WO2013068617A1 - Équipement pour la détermination de l'adsorption de mélanges binaires de gaz dans des solides adsorbants - Google Patents

Équipement pour la détermination de l'adsorption de mélanges binaires de gaz dans des solides adsorbants Download PDF

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Publication number
WO2013068617A1
WO2013068617A1 PCT/ES2012/070730 ES2012070730W WO2013068617A1 WO 2013068617 A1 WO2013068617 A1 WO 2013068617A1 ES 2012070730 W ES2012070730 W ES 2012070730W WO 2013068617 A1 WO2013068617 A1 WO 2013068617A1
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WIPO (PCT)
Prior art keywords
adsorption
cell
gas
equipment
determination
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Application number
PCT/ES2012/070730
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English (en)
Spanish (es)
Inventor
Juan ALCAÑIZ MONGE
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Universidad De Alicante
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Application filed by Universidad De Alicante filed Critical Universidad De Alicante
Publication of WO2013068617A1 publication Critical patent/WO2013068617A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N7/00—Analysing materials by measuring the pressure or volume of a gas or vapour
    • G01N7/02—Analysing materials by measuring the pressure or volume of a gas or vapour by absorption, adsorption, or combustion of components and measurement of the change in pressure or volume of the remainder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0454—Controlling adsorption

Definitions

  • the present invention falls in general within the field of technology and in particular refers to equipment for the determination of the individual amounts of a mixture of gases that are adsorbed in a porous solid.
  • Adsorption of gases in porous solids is a phenomenon of great industrial interest in processes of separation of gas mixtures, for example in the separation of air components, of purification of gas streams from industrial processes (NO x , S0 2 , CO, C0 2 , VOC, dioxins, HCI), purification of natural gas (H 2 S), recovery and concentration of gaseous fuels (obtaining of iron in the blast furnace, coke shops, refineries) [F. Rouquerol, J. Rouquerol, K. Sing, Adsorption by Powder and Porous Solids: Principies, Methodology and Applications. Academic Press Inc: Cornwall, 1999].
  • the pressure measurement only serves to determine the amount of the total moles initially set that have been adsorbed, but not the relative amounts of each of them.
  • the evaluation of the applicability of an adsorbent for the treatment of a certain gas mixture is commonly carried out by means of the experimental measurement of the individual components, and its subsequent estimation by theoretical models [AL Myers, JM Prausnitz, AlChE Journal 1 1 (1965) 121; O. Talu, I. Zwiebel, AlChE Journal 32 (1986) 1263 .; JU Keller, Physica A 166 (1990) 180; S. Jiang, PB Balbuena, KE Gubbins, J.
  • the composition of the gas mixture is determined by incorporating equipment capable of determining its density, based on two physical principles, such as the effusion of gases and the resonant frequency of a solid.
  • Effusion is the process of the flow of a gas from a region of high pressure to a low pressure through a small hole whose diameter is of the order of 10 times smaller than the average free path of the molecules that pass through it [M. Knudsen, Ann. Phyaik 28 (1909) 75]. Under these conditions the velocities of the passage of the molecules are inversely proportional to the square roots of their respective densities. The validity of this phenomenon for determining the densities of a gas mixture was demonstrated by K. Nash [F.E. Harris, L. K. Nash, Analytical Chemistry 22 (1950) 1552]. In the same vein, U.S. Patent 4934178 includes the design of an equipment based on this same principle to determine the density of a gas [US Patent 4934178 Issued 19 Juny, 1990].
  • the scheme of this equipment is detailed in Figure 1.
  • the equipment is composed of a calibration cell, whose volume is known (Vref), connected to an adsorption cell, where the porous solid to be analyzed is housed.
  • a certain amount of gas is initially introduced into the calibration cell, up to a certain pressure in said cell.
  • the expansion of the gas contained in the calibration cell to the adsorption cell is allowed.
  • a decrease in the pressure in the calibration cell takes place.
  • the present invention includes a volumetric adsorption equipment capable of measuring co-adsorption of two components of a mixture of gases
  • An element capable of determining the density of a gas mixture has been incorporated into said equipment, in this way the equipment finally consists of three cells: calibration cell where the quantity of gas to be supplied is controlled; adsorption cell, where the porous solid to be characterized is introduced; and auxiliary cell, in which the density of the existing gas mixture is determined when the equilibrium condition between the gas phase and the adsorption capacity of the porous solid is reached.
  • the temperature and pressure of each cell is determined by the inclusion of thermocouples and capacitance gauges.
  • the control of the inlet and distribution of the gas mixture to each of the cells is regulated by a valve system and a vacuum line connected to a vacuum pump.
  • the equipment is composed of a cell of known volume, calibration cell, which is connected to a cell where the sample is introduced and adsorption is performed, adsorption cell. Both cells have sensors to determine the pressure and temperature in them.
  • a system of automatic shut-off valves connected to each other allows both the inlet of the gas mixture to be controlled by the first metering valve to the calibration cell and expansion valve to the adsorption cell, as well as the emptying of both cells, by means of the valve of evacuation of the calibration cell and the evacuation valve of the absorption cell, which is done by means of a vacuum pump.
  • the equipment is completed with the incorporation of an auxiliary cell, where the expansion of the gas present in the calibration cell is carried out. This cell has a sensor to determine the pressure in it.
  • the most relevant technical aspect of this equipment is the design of the entrance to the auxiliary cell, which is restricted by the incorporation of an orifice membrane, which either has a hole smaller than 0.01 mm or a Venturi type restriction or subsonic root-square type.
  • the emptying of the auxiliary cell is regulated by incorporating a valve connected to the vacuum line.
  • the part where the calibration cell and the auxiliary cell are located, and the system of pipes and cut-off valves that are connected to the adsorption cell, are thermostatted, so that the temperature is kept constant throughout the experiment at 40 ° C.
  • the part of the adsorption cell is also thermostated, whose temperature can be adjusted to the conditions under which the adsorption experiment is to be performed.
  • Figure 1 shows the diagram of a volumetric adsorption equipment, composed of two cells: adsorption cell 5 and calibration cell 6; of a valve system: metering valve 1, expansion valve 2, evacuation valve of the calibration cell 3, evacuation valve of the adsorption cell 4; and of sensors to determine the pressure and temperature of the adsorption cell 5 (10 and 1 1, respectively) and of the calibration cell 6 (12 and 13, respectively).
  • the gas inlet and outlet of the equipment is controlled by a gas dispenser 15 and a vacuum pump 16.
  • Figure 2 shows the scheme of a modified volumetric adsorption equipment for the determination of the density of the gas in the equilibrium by its effusion to an auxiliary cell 9, with a valve system: metering valve 1, expansion valve 2, valve evacuation of the calibration cell 3, evacuation valve of the adsorption cell 4, expansion valve to the auxiliary cell 7 and evacuation valve of the auxiliary cell 8; and of sensors for determining the pressure and temperature of the adsorption cell 5 (10 and 1 1, respectively), of the calibration cell 6 (12 and 13, respectively) and of the auxiliary cell (14).
  • the gas inlet and outlet of the equipment is controlled by a gas dispenser 15 and a vacuum pump 16.
  • the equipment is composed of a calibration cell 6, which is connected to the adsorption cell 5, where the sample is introduced and the adsorption is performed.
  • These two cells have sensors to determine the pressure (10 and 12, respectively) and temperature (1 1 and 13, respectively) existing in them, and incorporate a system of automatic shut-off valves joined together that allows the gas inlet to be controlled through the gas dispenser 15, by means of the metering valve 1 and expansion valve 2, and the emptying of the cells, by means of the evacuation valve of the calibration cell 3 and the evacuation valve of the absorption cell 4, which It is carried out by means of a vacuum pump 16.
  • the area of the calibration cell 6, the ducting system and the shut-off valve that is connected to the adsorption cell 5, is thermostatted, so that the temperature of this whole part of the equipment is kept constant throughout the experiment, specifically at 40 ° C (determined by temperature sensor 13).
  • the part of the adsorption cell 5 is also thermostated, whose temperature can be adjusted to the conditions to which the adsorption experiment is to be performed (determined by the temperature sensor 11).
  • the adsorbed amount of a gas in a solid adsorbent is operated as follows.
  • a certain amount of gas is introduced through the gas dispenser 15 into the calibration cell 6 by opening the metering valve 1.
  • P ⁇ the pressure of this cell
  • V ref the volume of this cell
  • the expansion valve 2 is opened, the gas expanding to the adsorption cell 5. In this, the adsorption of part of the gas in the porosity of the adsorbent material takes place, thereby reducing the pressure (determined by the pressure sensor 12 ).
  • thermodynamic equilibrium between the amount of gas present in the gas phase and the amount of gas that the solid can adsorb under these conditions of pressure P e and temperature has been reached.
  • V ref calibration cells
  • V s adsorption system
  • n ⁇ P ⁇ V ref / Z ⁇ RT ref
  • n e P e V s / Z and RT e
  • a volumetric adsorption device determines a decrease in pressure (pressure sensor 12) after the expansion of the gas mixture from the calibration cell 6 to the adsorption cell 5, and with this the total amount is calculated of moles of adsorbed gases, but it cannot be discerned in what proportion they have been adsorbed.
  • FIG. 2 describes the design of a volumetric adsorption equipment (Zone A) with the incorporation of a device for the determination of gas density based on the phenomenon of gas effusion (Zone B).
  • a volumetric adsorption equipment only requires the incorporation of a new auxiliary cell 9, in which the expansion of the present gas is carried out. in the calibration cell 6, once equilibrium has already been reached in the adsorption cell 5.
  • the vacuum Prior to the introduction of the gas from the adsorption cell 5, the vacuum is carried out in the auxiliary cell 9 through the valve 8 by means of the vacuum pump 16.
  • the entrance to the auxiliary cell 9 is restricted by the incorporation of an orifice membrane 7 which has a hole smaller than 0.01 mm or a Venturi type or root-square subsonic type restriction.
  • the calibration procedure which only needs to be done once a year (and only for the purpose of checking that the pressure measurement systems of the adsorption cell 5 and the auxiliary cell 9 have not been adjusted), consists of introducing a certain quantity of gas to be analyzed (through the chlorinator 15) in the calibration cell 6 to a predetermined pressure ( ⁇ ⁇ ) (determined by the sensor 12).
  • ⁇ ⁇ predetermined pressure
  • the expansion valve is opened to the auxiliary cell 7, determining the passage time (ti) of the gas to the auxiliary cell 9.
  • a series of calibrations is carried out covering a wide pressure range This data is stored as part of the adsorption equipment program software The same procedure is performed with other pure gases.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Immunology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Biochemistry (AREA)
  • Combustion & Propulsion (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Pathology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Of Gases By Adsorption (AREA)
  • Measuring Fluid Pressure (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)

Abstract

L'invention concerne un équipement pour la détermination de l'adsorption de mélanges binaires de gaz dans des solides adsorbants. La présente invention concerne un équipement servant à déterminer les quantités individuelles de deux gaz qui sont adsorbés simultanément dans un solide poreux, lequel est en contact avec un mélange de deux gaz à une pression et dans une composition déterminées.
PCT/ES2012/070730 2011-11-07 2012-10-19 Équipement pour la détermination de l'adsorption de mélanges binaires de gaz dans des solides adsorbants WO2013068617A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ESP201101198 2011-11-07
ES201101198A ES2403016B2 (es) 2011-11-07 2011-11-07 Equipo para la determinación de la adsorción de mezclas binarias de gases en sólidos adsorbentes.

Publications (1)

Publication Number Publication Date
WO2013068617A1 true WO2013068617A1 (fr) 2013-05-16

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PCT/ES2012/070730 WO2013068617A1 (fr) 2011-11-07 2012-10-19 Équipement pour la détermination de l'adsorption de mélanges binaires de gaz dans des solides adsorbants

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ES (1) ES2403016B2 (fr)
WO (1) WO2013068617A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2257268T3 (es) * 1999-02-09 2006-08-01 Air Products And Chemicals, Inc. Metodo de control del flujo de gas y sistema de adsorcion por cambio de presion.
WO2008102027A1 (fr) * 2007-02-23 2008-08-28 Consejo Superior De Investigaciones Cientificas Procédé et dispositif permettant de déterminer la teneur en gaz et en agents volatils de matériaux solides ou de revêtements de surface

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2257268T3 (es) * 1999-02-09 2006-08-01 Air Products And Chemicals, Inc. Metodo de control del flujo de gas y sistema de adsorcion por cambio de presion.
WO2008102027A1 (fr) * 2007-02-23 2008-08-28 Consejo Superior De Investigaciones Cientificas Procédé et dispositif permettant de déterminer la teneur en gaz et en agents volatils de matériaux solides ou de revêtements de surface

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ALCANIZ-MONGE, J. ET AL.: "Fundamentals of vaporsadsorption onto activated carbon fibers assessedby the comparative analysis of N2 and C02 adsorption.", SEPARATION AND PURIFIACTION TECHNOLOGY, vol. 85, 2012, pages 83 - 89 *

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ES2403016A1 (es) 2013-05-13
ES2403016B2 (es) 2014-01-20

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