• 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:
    The invention relates to the use of zeolite adsorbent materials in the form of agglomerates comprising at least one type A zeolite, for separation in the gas phase, in particular the separation of carbon dioxide (CO2) in natural gas (NG) in pressure modulated processes and / or in temperature modulated processes. The invention also relates to the decarbonation process of natural gas implementing said zeolite adsorbent material, as well as the natural gas decarbonation unit comprising said zeolitic adsorbent material.
    公开号:FR3040636A1
    申请号:FR1558320
    申请日:2015-09-08
    公开日:2017-03-10
    发明作者:Jullian Vittenet；Cecile Lutz；Jean-Robert Lascoumettes
    申请人:Carbonisation et Charbons Actifs CECA SA；
    IPC主号:
    专利说明:

    USE OF MOLECULAR SIEVES FOR THE DECARBONATION OF NATURAL GAS
    The invention relates to the use of zeolite adsorbent materials in the form of agglomerates comprising at least one type A zeolite, for separation in the gas phase, in particular the separation of carbon dioxide (CO2) in natural gas (GN), in pressure-modulated processes, either of the PSA (Pressure Swing Adsorption) type or of the VSA (Vacuum Swing Adsorption) type, either of the VPSA type (hybrid process of the two previous ones), or of the RPSA type ("Rapid Pressure Swing Adsorption" in English), in temperature modulated processes of the TSA (temperature-swinging adsorption or "Temperature Swing Adsorption" type in English) and / or in pressure and temperature modulated processes of the PTSA type (Pressure and Temperature Swing Adsorption). English ngue).
    More particularly, the invention relates to the use of zeolitic adsorbent materials defined above and comprising calcium or calcium and sodium.
    The use of these zeolite adsorbent materials is particularly advantageous for separation in the gas phase, and especially for the separation of carbon dioxide (CO2) in natural gas, where the transfer kinetics and the volume capacity of adsorption, determining parameters for the efficiency and overall productivity of the process, are sought.
    [0004] Natural gas is used in various applications and its supply is generally provided by pipelines. In other cases, this resource is initially liquefied and then transported in the form of Liquefied Natural Gas (LNG). To avoid damage to the transport and liquefaction equipment, the NG must therefore be rid of various compounds such as water, CO2 and hydrogen sulphide (H2S).
    As regards CO2, the concentrations in natural gas can vary in large proportions, especially from 0.1% to more than 4% depending on the source of the operation and the pre-treatment (s) already carried out (s). ) on the gas. The specifications required for this compound in natural gas are 2% for pipeline transport and 50 ppm upstream of liquefaction processes in LNG plants and floating production, storage and offloading units, such as for example off-shore units, FLNG (Floating Liquefied Natural Gas, in English), FPSO (Floating Production Storage Offloading in English), and others.
    Various technologies have been developed to eliminate CO2 in natural gas, such as absorption on chemical or physical solvents, as described for example in US3161461. However, the use of such solvents is not easy to implement, especially in confined sites, such as for example FLNG, FPSO and others.
    Membrane systems are also techniques used for the separation of CO2 in gas mixtures as described for example in US8192524 and US2015 / 0059579. However, these processes do not make it possible to achieve the specifications of very low levels of CO2 required for the liquefaction of natural gas.
    Thus, to achieve low levels of CO2 in natural gas, of the order of a few ppm, it is most often used by adsorption separation processes. The flexibility and simplicity of these methods is an advantage for their use, especially on FPSOs, and they can be used in addition to other technologies. For example, documents US20140357925 and US5411721 propose to separate CO2 from natural gas using membranes coupled to TSA and PSA processes.
    The kinetics and the adsorption capacity of materials being major criteria for evaluating the efficiency and overall productivity of the adsorption processes, a lot of efforts have been made to develop increasingly effective and long-lasting materials. for the separation of CO2 in the gas phase, and more particularly for the separation of CO2 present in natural gas.
    Among the zeolitic adsorbent materials which are the most widespread in the decarbonation processes of natural gas, various structures and combinations of zeolites are available and available. For example, patent GB1120483 recommends the use of zeolite adsorbent materials with a pore diameter greater than 4 Å for the purification of natural gas. This document, however, does not indicate the nature of the binder used to agglomerate the zeolite crystals, and does not suggest any possibility of optimization of purification performance.
    Document FR2618085 describes the purification of air and hydrogen by adsorption, inter alia, of carbon dioxide with a molecular sieve type 5A in which the agglomeration binder is a clay binder of the family of kaolinites.
    Furthermore, it has been found that the zeolitic adsorbent materials used in the decarbonation of natural gas too often undergo premature aging, and this in particular because of the risks of amorphization and / or pseudomorphism to which they are exposed during the regeneration phase with a wet gas containing CO2. This premature aging obviously has a significant negative impact on the efficiency and overall productivity of the adsorption processes for the decarbonation of natural gas.
    Other materials such as porous organometallic materials ("Metal-Organic Framework materials" or MOF in English) are also suggested for the decarbonation of natural gas, as described for example in the application WO2007111738. However, these materials are only slightly stable or even unstable in the presence of moisture, as indicated in the document "Progress in adsorption-based CO2 capture by metal-organic frameworks" (J. Liu et al., Chemical Society Reviews, 41 , (2012), pp. 2308-2322).
    There remains therefore a need for adsorbent materials, in particular zeolite adsorbent materials effective for the decarbonation of natural gas, and having high adsorption capacity, better adsorption / desorption kinetics, thus allowing in particular to improve the decarbonation processes of natural gas, in particular the TSA, PSA or PTSA processes.
    There is also a need for zeolite adsorbent materials less impacted by the accelerated aging often observed in the decarbonation processes of natural gas.
    The Applicant has discovered that the aforementioned objectives can be achieved in whole, or at least in part, by using a zeolite adsorbent material specifically dedicated to the decarbonation process of natural gas, including natural gas before liquefaction, and such that they will be described now.
    Thus, and according to a first aspect, the invention relates to the use for the decarbonation of natural gas, of at least one zeolitic adsorbent material comprising: a) from 70% to 99% by weight, preferably 70% by weight; % to 95% by weight, more preferably 70% to 90% by weight, more preferably 75% to 90%, most preferably 80% to 90% of at least one A zeolite, based on weight total of the zeolitic adsorbent material, and b) from 1% to 30% by weight, preferably from 5% to 30% by weight, more preferably from 10% to 30% by weight, more preferably from 10% to 25% by weight. %, especially from 10% to 20% relative to the total weight of the zeolite adsorbent material of at least one agglomeration binder comprising at least one clay selected from fibrous magnesia clays.
    Unless otherwise specified, in this presentation, the range of value limits of the expressions "from ... to ...." or "between ... and ...." are included in the said ranges of values.
    By "fibrous magnesian clays" is meant fibrous clays containing magnesium and preferably the hormones, whose main representatives are sepiolite and attapulgite (or palygorskite). Sepiolite and attapulgite are the preferred hormones in the context of the present invention.
    Further preferred is a zeolitic adsorbent material whose binder comprises only one or more clays of the family of hormones. According to another embodiment, the binder comprises a mixture of clay (s) consisting of at least one fibrous magnesian clay, for example a hormite, and at least one other clay, for example chosen from montmorillonites, for example bentonite. According to another preferred embodiment, binders comprising at least 50% by weight of at least one hormone relative to the total weight of the binder are preferred. The preferred clay mixtures are the mixtures sepiolite / bentonite and attapulgite / bentonite, more preferably attapulgite / bentonite, and most preferably those mixtures in which the hormones (sepiolite or attapulgite) are present at least 50% by weight. weight relative to the total weight of the binder.
    As indicated above, the zeolitic adsorbent material useful in the context of the present invention comprises at least one zeolite A. Said zeolite A present in said zeolitic adsorbent material comprises one or more alkaline and / or alkaline earth ions, chosen from sodium, potassium, calcium, barium, lithium and cesium ions, preferably from sodium, potassium and calcium ions, more preferably from calcium and sodium ions. Most preferably, said zeolite A comprises calcium ions, and typically calcium ions and sodium ions.
    The zeolitic adsorbent material defined above may further comprise one or more additives and / or fillers well known to those skilled in the art, such as, for example, porogenic agents, carboxymethylcellulose (CMC), reinforcing agents in general, fibers (such as glass fibers, carbon, Kevlar® and others), carbon nanotubes (CNTs), colloidal silica, polymers, fabrics and others. The additive (s) and / or fillers represent at most 10% by weight, preferably at most 5% by weight relative to the total weight of the zeolitic adsorbent material that can be used in the context of the present invention.
    According to a preferred embodiment, the zeolitic adsorbent material used in the context of the present invention comprises calcium whose content, expressed as calcium oxide (CaO) is between 9.0% and 21.0%, preferably between 10.0% and 20.0%, and even more preferably between 12.0% and 17.0%, limits included, expressed by weight of CaO relative to the total weight of the zeolitic adsorbent material.
    Zeolite A means any LTA zeolite, and in particular zeolites 5A whose pore opening is 5, and zeolites 5APH or zeolites 5A porosity.
    Hierarchized as described for example in the application W02015 / 019013. The zeolites A are generally characterized by an Si / Al atomic ratio equal to 1 ± 0.05. According to a preferred embodiment, the zeolite A is chosen from 5A zeolites and 5APH zeolites. In a preferred embodiment, the zeolite adsorbent used in the process of the invention has a single zeolitic crystalline phase of LTA type.
    According to a preferred embodiment, the zeolite 5A included in the zeolitic adsorbent material used in the context of the present invention has a calcium content, expressed as calcium oxide (CaO), of between 12.0% and 21.0%, preferably between 13.0% and 20.0%, and even more preferably between 14.0% and 19.0%, limits included, expressed by weight of CaO relative to the total weight of the zeolite.
    The size (number average diameter) of the LTA zeolite crystals used to prepare the zeolite adsorbent material of the invention, as well as the size of the LTA zeolite elements in the zeolitic adsorbent material, are measured by observation under an electron microscope. scanning (SEM). Preferably, the mean diameter of the LTA zeolite crystals is between 0.1 μm and 20 μm, preferably between 0.5 μm and 20 μm, and more preferably between 0.5 μm and 10 μm.
    According to another preferred embodiment, the zeolitic adsorbent material used in the context of the present invention has an H50 water adsorption capacity of between 16% and 25%, preferably between 18% and 23%. and even more preferably between 19% and 22%. The measurement of the water adsorption capacity H50 is explained later in the description.
    According to a preferred embodiment of the present invention, the Si / Al atomic ratio of the zeolitic adsorbent material is generally between 0.5 and 2.5, inclusive, preferably between 1.0 and 2.0, more preferably between 1.0 and 1.8, and even more preferably between 1.0 and 1.6 inclusive. The Si / Al atomic ratio of the zeolitic adsorbent material is determined according to the method described later in the present description.
    The zeolitic adsorbent material as it has just been defined for the decarbonation of natural gas, can be prepared according to any method known to those skilled in the art or from known methods, such as those described in US Pat. "Zeolite Molecular Sieves: Structure, Chemistry, and Use" (DW Breck, (1974), Ed., John Wiley & Sons, pp. 267-274, and pp. 537-541).
    The zeolitic adsorbent material described above can be in all types of forms known to those skilled in the art, such as, for example, beads, extruded, trilobed, and others. The trilobal extrusions have the advantage, in use, to limit the pressure drop, compared to other types of extrudates, especially "spun" in the English language. Thus agglomerated and shaped zeolite adsorbent materials made according to any techniques known to those skilled in the art are preferred, such as extrusion, compacting, agglomeration on a granulating plate, granulating drum, atomization and the like.
    The average volume diameter (D50 or "volume mean diameter") of the zeolitic adsorbent material used in the process according to the invention is generally between 0.4 mm and 5.0 mm, preferably between 0.5 mm and 4.0 mm, more preferably between 0.6 mm and 3.8 mm. The method for measuring the average volume diameter of the zeolite adsorbent material is explained later in the description.
    The zeolitic adsorbent material useful in the context of the present invention also has mechanical properties that are particularly suitable for the applications for which it is intended, and in particular: • a crush resistance in bed (REL) measured according to the standard ASTM 7084-04 between 0.5 MPa and 6 MPa, preferably between 0.5 MPa and 4 MPa, more preferably between 0.5 MPa and 3 MPa, more preferably between 0.75 MPa and 2.5 MPa, for a material of medium volume diameter (D50) or a length (larger dimension when the material is not spherical), less than 1 mm, or • a crush resistance in grain, measured according to the ASTM D 4179 (2011) and ASTM D 6175 (2013) standards, between 0.5 daN and 20 daN, preferably between 1 daN and 10 daN, more preferably between 1 daN and 8 daN, for a material of diameter medium volume (D50) or a length (larger dimension lo the material is not spherical), greater than or equal to 1 mm.
    According to the present invention, the zeolitic adsorbent materials described above are particularly suitable and effective in the processes for the decarbonation of natural gas, in particular in pressure-modulated processes, either of the PSA type or of the type VSA, either of the VPSA type or of the RPSA type, or in TSA type temperature-modulated processes and / or in PTSA type processes.
    More specifically, the present invention relates to the use of at least one zeolitic adsorbent material, comprising at least one LTA zeolite, preferably of type 5A, as defined above, for the decarbonation of natural gas from using the separation methods mentioned above, preferably the TSA, PSA and PTSA methods, and even more preferably the TSA method.
    According to a preferred aspect of the present invention, the zeolitic adsorbent materials that can be used for the decarbonation of natural gas are particularly suitable for the separation of CO2 from a natural gas containing less than 5% by volume of CO2, preferably less than 3% by volume of CO2, preferably less than 2% by volume of CO2.
    According to a preferred aspect of the present invention, the zeolitic adsorbent materials that can be used for the decarbonation of natural gas are particularly suitable for the decarbonation of natural gas for NG plants, LNG plants and floating units, as described above, at the same time. using the separation methods defined above.
    According to a preferred aspect of the present invention, the zeolitic adsorbent materials that can be used for the decarbonation of natural gas can be combined with other adsorbent materials in the same separation process defined previously. In particular, the zeolite adsorbent materials defined according to the invention may be used in combination, in a mixture, or separately with one or more other zeolite adsorbent materials containing a zeolite chosen from zeolites 3A, 4A and 13X, and mixtures thereof, in order to perform additional and / or additional decarbonation treatment, and / or to remove other impurities, such as water, aromatics and hydrocarbons.
    In the case where the natural gas contains impurities such as water in large quantities, it can be envisaged to remove the water by specific adsorption on a specific zeolite adsorbent material, comprising a zeolite of type by Example 3A and / or 4A or other adsorbents well known to those skilled in the art, then to lead the natural gas containing more water or only minimal traces of water, in the decarbonation process according to the present invention.
    In the case where the natural gas contains impurities such as aromatic hydrocarbons in large quantities, it may be envisaged to remove these impurities by specific adsorption on a zeolite adsorbent material, advantageously comprising a 13X zeolite, or on silica gel or other adsorbents well known to those skilled in the art, then to lead natural gas containing more water or only minimal traces of water, in the decarbonation process according to the present invention.
    When the natural gas contains several impurities, in particular those defined above, it is thus possible to envisage one or more adsorption treatments on zeolitic adsorbent materials, then perform the decarbonation treatment of natural gas according to the present invention. The impurity removal method defined above combined with the decarbonation treatment defined above is also part of the present invention.
    It is also possible to carry out all these treatments after or before or simultaneously with the decarbonation treatment of natural gas as defined above, by adsorbent beds (zeolite adsorbent materials or other adsorbents well known to those skilled in the art, for example silica gel, activated charcoal, activated alumina, metal oxide, and the like), separated and / or mixed. The term "mixed beds" means mixtures of two or more different adsorbents or superimpositions of two or more different adsorbents, or alternating or non-alternating layers of different adsorbents.
    According to another aspect, the present invention relates to a decarbonation process of natural gas comprising at least the following steps: • supply of a natural gas comprising carbon dioxide, • contacting said natural gas with at least a zeolitic adsorbent material as defined above, and • recovery of the decarbonated natural gas.
    The decarbonation process according to the present invention is particularly suitable for the decarbonation of natural gas containing less than 5% by volume of CO2, preferably less than 3% vol. of CO2, preferably less than 2% by volume of CO2.
    As indicated above, the decarbonation process of natural gas discussed above in the context of the present invention is particularly suitable for GN plants, LNG and floating units, such as off-shore units, FLNG units (Floating Liquefied Natural Gas), FPSO units (Floating Production Storage Offloading), and others.
    Thus, and according to yet another aspect, the present invention relates to a natural gas decarbonation unit, for example as defined above, comprising at least one zeolite adsorbent material as described above for the decarbonation of natural gas.
    Characterization Techniques The physical properties of the zeolitic adsorbent materials that can be used in the present invention are evaluated by the methods known to those skilled in the art and defined below.
    Size of LTA zeolite crystals: The estimation of the average number diameter of the zeolite LTA crystals contained in the zeolite adsorbent materials, and which are used for the preparation of said zeolitic adsorbent material, is carried out by observation under an electron microscope. scanning (SEM), possibly after fracture samples of zeolite adsorbent material.
    In order to estimate the size of the zeolite crystals on the samples, a set of images is carried out at a magnification of at least 5000. The diameter of at least 200 crystals is then measured using a dedicated software, for example the Smile View software from the LoGraMi editor. The accuracy is of the order of 3%.
    Granulometry of Zeolitic Adsorbent Materials Determination of the average volume diameter (D50 or "volume mean diameter", or length, ie greater dimension when the material is not spherical) of the zeolite adsorbent material of the method according to the invention is carried out by analysis of the particle size distribution of a sample of adsorbent material by imaging according to ISO 13322-2: 2006, using a conveyor belt allowing the sample to pass the objective of the camera.
    The volume mean diameter is then calculated from the particle size distribution by applying the ISO 9276-2: 2001 standard. In this document, the term "volume mean diameter" or "size" is used for zeolite adsorbent materials. The accuracy is of the order of 0.01 mm for the size range of the adsorbent materials useful in the context of the present invention.
    Chemical analysis of zeolitic adsorbent materials - Si / Al atomic ratio and calcium oxide (CaO) content [0051] Elementary chemical analysis of a zeolitic adsorbent material described above can be carried out according to various analytical techniques known to man of the art. job. Among these techniques, mention may be made of the technique of chemical analysis by X-ray fluorescence as described in standard NF EN ISO 12677: 2011 on a wavelength dispersive spectrometer (WDXRF), for example Tiger S8 of the company Bruker.
    X-ray fluorescence is a non-destructive spectral technique exploiting the photoluminescence of atoms in the X-ray domain, to establish the elemental composition of a sample. The excitation of the atoms, which is most often and usually performed by an X-ray beam or by electron bombardment, generates specific radiation after the atom has returned to the ground state. A measurement uncertainty of less than 0.4% by weight is obtained conventionally after calibration for each oxide.
    Other methods of analysis are for example illustrated by the methods of atomic absorption spectrometry (AAS) and atomic emission spectrometry with inductively coupled plasma (ICP-AES) described in NF EN ISO standards. 21587-3 or NF EN ISO 21079-3 on a device of the type for example Perkin Elmer 4300DV.
    The X-ray fluorescence spectrum has the advantage of depending very little on the chemical combination of the element, which offers a precise determination, both quantitative and qualitative. A measurement uncertainty of less than 0.4% by weight is obtained conventionally after calibration for each oxide S102 and Al2O3, as well as CaO.
    The elementary chemical analyzes described above make it possible both to verify the Si / Al atomic ratio of the zeolite used in the zeolitic adsorbent material, the Si / Al atomic ratio of the zeolitic adsorbent material, and the oxide content of the zeolite. calcium, expressed by weight of CaO, of the zeolitic adsorbent material. In the description of the present invention, the measurement uncertainty of the Si / Al atomic ratio is ± 5%. Measurement of the Si / Al atomic ratio of the zeolite present in the adsorbent material can also be measured by solid nuclear magnetic resonance (NMR) spectroscopy of silicon. Mechanical Resistance of Zeolite Adsorbent Materials: The bed crush strength (REL) of the zeolite adsorbent materials as described in the present invention is characterized according to ASTM 7084-04. The mechanical crushing strengths in grain are determined with a device "Grain Crushing Strength" marketed by Vinci Technologies, according to the standards D 4179 (2011) and ASTM D6175 (2013).
    Loss on ignition of zeolitic adsorbents: The loss on ignition is determined in an oxidizing atmosphere, by calcination of the sample in air at a temperature of 950 ° C. ± 25 ° C., as described in standard NF EN 196 -2 (April 2006). The standard deviation of measurement is less than 0.1%.
    Qualitative and quantitative analysis by X-ray diffraction
    The zeolite A content in the zeolite adsorbent material is evaluated by X-ray diffraction analysis (XRD), according to methods known to those skilled in the art. This identification can be carried out using a Bruker DRX device.
    This analysis makes it possible to identify the various zeolites present in the zeolite adsorbent material because each of the zeolites has a single diffractogram defined by the positioning of the diffraction peaks and their relative intensities.
    The zeolitic adsorbent materials are crushed then spread and smoothed on a sample holder by simple mechanical compression.
    The diffractogram acquisition conditions performed on the Brucker D5000 device are as follows: • Cu tube used at 40 kV - 30 mA; • size of the slots (divergent, diffusion and analysis) = 0.6 mm; • filter: Ni; • rotating sample device: 15 rpm; • measuring range: 3 ° <2Θ <50 °; • not: 0.02 °; • counting time in steps: 2 seconds.
    The interpretation of the diffractogram obtained is carried out with the EVA software with identification of zeolites using the ICDD database PDF-2, release 2011.
    The quantity of zeolite fractions A, by weight, is measured by XRD analysis, this method is also used to measure the amount of zeolite fractions other than A. This analysis is carried out on the Bruker D5000 device, then the amount by weight of the zeolite fractions is evaluated using the software TOPAS Bruker company.
    Measurement of the water adsorption capacity H50 The measurement of the water adsorption capacity H50 is carried out by a static method which consists in measuring the increase in weight of the zeolitic adsorbent material placed in an enclosure sealed for 24 hours in equilibrium with a controlled atmosphere at 50% relative humidity and at room temperature (22 ° C). The percent water adsorption capacity is expressed as the weight difference between the zeolite adsorbent material after and before the test described above divided by the weight of the zeolite adsorbent material prior to the test described above. The standard deviation of measurement is less than 0.3%.
    Examples [0065] The present invention is now illustrated by means of the following examples and which in no way limit the scope of the invention whose scope of protection is conferred by the claims. In what follows, a mass expressed in "anhydrous equivalent" means a mass of product less its loss on ignition.
    The zeolitic adsorbent materials used in the following examples are prepared as extrudates of 1.6 mm in diameter and 5 mm to 7 mm in length. The zeolitic adsorbent materials tested are described below: Sample A: Siliporite® NK 10 zeolite adsorbent material, sold by CECA SA Sample B: Siliporite® G5 zeolite adsorbent material 13X, sold by CECA SA Sample C: Preparation of a zeolitic adsorbent material obtained by spinning a mixture of zeolite 5A (80% by weight of anhydrous equivalent) and kaolin (20% by weight of anhydrous equivalent) as agglomeration binder, according to the well known techniques of the skilled in the art, as described for example in US3219590. The size of the zeolite crystals 5A is 7.5 μm. The CaO content of the zeolite adsorbent material is 12.3% by weight. Sample D: Preparation of a zeolite adsorbent material 5A similar to Sample C, replacing kaolin with attapulgite. The CaO content of the zeolite adsorbent material is 12.4% by weight. Sample E: Preparation of a zeolite adsorbent material similar to Sample D, replacing zeolite 5A with zeolite Y (CBV 100 from Zeolyst International).
    A quantity of 725 g of each of the samples is charged in a pilot decarbonation plant (pilot plant for adsorption of carbon dioxide) of natural gas equipped with an adsorption column whose internal diameter is 27 mm. and where the height of the adsorbent bed is 2 m. The incoming natural gas comprises 1.2% (% by volume) of CO2 and 91% (% by volume) of methane, the remainder being other hydrocarbons (ethane, propane). The flow rate is 12m3 / h, the pressure is 6 MPa, and the temperature is 40 ° C.
    Example 1 [0068] The adsorption capacities of CO2, expressed as a percentage by weight (g of adsorbed CO2 per 100 g of zeolitic adsorbent material) are presented in Table 1 and are calculated from the following equation:
    • "Qgaz" represents the average flow rate of the gas flow in Nm3 / h, • "[CO2]" represents the average CO2 input concentration in ppm, • "" tso "represents, in hours, the time reached when the concentration in CO2 at the outlet of the column is equal to 50% of the average CO2 concentration at the column inlet, and • "Mass" represents the mass of zeolitic adsorbent material (in grams).
    The results of the tests on the pilot indicate that the sample D, consisting of CaO content 5A zeolite of 12.4%, and agglomerated with an attapulgite-type binder has the greatest adsorption capacity of CO2. The results are shown in Table 1 below: - Table 1 -
    Example 2 The mass transfer zones (ZTM), expressed in centimeters, of CO2 on the zeolite adsorbent materials are presented in Table 2 and are calculated from the following equation below. The lower the ZTM value of the zeolitic adsorbent material, the faster the adsorption kinetics of the zeolite adsorbent material. or
    • "ZTM" represents the mass transfer area, in centimeters, • Hcolonne represents the height of the column, in centimeters, • "tpercée" represents the breakthrough time, in hours, as described in the book "Encyclopedia of Chemical Processing and Design ", May 28, 1999, Vol. 67, pp. 384-385: "Zeolites", John J. McKetta Jr., CRC Press, 500 pages, • "tso" represents, in hours, the time reached when the CO2 concentration at the outlet of the column is equal to 50% of the average concentration of CO2 at the column inlet, the results of the tests on the pilot indicate that the sample D, consisting of zeolite 5A agglomerated with attapulgite, has a shorter ZTM and therefore a kinetics of adsorption of the CO2 faster than agglomerated material with kaolin (sample C).
    The zeolite adsorbent material based on zeolite 5A agglomerated with attapulgite is therefore particularly suitable for the decarbonation of natural gas. The results are shown in Table 2 below. - Table 2 -
    权利要求:
    Claims (13)
    [1" id="c-fr-0001]
    1. Use for the decarbonation of natural gas of at least one zeolitic adsorbent material comprising: a) 70% to 99% by weight, preferably 70% to 95% by weight, more preferably 70% to 90% by weight % by weight, more preferably from 75% to 90%, most preferably from 80% to 90% of at least one zeolite A, based on the total weight of the zeolite adsorbent material, and b) from 1% to 30% by weight, preferably from 5% to 30% by weight, more preferably from 10% to 30% by weight, more preferably from 10% to 25%, most preferably from 10% to 20% by weight relative to the total weight zeolitic adsorbent material of at least one agglomeration binder comprising at least one clay selected from fibrous magnesium clays.
    [2" id="c-fr-0002]
    2. Use according to claim 1, wherein the fibrous magnesian clays are hormites, and preferably are selected preferably from sepiolite and attapulgite.
    [3" id="c-fr-0003]
    3. Use according to claim 1 or claim 2, wherein the binder comprises a mixture of clay (s) consisting of at least one fibrous magnesian clay, and at least one other clay.
    [4" id="c-fr-0004]
    Use according to any one of the preceding claims, wherein zeolite A comprises calcium ions, and typically calcium ions and sodium ions.
    [5" id="c-fr-0005]
    5. Use according to any one of the preceding claims, wherein the zeolitic adsorbent material comprises calcium whose content, expressed as calcium oxide (CaO) is between 9.0% and 21.0%, preferably between 10% and 10%. , 0% and 20.0%, and even more preferably between 12.0% and 17.0%, limits included, expressed by weight of CaO relative to the total weight of the zeolitic adsorbent material.
    [6" id="c-fr-0006]
    6. Use according to any one of the preceding claims, wherein the zeolite A is selected from 5A zeolites and 5APH zeolites.
    [7" id="c-fr-0007]
    7. Use according to any one of the preceding claims, wherein the Si / Al atomic ratio of the zeolitic adsorbent material is between 0.5 and 2.5, preferably between 1.0 and 2.0, more preferably between 1.0 and 1.8, and even more preferably between 1.0 and 1.6 inclusive.
    [8" id="c-fr-0008]
    8. Use according to any one of the preceding claims, wherein the decarbonation process of natural gas is a TSA process, or a PSA process or a PTSA process, and more preferably a TSA process.
    [9" id="c-fr-0009]
    9. Use according to any one of the preceding claims, wherein the zeolite adsorbent material is used in combination, in admixture, or separately with one or more other zeolite-containing zeolite adsorbent materials selected from zeolites 3A, 4A and 13X , and their mixtures.
    [10" id="c-fr-0010]
    10. Process for decarbonating natural gas comprising at least the following steps: • supply of a natural gas comprising carbon dioxide, • contacting said natural gas with at least one zeolitic adsorbent material as defined in one of the following: any of claims 1 to 7, and • recovery of decarbonated natural gas.
    [11" id="c-fr-0011]
    11. The method of claim 10, wherein the natural gas brought into contact with said at least one zeolitic adsorbent material, contains less than 5% by volume of CO2, preferably less than 3% by volume of CO2, preferably less than 2% by volume. of CO2.
    [12" id="c-fr-0012]
    12. Unit for decarbonating natural gas comprising at least one zeolitic adsorbent material as defined in any one of claims 1 to 7.
    [13" id="c-fr-0013]
    The natural gas decarbonation unit of claim 12, which is a NG plant, an LNG plant, a floating unit, an offshore floating unit, an FLNG unit, or an FPSO unit.
    类似技术:
    公开号 | 公开日 | 专利标题
    EP2931417B1|2021-11-03|Zeolitic adsorbents and uses thereof
    EP3347116B1|2021-12-08|Use of molecular sieves for decarbonating natural gas
    EP2694188B1|2017-06-21|Mixture of an adsorbent and a phase change material with an adapted density
    WO2015032923A1|2015-03-12|Zeolitic adsorbents with large external surface area, process for preparing same and uses thereof
    EP3253483A1|2017-12-13|Zeolite adsorbents having a high external surface area and uses thereof
    EP2991760A1|2016-03-09|Zeolite adsorbents comprising emt zeolite, method for preparing same and uses thereof
    EP3253484B1|2021-04-21|Use of zeolite adsorbents having a high external surface area
    EP3319723B1|2021-11-10|Zeolitic adsorbents, method for the production thereof, and uses of same
    FR2792850A1|2000-11-03|HIGH MACROPOROSITY ADSORBENT FOR USE IN A GAS ADSORPTION PROCESS, IN PARTICULAR A PSA PROCESS
    CA3044620C|2021-03-23|Zeolite adsorbent material, method of preparation and use for non-cryogenic separation of industrial gases
    WO2021105598A1|2021-06-03|Separation of gases from air
    EP3768410A1|2021-01-27|Method of decarbonating gaseous flows
    WO2006106226A1|2006-10-12|Method for purifying natural gas by mercaptan adsorption
    WO2014108568A1|2014-07-17|Reactive medium comprising a porous substrate impregnated with an organic compound capable of forming gas clathrates, and use thereof for separating and storing co2
    FR3105021A1|2021-06-25|Zeolite adsorbent for the separation of hydrocarbon isomers
    FR3105020A1|2021-06-25|Zeolite adsorbent for the separation of hydrocarbon isomers
    FR3090412A1|2020-06-26|ZEOLITHIC AGGLOMERATED MATERIAL, PREPARATION METHOD AND USE FOR NON-CRYOGENIC GAS SEPARATION
    WO2019122649A1|2019-06-27|Zeolitic adsorbents containing strontium
    FR3033714A1|2016-09-23|LOW REACTIVITY ADSORBENTS FOR DRYING GASES AND / OR LIQUIDS
    同族专利:
    公开号 | 公开日
    EP3347116B1|2021-12-08|
    WO2017042466A1|2017-03-16|
    AU2016319478A1|2018-03-29|
    FR3040636B1|2019-11-01|
    BR112018004205A2|2018-09-25|
    AU2016319478B2|2019-10-31|
    EP3347116A1|2018-07-18|
    CN108348834A|2018-07-31|
    DK3347116T3|2022-02-28|
    ZA201801955B|2019-09-25|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2973327A|1955-07-01|1961-02-28|Union Carbide Corp|Bonded molecular sieves|
    GB1120483A|1965-03-01|1968-07-17|Union Carbide Canada Ltd|Natural gas purification|
    US4420419A|1981-03-10|1983-12-13|Mizusawa Kagaku Kogyo Kabushiki Kaisha|Abrasion-resistant granular zeolite and process for preparation thereof|
    FR2618085A1|1987-07-17|1989-01-20|Rhone Poulenc Chimie|ADSORBENT FOR GAS PURIFICATION AND PURIFICATION PROCESS|
    EP0433156A1|1989-12-12|1991-06-19|Ceca S.A.|Process for preparation of zeolites 5A of great stability and applicable particularly in the separation of paraffins|
    US5089034A|1990-11-13|1992-02-18|Uop|Process for purifying natural gas|
    FR2678525A1|1992-07-06|1993-01-08|Bitterfeld Wolfen Chemie|Adsorption agent based on molecular sieve for the purification of natural gas from sulphur compounds|
    WO1996003199A1|1994-07-26|1996-02-08|Ceca S.A.|Zeolitic desulfurazation agents and their application to co2-containing gas treatment|EP3813988A4|2018-06-27|2022-01-26|Uop Llc|Adsorption process for treating natural gas|CN101381478B|2008-10-28|2011-01-26|南京亚东奥土矿业有限公司|Inorganic high molecular plastics and rubber toughening agent|FR3078897A1|2018-03-18|2019-09-20|Arkema France|PROCESS FOR DECARBONATING GAS FLOWS|
    CN109513421B|2018-10-24|2021-08-17|浙江省化工研究院有限公司|CO in gas2Adsorption method of |
    法律状态:
    2016-08-16| PLFP| Fee payment|Year of fee payment: 2 |
    2017-03-10| PLSC| Publication of the preliminary search report|Effective date: 20170310 |
    2017-08-10| PLFP| Fee payment|Year of fee payment: 3 |
    2017-10-27| TP| Transmission of property|Owner name: ARKEMA FRANCE, FR Effective date: 20170922 |
    2018-08-13| PLFP| Fee payment|Year of fee payment: 4 |
    2019-08-15| PLFP| Fee payment|Year of fee payment: 5 |
    2020-08-12| PLFP| Fee payment|Year of fee payment: 6 |
    2021-08-12| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1558320A|FR3040636B1|2015-09-08|2015-09-08|USE OF MOLECULAR SIEVES FOR THE DECARBONATION OF NATURAL GAS|
    FR1558320|2015-09-08|FR1558320A| FR3040636B1|2015-09-08|2015-09-08|USE OF MOLECULAR SIEVES FOR THE DECARBONATION OF NATURAL GAS|
    AU2016319478A| AU2016319478B2|2015-09-08|2016-09-06|Use of molecular sieves for decarbonating natural gas|
    BR112018004205-6A| BR112018004205A2|2015-09-08|2016-09-06|use of molecular sieves for the decarbonation of natural gas|
    EP16775784.8A| EP3347116B1|2015-09-08|2016-09-06|Use of molecular sieves for decarbonating natural gas|
    DK16775784.8T| DK3347116T3|2015-09-08|2016-09-06|USE OF MOLECULAR SCREENS FOR DECARBONIZATION OF NATURAL GAS|
    CN201680064923.0A| CN108348834A|2015-09-08|2016-09-06|Purposes of the molecular sieve in natural gas decarbonization|
    PCT/FR2016/052203| WO2017042466A1|2015-09-08|2016-09-06|Use of molecular sieves for decarbonating natural gas|
    ZA2018/01955A| ZA201801955B|2015-09-08|2018-03-23|Use of molecular sieves for decarbonating natural gas|
    [返回顶部]