238986A1|2018-06-14|2019-05-28|Equipment for determining the isobaric vapour-liquid-solid and vapour-liquid-liquid-solid equilibrium|
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