Use Of Molecular Sieves For Decarbonating Natural Gas

Patent Information

Abstract

Abstract: The invention concerns the use of zeolite adsorbent materials in agglomerate form comprising at least one zeolite of type A for gas phase separation in particular the separation of carbon dioxide (CO2) from Natural gas (GN) in pressure modulated methods and/or in temperature modulated methods. The invention also concerns the method for decarbonating natural gas employing said zeolite adsorbent material and the natural gas decarbonation unit comprising said zeolite adsorbent material.

Applicants

Inventors

Specification

[0001] The invention relates to the use of zeolitic adsorbents materials in agglomerate form comprising at least one zeolite of type A, for the separation in the gas phase, in particular the separation of carbon dioxide (CO2) in Natural Gas (GN), in processes modulated pressure, or PSA (pressure Swing Adsorption or "pressure Swing Adsorption" in English) is of type VSA (vacuum Swing Adsorption or "vacuum Swing Adsorption" in English), or VPSA type (hybrid process of the previous 2) or type RPSA ( "Rapid Pressure Swing Adsorption" in English),in processes modulated TSA temperature (temperature swing adsorption or "Temperature Swing Adsorption" in English) and / or in processes modulated pressure and PTSA type temperature (Pressure Swing Adsorption and Temperature or "Pressure and Temperature Swing Adsorption "in English).

[0002] More particularly, the invention relates to the use of zeolitic adsorbents materials defined above and comprising calcium or calcium and sodium.

[0003] The use of such zeolitic adsorbent materials is particularly advantageous for the separation in the gas phase, particularly for the separation of carbon dioxide (CO2) from natural gas, where the transfer kinetics and the volume capacity of adsorption, determining parameters for the efficiency and the overall productivity of the process, are searched.

[0004] Natural gas is used in various applications and supply is generally provided by the pipes. In other cases, this resource is initially liquefied and transported as liquefied natural gas (LNG). To prevent damage to the transport equipment and liquefaction, the GN must therefore be stripped of various compounds such as water, CO2 and hydrogen sulphide (H2S).

[0005] With regard to the CO2 concentrations in the natural gas may vary within wide proportions, in particular from 0.1% to more than 4% according to the operating and the source (s) pretreatment (s) already realized (s ) on gas. The specifications required for this compound in natural gas is 2% for transport in pipelines and 50 ppm upstream of the liquefaction processes in the factories of LNG and floating production, storage and unloading, such for example off-shore units, FLNG ( "Floating Liquefied Natural Gas" in English), FPSO ( "Floating Production Storage Offloading" in English), and others.

[0006] Various technologies have been developed to remove CO2 from natural gas, such as absorption of chemical or physical solvents, as described for example in the patent US3161461. However, use of such solvents is not easy to implement, especially in confined sites that are eg FLNG, FPSO and others.

[0007] The membrane systems are also techniques for the separation of CO2 in gas mixtures as described for example in US8192524 documents and US2015 / 0059579. However, these methods do not achieve the specifications very low CO2 levels required for liquefaction of natural gas.

[0008] Thus, to achieve low CO2 content in natural gas, on the order of a few ppm, it is most often used the adsorptive separation processes. The flexibility and simplicity of these processes are an advantage for their use, including FPSOs, and they can be used to complement other technologies. For example, the US20140357925 documents US541 1721 proposed to separate C0 2 from natural gas using membranes coupled with TSA and PSA processes.

[0009] The kinetics and the adsorption capacity of the materials being the major criteria for evaluating the effectiveness and overall productivity for adsorption processes, many efforts have been made to develop increasingly efficient materials and long-term life, for the separation of CO2 in the gas phase, more particularly for the separation of CO2 from natural gas.

[0010] Among the zeolite adsorbent materials that are most widespread in the natural gas decarbonization processes, structures and various combinations of zeolites are offered and available. For example, patent GB 1 120 483 recommends the use of zeolitic adsorbents materials of higher pore diameter 4 Å for the purification of natural gas. This document does not indicate the nature of the binder used to agglomerate the zeolite crystals, and suggests any possibility of purification performance optimization.

[0011] FR2618085 discloses the purification of air and hydrogen by adsorption, inter alia, carbon dioxide with a 5A molecular sieve wherein the agglomeration binder is a clayey binder of the family of kaolinite.

[0012] Furthermore, it has been found that zeolite adsorbent materials used in the decarbonization of natural gas too often suffer premature aging, and this particularly because of the risk of amorphization and / or pseudomorphisme and / or

mechanical degradation which they are exposed during the regeneration phase with a wet gas or not containing CO2. This premature aging obviously has a significant negative impact on the efficiency and overall productivity of the adsorption processes for decarbonization of natural gas.

[0013] Other materials such as porous organometallic materials ( "Metal-Organic Framework materials", or MOF in English) are also suggested for the decarbonization of natural gas, for example as described in the application 1738. However WO20071 1 , these materials are only slightly stable or unstable in presence of moisture, as shown in document "Progress in adsorption-based CO2 capture by metal-organic frameworks" (J. Liu et al., Chemical Society Reviews, 41, (2012), pp. 2308-2322).

[0014] There remains a need for adsorbent materials, particularly effective zeolite adsorbent materials for the decarbonization of natural gas, and with large adsorption capacity, better kinetic adsorption / desorption, allowing in particular for improve natural gas decarbonization processes, especially the TSA processes, PSA or PTSA.

[0015] There also remains a need for the zeolite adsorbent materials less impacted by the accelerated aging often observed in the decarbonization of natural gas processes.

[0016] We have discovered that the above objectives can be met in full, or at least in part, by implementing a zeolite adsorbent material dedicated to the decarbonization of natural gas process, in particular natural gas before liquefaction, and such they will now be described.

[0017] Thus, 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 % to 95 wt%, more preferably from 70% to 90% by weight, more preferably from 75% to 90%, most preferably from 80% to 90% of at least one zeolite a, based on the weight total 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%, most preferably 10% to 20% relative to the total weight of the zeolitic adsorbent material of at least one agglomeration binder comprising at least one clay selected from fibrous magnesian clays.

[0018] Unless otherwise specified, in this paper, the terminals of expressions ranges "from ... to ...." or "between ... and ...." are included in those beaches values.

[0019] By "fibrous magnesian clays" means the fibrous clays containing magnesium and preferably hormites, whose main representatives are sepiolite and attapulgite (or palygorskite). Sepiolite and attapulgite are preferred hormites in the context of the present invention.

[0020] Further preferred are a zeolite adsorbent material whose binder only includes one or more clays of the family of hormites. According to another embodiment, the binder comprises a mixture of clay (s) consisting of at least one fibrous clay magnesium, e.g. hormite, and at least one other clay, e.g. selected from the montmorillonites, e.g. bentonite. According to another preferred embodiment, preferred are binders comprising at least 50% by weight of at least one hormite relative to the total weight of the binder. Mixtures of preferred clays are mixtures meerschaum / bentonite and attapulgite / bentonite, preferably attapulgite / bentonite

[0021] 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 alkali metal ions and / or alkaline earth metal selected from sodium, potassium, calcium, barium, lithium, cesium, preferably from sodium, potassium and calcium, more preferably from calcium and sodium ions. So Most preferably, said zeolite A comprises calcium ions, typically calcium and sodium ions.

[0022] The zeolitic adsorbent material defined above may further comprise one or more additives and / or fillers known to those skilled in the art, such as for example blowing agents, carboxymethylcellulose (CMC), typically reinforcing agents, fibers (such as fiberglass, carbon, Kevlar ® and others), carbon nanotubes (CNTs), colloidal silica, polymers, and other tissues. The additive or additives and / or fillers represents at most 10% by weight, preferably at most 5% by weight relative to the total weight of the zeolitic adsorbent material usable in the context of the present invention.

[0023] 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%, inclusive, by weight CaO based on the total weight of the zeolitic adsorbent material.

[0024] The zeolite A is any zeolite LTA, and in particular, preferably zeolites 5A pore opening of which is 5a, and zeolites or zeolites 5APH 5A to hierarchical porosity as described for example in WO2015 request / 019013. A zeolites are characterized generally by an atomic Si / Al ratio equal to 1 ± 0.05. According to a preferred embodiment, the zeolite is selected from zeolites and zeolites 5A 5APH. In a preferred embodiment, the zeolite adsorbent used in the process of the invention has a single zeolitic crystalline phase LTA type.

[0025] According to a preferred embodiment, zeolite 5A within the zeolitic adsorbent material used in the context of the present invention has a content of calcium expressed as calcium oxide (CaO), between 12.0% and 21, 0%, preferably between 13.0% and 20.0%, and even more preferably between 14.0% and 19.0%, inclusive, by weight CaO based on the total weight of the zeolite.

[0026] The size (mean diameter in number) of LTA zeolite crystals used to prepare the zeolite adsorbent material of the invention, as well as the size of zeolite LTA elements in the zeolitic adsorbent material, are measured by electron microscopic observation (SEM). Preferably, the average diameter of LTA zeolite crystals is between 0.1 and 20 μηι μηι preferably between 0.5 and 20 μηι μηι, and more preferably between 0.5 and 10 μηι μηι.

[0027] According to another preferred embodiment, the zeolitic adsorbent material used in the context of the present invention has a water adsorption capacity between 16% H50 and 25%, preferably between 18% and 23%, and even more preferably between 19% and 22%. The measure H50 water adsorption capacity is explained below in the description.

[0028] According to a preferred embodiment of the present invention, the atomic ratio Si / Al 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 1, 0 and 1, 6, inclusive. The atomic Si / Al ratio of the zeolitic adsorbent material is determined by the method described later in the present description.

[0029] The zeolitic adsorbent material as just 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

dans le document « Zeolite Molecular Sieves : Structure, Chemistry, and Use » (D. W. Breck, (1974), Ed. John Wiley & Sons, pp. 267-274, et pp. 537-541 ).

[0030] The zeolite adsorbent material described above can be in all kinds of forms known in the art, such as for example, beads, extruded, trefoil, and others. Extruded trefoil have the advantage, in use, to limit losses, compared to other types of extruded yarn ( "pellets" in English) in particular. It is thus preferred agglomerated zeolite adsorbent materials and shaped performed according to all techniques known to those skilled in the art such as extrusion, compacting, agglomeration on granulating plate, drum granulator, spray and others.

[0031] The volume average 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 measurement method of the volume average diameter of the zeolitic adsorbent material is explained later in the description.

[0032] The zeolitic adsorbent material useful in the context of the present invention further has mechanical properties particularly suited to the applications for which it is intended, and in particular:

• a crushing strength in bed (REL) measured according to ASTM 7084-04 of from 0.5 MPa to 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 an average volume diameter of material (D50) or a length (largest dimension when the material is not spherical), lower (e) to 1 mm , or

• a grain crush resistance, measured according to ASTM D 4179 (201 1) and ASTM D 6175 (2013), of between 0.5 daN and 20 daN and preferably between 1 daN and 10 daN, of preferably between 1 daN and 8 daN, with an average volume diameter of material (D50) or a length (largest dimension when the material is not spherical), higher (e) or equal (e) to 1 mm.

[0033] According to the present invention, the zeolitic adsorbent materials described above is shown particularly appropriate and effective in the methods for the decarbonation of natural gas, particularly in processes modulated pressure or PSA type or type VSA or VPSA type or type RPSA or in processes modulated TSA temperature and / or in PTSA type processes.

[0034] More specifically, the present invention relates to the use of at least one zeolitic adsorbent material comprising at least a LTA zeolite, preferably Type 5A, as defined above, for the decarbonation of natural gas to the using the separation methods mentioned above, preferably the methods TSA, PSA and PTSA, and even more preferably the TSA process.

[0035] According to a preferred aspect of the present invention, the zeolitic adsorbent materials suitable 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 C0 2 .

[0036] In a preferred aspect of the present invention, the zeolite adsorbent materials used for the decarbonization of natural gas, are particularly suitable for the decarbonization of natural gas for GN plants, LNG and floating units, as described above, to using the separation processes hereinbefore defined.

[0037] According to a preferred aspect of the present invention, the zeolitic adsorbent materials suitable for the decarbonation of natural gas can be combined with other adsorbent materials in a single separation method defined previously. In particular, the zeolitic adsorbent materials defined according to the invention can be used in combination, as a mixture, or separately with one or more other zeolitic adsorbent materials containing a zeolite selected from zeolites 3A, 4A and 13X, and mixtures thereof, to perform a complementary decarbonation treatment and / or additional and / or to remove other impurities such as water and aromatic hydrocarbons.

[0038] In the case where the natural gas contains impurities such as water in large quantities, it may be contemplated to remove the water by specific adsorption on a specific zeolitic adsorbent material comprising a zeolite of by example 3A and / or 4A or other adsorbents well known to those skilled in the art, and then to drive the natural gas containing only water, or minimal traces of water in the decarbonation process of the present invention.

[0039] In the case where the natural gas contains impurities such as aromatic hydrocarbons in large quantities, but also water, it may be contemplated to remove these impurities by specific adsorption on a zeolite adsorbent material, preferably comprising a zeolite type 13X or silica gel or other adsorbents well known to those skilled in the art, and then to drive the natural gas containing more aromatic hydrocarbons or water or only minimal traces

aromatic hydrocarbons and water, in the calcining method of the present invention.

[0040] When the natural gas contains several impurities, in particular those defined above, one may thus envisage one or more treatments by adsorption on zeolitic adsorbent materials and then carry out the treatment of decarbonation of natural gas according to the present invention. The method for removing impurities defined above combined processing of decarbonation defined above is also part of the present invention.

[0041] It is also possible to perform all these treatments after or before or simultaneously with the treatment of decarbonization of natural gas as defined above, by beds of adsorbents (zeolite adsorbent material or other adsorbents well known to the skilled person, for example silica gel, activated carbon, activated alumina, metal oxide, and others), separated and / or mixed. By "mixed bed" means mixtures of two or more different adsorbents and layers of two or more different adsorbents or alternating layers of different adsorbents or not.

[0042] According to another aspect, the present invention relates to a natural gas decarbonation process comprising at least the steps of:

• providing a natural gas comprising carbon dioxide,

• contacting the said natural gas with at least one zeolitic adsorbent material as defined above, and

• recovery of natural gas decarbonated.

[0043] The calcining method of 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. CO2, preferably less than 2% by volume of CO2.

[0044] 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 offshore units, FLNG units ( "Floating Liquefied Natural Gas" in English), FPSO units ( "Floating Production Storage Offloading" in English), and others.

[0045] 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 adsorbent material zeolite as described above for the calcining natural gas.

Characterization Techniques

[0046] The physical properties of the zeolitic adsorbent materials useful in the present invention are evaluated by methods known to those skilled in the art and defined below.

Size of the zeolite crystals ETA:

[0047] The estimate of the number average diameter of the zeolite crystals contained in the LTA zeolitic adsorbent materials, which are used for preparing said zeolitic adsorbent material is carried out by observation with a scanning electron microscope (SEM), optionally after fracture samples of zeolite adsorbent material.

[0048] In order to estimate the size of zeolite crystals on the samples is carried out a set of photographs at a magnification of at least 5000 is then measured diameter of at least 200 crystals using a dedicated software, such as Smile View software of LOGRAMI editor. Accuracy is of the order of 3%.

Particle size of the zeolite adsorbent materials

[0049] The determination of the volume mean diameter (D50 or "volume average diameter" or length, that is to say larger when the material is not spherical) of the zeolitic adsorbent material of the process according to the invention is carried out by analyzing the size distribution of an imaging adsorbent material sample according to ISO 13322-2: 2006, using a treadmill allowing the sample to pass the camera lens.

[0050] The volume average diameter is then calculated from the particle size distribution by applying the standard ISO 9276-2: 2001. In this document, the term is used "volume mean diameter" or "size" for the zeolite adsorbent materials. The accuracy is of the order of 0.01 mm for the size range of adsorbent materials useful in the context of the present invention.

Chemical analysis of adsorbent materials zéolithiques- atomic ratio Si / AI and calcium oxide (CaO)

[0051] An elementary chemical analysis of a zeolite adsorbent material described above, can be performed by various analytical techniques known in the art. Such techniques include the art of chemical analysis by X-ray fluorescence as described in the standard NF EN ISO 12677: 201 1 of a dispersive spectrometer wavelength (WDXRF), e.g. Tiger S8 of Bruker.

[0052] The X-ray fluorescence is nondestructive spectral technical operator photoluminescence atoms in the field of X-ray to establish the composition

Elemental a sample. The excitation of the atoms, which is usually and generally carried out by an X-ray beam or by bombardment with electrons, generates specific radiation after returning to the ground state of the atom. conventional manner obtained after calibration for each oxide measurement uncertainty less than 0.4% by weight.

[0053] Other analytical methods are illustrated for example by the methods by atomic absorption spectrometry (AAS) and atomic emission spectrometry with inductively coupled plasma (ICP-AES) as described in EN ISO 21587-3 or EN ISO 21079-3 on a type of device such as Perkin Elmer 4300DV.

[0054] The fluorescence spectrum X has the advantage of very little depend on the chemical combination of the element, which provides an accurate determination, both quantitative and qualitative. conventional manner obtained after calibration for each S1O2 oxide and Al2O3, and CaO, a measurement uncertainty of less than 0.4% by weight.

[0055] The elemental chemical analysis described above can both verify the Si / Al ratio of the zeolite used in the zeolite adsorbent material, the atomic Si / Al ratio of the zeolite adsorbent material and the oxide content of calcium, expressed in weight of CaO, zeolite adsorbent material. In describing the present invention, the measurement uncertainty of Si / Al is ± 5%. The measurement of the atomic Si / Al ratio of the zeolite present in the adsorbent material can also be measured by spectroscopy Nuclear Magnetic Resonance (NMR) solid silicon.

Strength of zeolite adsorbent materials:

[0056] The crushing strength in bed (REL) of the zeolitic adsorbent materials as described in the present invention is characterized according to the ASTM 7084-04 standard.

Mechanical resistance to grain crushing are determined with an apparatus

"Grain Crushing strength" sold by Vinci Technologies, according to standards

D 4179 (201 1) an ASTM D 6175 (2013).

Fire loss zeolite adsorbents:

[0057] 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 the standard NF EN 196-2 (April 2006). The standard deviation measurement is less than 0.1%.

qualitative and quantitative analysis by X-ray diffraction

[0058] The amount of zeolite A in the zeolitic adsorbent material is evaluated by diffraction of X-ray analysis (XRD), according to methods known to those skilled in the art. This identification can be performed using a Bruker XRD unit of the brand.

[0059] This analysis identifies the different zeolites present in the zeolite adsorbent material for each zeolite has a unique diffraction pattern defined by the positioning of the diffraction peaks and their relative intensities.

[0060] The zeolitic adsorbent materials are then crushed and spread on a sample holder smoothed by simple mechanical compression.

[0061] The conditions of acquisition of diffraction performed on the D5000 Brucker device are:

Cu tube used at 40 kV - 30 mA;

size of the slits (divergent, disseminating and analytical) = 0.6 mm;

• Filters: Nine;

sample rotating device 15 tr.min "1 ;

measuring range: 3 ° <2Θ <50 °;

Step: 0.02 °;

counting time per step: 2 seconds.

[0062] The interpretation of the resulting diffraction pattern is made with EVA software with identification of zeolites using the base ICDD PDF-2, release 1 201.

[0063] The amount of zeolite fractions A, by weight, measured by XRD, this method is also used to measure the amount of zeolitic fractions other than A. This analysis was performed on Bruker D5000 apparatus of the mark, then the amount by weight of the zeolite fractions was assessed using the TOPAS software Bruker.

Measuring the H50 water adsorption capacity

[0064] The measurement of the H50 water adsorption capacity is carried out by a static method of measuring the weight increase of the zeolitic adsorbent material, placed in a sealed container for 24 hours in equilibrium with a controlled atmosphere 50% relative humidity and at ambient temperature (22 ° C). It expresses the capacity of adsorption of water, as a percentage, the difference in weight between the zeolitic adsorbent material before and after the test described above, divided by the weight of the zeolitic adsorbent material prior to the test described above. The standard deviation measurement is less than 0.3%.

Examples

[0065] The present invention is now illustrated by the following examples which do not limit in any way the scope of the invention whose scope of protection conferred by the claims. In what follows, a mass in "anhydrous equivalent" means decreased product mass of ruin fire.

[0066] The zeolitic adsorbent materials used in the following examples are prepared in the form of extrudates of 1, 6 mm in diameter and 5 mm to 7 mm in length. The zeolite adsorbent materials tested are described below:

Sample A: zeolite adsorbent material 4A Siliporite® NK 10, marketed by CECA SA

Sample B: zeolite adsorbent material 13X Siliporite® G5, marketed by CECA SA

Sample C Preparation of a zeolitic adsorbent material obtained by spinning a mixture of zeolite 5A (80% by weight anhydrous equivalent) and kaolin (20% by weight anhydrous equivalent) as the agglomeration binder, according to the techniques well known to those skilled in the art, as described for example in US3219590. The size of 5A zeolite crystals is 7.5 μηη. The CaO content of the zeolitic adsorbent material is 12.3% by weight, Si / Al ratio is 1, 01 and its water adsorption capacity was 20.5% H50

Sample D: preparation of a zeolite 5A adsorbent material similar to the sample

C, substituting kaolin attapulgite. The CaO content of the zeolitic adsorbent material is 12.4% by weight, Si / Al ratio is 1, 33 and its water adsorption capacity was 20.6% H50

Sample E: preparation of a zeolitic adsorbent material similar to the sample D by replacing zeolite 5A zeolite Y (CBV 100 from Zeolyst International). Sample F: preparation of a zeolite 5A adsorbent material similar to the sample

D, replacing attapulgite by a mixture 2/3 by weight of attapulgite and montmorillonite 1/3. The CaO content of the zeolitic adsorbent material is 12.2% by weight, Si / Al ratio is 1, 30 and its water adsorption capacity was 20.5% H50

[0067] An amount of 725 g of each sample is loaded into a pilot plant decarbonation (installation carbon dioxide adsorption driver) fitted natural gas to an adsorption column having an internal diameter of 27 mm and wherein 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 12 m 3 / h, pressure 6 MPa, and the temperature is 40 ° C.

example 1

[0068] CO2 adsorption capacities, expressed by percentage weight (g CO2 adsorbed per 100 g of zeolite adsorbent material) are shown in Table 1 and are calculated from the following equation:

Qgaz x [CO2 ] x t50

Capacity

χ 10 Ground

or

• "Qgas" represents the average rate of gas flow in Nm 3 / h,

• "[CO2]" represents the average CO2 concentration into ppm,

• "t 5 o" represents the time in hours stoichiometric, when time reaches the CO2 concentration at the outlet of the column is equal to 50% of the average concentration of CO2 in the column inlet, and

• "mass" is the mass of zeolite adsorbent material (in grams).

[0069] The test results indicate that the pilot sample D consisting of zeolite 5A CaO content of 12.4%, and agglomerated with an attapulgite binder has the highest CO2 adsorption capacity. The results are presented in Table 1 below:

~ Table 1 -

example 2

[0070] The mass transfer zones (ZTM), in centimeters, of CO2 on the zeolitic adsorbent materials are shown in Table 2 and are calculated from the equation below. The higher the value of the ZTM zeolite adsorbent material, the lower the adsorption kinetics of the zeolite adsorbent material is fast.

2 x (t 50 L breakthrough '

ZTM = Hcolome x - l50

or

• "ZTM" represents the mass transfer area, in centimeters,

• "Hcobnne" represents the height of the column, in centimeters,

• "ercée t" ​​represents the time of breakthrough, in time, as described in the book "Encyclopedia of Chemical Processing and Design", 28 May 1999 Vol. 67, pp. 384-385: "Zeolites" John J. McKetta Jr., CRC Press, 500 pages,

• "t 5 o" shows, in time, when the time reaches the CO2 concentration at the outlet of the column is equal to 50% of the average CO2 concentration at the column entrance,

[0071] The test results indicate that the pilot sample D consisting of 5A zeolite agglomerated with attapulgite, has a ZTM shorter and thus an adsorption kinetics faster than CO2 with the agglomerated material kaolin (sample C).

[0072] The zeolitic adsorbent material based on a 5A zeolite agglomerated with attapulgite is particularly suitable for the decarbonation of natural gas. The results are presented in Table 2 below.

- Table 2 -

[0073] Example 3Des accelerated aging tests are carried out on samples of adsorbent materials zeolitic C and D by contacting each sample with pure carbon dioxide at a temperature close to that used during the regeneration of the zeolitic adsorbent materials in a TSA industrial process (180 ° C) for 3 months. This period of 3 months is representative of the total time of contacting with the hot regeneration gas in an industrial unit. The pressure of CO2 is maintained at 5 bar for the duration of the tests. After cooling, nitrogen inerting, the zeolitic adsorbent material sample is discharged for evaluation of mechanical resistance to crushing (RM).

[0074] Table 3 shows mechanical resistance to initial crushing of adsorbents zeolitic materials C and D, and the values ​​obtained after accelerated aging tests described above.

- Table 3 -

Sample C sample D sample E

RM 4.0 3.5 3.7 Initial

RM after

2,2 3,0 3,2

aging

CLAIMS

1. The use for the decarbonation of natural gas, of at least one zeolitic adsorbent material comprising:

a) from 70% to 99% by weight, preferably from 70% to 95% by weight, more preferably from 70% to 90% by weight, more preferably from 75% to 90%, most preferably 80% to 90% of at least one zeolite a, relative to the total weight 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%, most preferably 10% to 20% relative to the total weight of the zeolitic adsorbent material of at least one agglomeration binder comprising at least one clay selected from fibrous magnesian clays.

2. Use according to claim 1, wherein the fibrous magnesian clays are hormites, and preferably are preferably chosen from sepiolite and attapulgite.

3. Use according to claim 1 or claim 2, wherein the binder comprises a mixture of clay (s) consisting of at least one fibrous clay magnesium, and at least one other clay.

4. Use according to any preceding claim wherein the zeolite A comprises calcium ions, typically calcium and sodium ions.

5. Use according to any preceding claim, wherein the zeolitic adsorbent material 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%, inclusive, by weight CaO based on the total weight of the zeolitic adsorbent material.

6. Use according to any preceding claim, wherein the zeolite is selected from zeolites and zeolites 5A 5APH.

7. Use according to any preceding claim, wherein the atomic Si / Al 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 1, 0 and 1, 6, inclusive.

8. Use according to any preceding claim, wherein the natural gas decarbonation process is a TSA process, or a PSA or PTSA method, and more preferably a TSA process.

9. Use according to any preceding claim, wherein the zeolitic adsorbent material is used in combination, as a mixture, or separately with one or more other zeolitic adsorbent materials containing a zeolite selected from zeolites 3A, 4A and 13X and mixtures thereof.

10. Natural gas decarbonation process comprising at least the steps of:

• providing a natural gas comprising carbon dioxide,

• contacting the said natural gas with at least one zeolitic adsorbent material as defined in any one of claims 1 to 7, and

• recovery of natural gas decarbonated.

11. The method of claim 10, wherein the gas contacted 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 CO2.

12. Natural gas decarbonation unit comprising at least one zeolitic adsorbent material as defined in any one of claims 1 to 7.

13. Natural gas decarbonation unit according to claim 12 which is a GN plant, an LNG plant, a floating unit, a floating offshore, a FLNG unit, or an FPSO.

Eregister

Legal Status: Inforce Grant Date: 26/08/2019 Patent Date: 06/09/2016

Specification

Documents

Application Documents

	Name	Date
1	201817008201-RELEVANT DOCUMENTS [09-06-2023(online)].pdf	2023-06-09
2	201817008201-RELEVANT DOCUMENTS [14-06-2022(online)].pdf	2022-06-14
3	201817008201-RELEVANT DOCUMENTS [20-07-2021(online)]-1.pdf	2021-07-20
4	201817008201-RELEVANT DOCUMENTS [20-07-2021(online)]-2.pdf	2021-07-20
5	201817008201-RELEVANT DOCUMENTS [20-07-2021(online)].pdf	2021-07-20
6	201817008201-RELEVANT DOCUMENTS [21-03-2020(online)].pdf	2020-03-21
7	201817008201-IntimationOfGrant26-08-2019.pdf	2019-08-26
8	201817008201-PatentCertificate26-08-2019.pdf	2019-08-26
9	201817008201-Correspondence-130819.pdf	2019-08-19
10	201817008201-Power of Attorney-130819.pdf	2019-08-19
11	201817008201-ABSTRACT [12-08-2019(online)].pdf	2019-08-12
12	201817008201-CLAIMS [12-08-2019(online)].pdf	2019-08-12
13	201817008201-COMPLETE SPECIFICATION [12-08-2019(online)].pdf	2019-08-12
14	201817008201-FER_SER_REPLY [12-08-2019(online)].pdf	2019-08-12
15	201817008201-FORM-26 [12-08-2019(online)].pdf	2019-08-12
16	201817008201-OTHERS [12-08-2019(online)].pdf	2019-08-12
17	201817008201-PETITION UNDER RULE 137 [12-08-2019(online)].pdf	2019-08-12
18	201817008201-FER.pdf	2019-05-20
19	201817008201-FORM 3 [04-12-2018(online)].pdf	2018-12-04
20	201817008201-Correspondence-060618.pdf	2018-06-18
21	201817008201-OTHERS-060618.pdf	2018-06-18
22	201817008201-Proof of Right (MANDATORY) [05-06-2018(online)].pdf	2018-06-05
23	201817008201.pdf	2018-04-07
24	201817008201-COMPLETE SPECIFICATION [06-03-2018(online)].pdf	2018-03-06
25	201817008201-DECLARATION OF INVENTORSHIP (FORM 5) [06-03-2018(online)].pdf	2018-03-06
26	201817008201-FORM 1 [06-03-2018(online)].pdf	2018-03-06
27	201817008201-FORM 18 [06-03-2018(online)].pdf	2018-03-06
28	201817008201-POWER OF AUTHORITY [06-03-2018(online)].pdf	2018-03-06
29	201817008201-PRIORITY DOCUMENTS [06-03-2018(online)].pdf	2018-03-06
30	201817008201-REQUEST FOR EXAMINATION (FORM-18) [06-03-2018(online)].pdf	2018-03-06
31	201817008201-STATEMENT OF UNDERTAKING (FORM 3) [06-03-2018(online)].pdf	2018-03-06
32	201817008201-TRANSLATIOIN OF PRIOIRTY DOCUMENTS ETC. [06-03-2018(online)].pdf	2018-03-06

Search Strategy

1	2019-05-2012-26-25_20-05-2019.pdf