adsorbed composition heat treated, and used in adsorption and gas separation processes, adsorption p

专利摘要:
THERMALLY TREATED ADSORVENT, AND USED IN GAS SORING AND SEPARATION PROCESSES, ADSORPTION PROCESS TO SEPARATE N FROM A 2 GAS MIXTURE CONTAINING N, AND, METHOD TO MAKE A 2 COMPOSITION ‡ SUMMARY ADSORBENTâ € Adsorbent compositions used in adsorption and separation processes are produced using silicone-derived binding agents. The adsorbent compositions are produced from crystallite aluminosilicate particles bonded with silicone derived binding agents, and optionally small amounts of a clay binder, to form agglomerated crystallite particles and are calcined to volatilize the organic components associated with silicone-derived binding agents. The agglomerated crystallite particles have superior pore structures and crushing strengths superior to low concentrations of binders and have enhanced N adsorption rates and capacities when used in air separation processes.
公开号:BR112014032145B1
申请号:R112014032145-0
申请日:2013-06-20
公开日:2021-02-23
发明作者:Philip Alexander Barrett；Steven John Pontonio；Persefoni Kechagia；Neil Andrew Stephenson；Kerry C. Weston
申请人:Praxair Technology, Inc；
IPC主号:

专利说明:

Field of the Invention
[001] The present invention is directed to novel adsorbent compositions used in gas adsorption and separation processes. More particularly, the invention is directed to adsorbents produced from agglomerated crystalline particles bonded with silicone derived binders and optionally small amounts of a clay binder. The present adsorbents have superior pore structures and crushing strengths superior to low concentrations of binder and exhibit enhanced N2 adsorption rates and capacities when used in air separation processes. Fundamentals of the Invention
[002] The adsorbents of this invention are used in adsorption and separation of gases. Preferably, the adsorbent compositions are used in processes to separate N2 from mixtures containing N2 and other gases by bringing the mixture into contact with an adsorbent composition that selectively adsorbs the N2 with one or more of the less strongly adsorbable components recovered as a product.
[003] Of particular interest is the use of these adsorbents in non-cryogenic gas separation processes. For example, the separation of nitrogen from gas mixtures is the basis for several industrial adsorption processes, including the production of oxygen from the air. In the cyclical production of oxygen from the air, air passes through an adsorbent bed with a preference for nitrogen adsorption molecules and leaving oxygen and argon (the least strongly adsorbable components) to be produced. The adsorbed nitrogen is then desorbed through a purging step, usually through a change in pressure, including vacuum, and / or through temperature changes to regenerate the adsorbent and the cycle is repeated. Such processes include pressure swing adsorption (PSA), temperature swing adsorption (TSA), vacuum swing adsorption (VSA) and vacuum pressure swing adsorption (VPSA) and such processes are commonly used in operations commercial air separation systems as well as other industrial processes.
[004] Clearly, the particular adsorbent used in these processes is an important factor in obtaining an efficient, effective and competitive process. The performance of the adsorbent depends on several factors, including the adsorption capacity for N2, the selectivity between gases, which will impact the production yield, the adsorption kinetics, which will allow the adsorption cycle times to be optimized to improve productivity of the process. The crushing resistance / attrition rate of the agglomerated particles is also very important, particularly in relation to obtaining a satisfactory adsorbent life in the adsorption process and system. Many of these factors depend directly on the particle pore structure and the total pore architecture.
[005] The present invention is directed to novel adsorbent compositions, comprised of agglomerated adsorbent particles composed of at least one active component and a silicone-derived binding agent. The adsorbents produced from this show a surprising increase in adsorption capacity versus state-of-the-art clay compositions. In addition, adsorbents are produced during the manufacturing process to enhance their adsorption rate (kinetic) properties through improved composition (ie, very high active phase concentration) and pore structure architecture. Such adsorbents have high values of crush resistance and higher properties of the adsorption rate and especially allow intensification of the PSA / TSA / VSA / VPSA process, a term commonly used to describe fast cycles with high rate adsorbents. When effectively used in these adsorption processes, such adsorbents lead to lower capital costs, reduced energy consumption and / or greater product recovery.
[006] Conventional agglomerated adsorbents used for such processes are composed of zeolite powders (crystalline particles), including zeolite powders subjected to ion exchange depending on the process and binding agent. The bonding agent aims to guarantee the cohesion of the agglomerated particles which are generally in the form of microglobules, precipitated, and extruded. Bonding agents generally have no adsorbent properties and their function is only to give the agglomerated particles sufficient mechanical strength to withstand the unfolding rigors in packaged bed adsorption systems and the vibrations and stresses to which they are subjected during the particular adsorption process. , such as pressurization and depressurization. The particular bonding agent and its concentration impact the final pore structure of the agglomerated particles, thereby affecting the properties of the adsorbent. It is known that the concentration of binding agent should be as low as possible to reduce resistance to mass transfer that can be negatively impacted by the excess binder present in the pores. Certain binding agents, temporary binders and other processing aids can also partially fill or otherwise partially block the particle pores while other binding agents can have an adverse effect on the final pore structure depending on the particular solvents that carry the particular binding agents.
[007] One of the most common methods to obtain adsorbent particles agglomerated with low concentrations of binders, improved pore architectures and low resistance to mass transfer, is the use of the caustic digestion method to prepare adsorbents without binder. Binder-free adsorbents represent an approach to obtain a low binder content, but at the expense of additional manufacturing steps and higher costs. The conventional approach to caustic digestion is to employ clay binding agents that can be converted into active adsorbent material through caustic treatment. Several previous descriptions have claimed unprecedented pore structures and have demonstrated various levels of improvement in the adsorption rate properties from the use of these adsorbents without binder.
[008] For example, US patent No. 6,425,940 B1 describes a high-rate adsorbent produced substantially without binder and with a median pore diameter> 0.1 μo and, in some cases, a bimodal pore distribution with pores larger, 2 to 10 microns, designed using combustible fibers such as nylon, rayon and sisal, added during the forming process. In US Patent No. 6,652,626 B1, a process for producing agglomerated bodies of zeolite X is described in which a binder containing at least 80% of a clay convertible to zeolite, after calcination, is brought into contact with a caustic solution for obtain an agglomerated zeolite material composed of at least 95% of a Li exchange zeolite X, with a Si / Al = 1. The products are reported with N2 capacities at 1 bar, 25 ° C of 26 mL / g which correspond to less than 26 mL / g 1 atm and 27 ° C. No pore structure or diffusivity information is described. In U.S. Patent Application Publication No. 2011/104494, an adsorbent granule based on zeolite is described, comprising a zeolite of the Faujasite structure and with a molar ratio of SiO2 / AhO3> 2.1 to 2.5. The adsorbent granulate has an average transport pore diameter of> 300 nm and a mesoporous fraction <10% and preferably <5%. The adsorbent granulate is prepared by mixing a type X zeolite with a heat-treated culinite clay in the presence of sodium silicate, sodium aluminate and sodium hydroxide.
[009] A significant drawback for the manufacture of these adsorbents without binder is their high manufacturing cost due to the processing steps, reagents and additional time required for the conversion of binder. Another disadvantage of making adsorbents without a binder stems from the need to handle, store and dispose of large quantities of the highly caustic solutions required in the adsorbent manufacturing process. This increases costs and environmental concerns for the process.
[0010] Another class of previous adsorbents provides for unprecedented pore architectures through the use of novel binding agents or traditional binding agents with improved agglomeration processing. US patent No. 6,171,370 B1 describes an adsorbent having utility in a PSA process that is characterized by having macropores with an average diameter greater than the average free path of an adsorbable component, during desorption of said component, and in which at least 70 % of the volume of the macropores are occupied by macropores with a diameter greater than or equal to the average free path of the adsorbable component. The use of clay binders including atapulgite and sepiolite in concentrations of 5 to 30% by weight is described. U.S. patent 8,123,835 B2 describes the use of colloidal silica binders to produce superior adsorbents for gas separation applications including air separation. This precept uses colloidal silica binding agents producing macropores substantially free of binding agent. The adsorbents are characterized by an adsorption rate, expressed as a relative rate compensated by size / porosity, of at least 4.0 mmol mm2 / g s. The binder content is less than or equal to 15% by weight and the average crush resistance is greater than or equal to 0.408 kgF (0.9 lbF) measured on particles with an average size of 1.0 mm.
[0011] Other precepts use silicones as the precursor of binders in various catalysts and related shaped bodies, such as honeycomb-like catalytic structures. For example, US patent 7,582,583 B2 provides for modeled bodies, such as honeycomb structures, containing microporous material and a binder containing silicon used for the production of triethylenediamine (TEDA). The catalyst is formed by mixing the microporous material, the binder, a constitution aid and the solvent; forming, drying and calcining the structure. The constitution aid is cellulose or cellulose derivative, and the solvent can be selected from a list of various organic solvents. US patent 5,633,217 provides for a method of making a catalyst, catalyst support or adsorbent body by forming a mixture of ceramic and / or molecular sieves, silicone resin, a dibasic ester solvent, organic binder, and water. The mixture is modeled on a green, dry and heated body. US patent 6,458,187 provides for a body containing modeled zeolite prepared from a particular class of siloxane-based binders in combination with zeolite, plasticizer, and methylcellulose. The body is formed by mixing the components and calcining at temperatures below 300 ° F in order not to volatilize methyl cellulose or other volatiles.
[0012] In accordance with this invention, adsorbents are provided for gas separation processes that are produced from fluid agglomerated particles. These adsorbents have high N2 adsorption rates, high N2 adsorption capacities, high crushing strengths and frictional resistance, and are linked with low concentrations of total bonding agents using less expensive and traditional manufacturing processes. In addition, the adsorbent compositions are characterized by an adsorption capacity of N2 at 27 ° C and 1 atm which is greater than an equivalent composition containing all clay binding agents. Summary of the Invention
[0013] The present invention provides superior agglomerated adsorbent compositions used in adsorption and separation processes, including cyclic gas separation processes, such as air separation. These adsorbents are comprised of active adsorbent materials such as aluminosilicate powders or crystallites which are agglomerated using low concentrations of a silicone derived binder. Optionally, a granulation seed process is used for the production of the commercial adsorbent composition, in which the seed comprises less than 25% by volume of the total adsorbent composition. The seed composition comprises an aluminosilicate powder or crystallite and a binder comprising a binding agent derived from silicon and / or clay, and when clay is used, the clay comprises less than 3% by weight of the adsorbent composition. The agglomerated particles have high values of crush resistance, superior pore structures and connectivity, and enhanced adsorption rate and capacity properties.
[0014] In one embodiment, a heat-treated adsorbent composition comprising a mixture of at least one active material and a silicone derived bonding agent formed as agglomerated particles comprised of 90% or more of at least one active material calculated on the basis is provided in the final product in dry weight and with a median pore diameter greater than or equal to 0.47 μo. 10% or less of macropores and mesopores are less than or equal to 0.1 μo. a hysteresis factor greater than or equal to 0.6, and a crush resistance value greater than or equal to that obtained from the value determined by the relationship y = 1.2x - 0.3 where y is the average crush resistance in kgF (lbF ) ex is the average particle size in mm. In addition, the adsorbent composition comprising agglomerated crystallite zeolite particles bonded with a silicone derived binder and a clay binder in concentrations of no more than 1 part of clay binder to 5 parts of silicone binder, and with the crystallite zeolite particles comprising one or more type X zeolites with a SiO2 / Al2O3 ratio less than or equal to 2.5 have substantially no visible silicone-derived binding agent in the pores of the agglomerated particles when viewed in SEM at a magnification of 4,500x.
[0015] In yet another embodiment, an adsorption process is provided to separate N2 from a gas mixture containing N2 and at least one less strongly adsorbable component comprising bringing the mixture into contact with an adsorbent composition that selectively adsorbes N2 and hair less a less strongly adsorbable component is recovered as a product; the adsorbent composition comprising fluid agglomerated particles of a type X zeolite bonded together by a silicone derived binding agent and wherein the composition's N2 capacity is greater than or equal to 26 ml / g at 1 atm and 27 ° C.
[0016] In another embodiment, a method is provided for making an agglomerated adsorbent composition comprising: (a) preparing a mixture comprising one or more activated zeolite materials and a silicone derived binder, (b) mixing seed material comprising one or more of the activated zeolite materials and a clay binder with the mixture and water to form agglomerated adsorbent particles, (c) drying the agglomerated adsorbent particles, (d) calcining the dry agglomerated adsorbent particles to form a calcined and optionally composition , (e) rehydrating the calcined composition to form rehydrated agglomerated adsorbent particles, (f) treating the rehydrated agglomerated adsorbent particles with a metal salt solution to perform an ion exchange of cations to form agglomerated adsorbent particles subjected to ion exchange, and (g) dry and activate the particles subjected to ion exchange by heating under dry purge gas that of agglomerated ion exchange particles to form the agglomerated adsorbent composition. Brief Description of Drawings
[0017] Figure 1 is a set of 4 images of Scanning Electron Microscope each showing a cross section of an adsorbent microglobe manufactured using a conventional bonding agent (a) and (b) and the silicone derived bonding agent of the present invention (c) and (d).
[0018] Figure 2 is a graph showing limiting crush resistance versus average particle size for compositions using conventional binders compared to the silicone derived binder of the present invention.
[0019] Figure 3 is X-ray diffraction data for a comparative adsorbent composition using silicon derived binding agents in a dibasic ester solvent.
[0020] Figure 4 is a graph of the nitrogen adsorption capacities (27 ° C, 101.3 kPa (760 Torr)) for inventive and comparative commercial and laboratory-prepared samples. Detailed Description of the Invention
[0021] The present invention is directed to adsorbent compositions that are modeled on the fluid agglomerated particles or microglobules used in adsorption and gas separation processes. They are particularly used for the separation of nitrogen gas or nitrogen gas species from air and other gas mixtures. Processes that require adsorbents with high N2 adsorption capacities, high adsorption rates, high values of crush resistance and friction resistance are preferred, and which require the ability to withstand demands of packaged bed adsorption processes including pressurization stresses / depressurization.
[0022] Although used in other processes, the adsorbent compositions are preferably used in cyclic adsorption processes for the adsorption of nitrogen gases from the air in PSA, TSA, VSA or VPSA type processes or a combination of these for the production of oxygen from the air. air. PSA, TSA, VSA or VPSA process or systems separate gas species from a mixture of gases at high pressure and / or temperature according to the molecular characteristics of gas species and affinity with the adsorbent. The feed air passes through a first packaged porous bed containing the adsorbent material that adsorbs the target gas species (nitrogen) at higher pressures and then the process reverts to a lower pressure and process gas is used to purge and desorb the species of adsorbed gas (nitrogen) from the adsorbent material in the bed. Typically, this process alternates between two or more microglobules, maintaining continuous operation, although single bed systems are known. The steps in a multi-layer air separation adsorption cycle generally include: (1) high pressure adsorption (feed), (2) countercurrent discharge to reduce pressure, or vacuum, (3) countercurrent purge with a relatively free gas impurities, and (4) repressurization at a higher pressure, with both supply air and purified air. The regeneration of the adsorbents in the process is achieved by a combination of a simple reduction in pressure, including vacuum, and / or elevation of temperature and subsequent purging with a gas without impurity. Any reactor or vessel configuration can be employed, such as that with a radial or axial configuration.
[0023] The adsorbent compositions of this invention must be able to withstand strict conditions of cyclic adsorption and are derived from mixtures of at least one active material and a precursor of silicone binder which, after subsequent heat treatment, turns into the binding agent. The active materials used for nitrogen adsorption include one or more natural and synthetic aluminosilicates and / or molecular sieves. Preferred are zeolites that are thermally stable (that is, they retain appreciable surface area measured, for example, by the established BET method, see Chapter 3 in Analytical Methods in Fine Particcle Technology, Paul A. Webb & Clyde Orr, Published by Micromeritics Instruments Corp., 1997 ISBN0-9656783-0-X) at the temperatures required to volatize the organic matter associated with the silicone binder precursor. Such materials are subjected to strict process conditions and must have internal support structures that can withstand such conditions for extended periods. Preferred are one or more type X zeolites that can incorporate cations, such as Li, Ca, K, Na, Ag and mixtures thereof, exchanged in the lattice structure and with a SiO2 / Al2O3 ratio less than 15, more preferably less than 5, and above all preferably less than or equal to 2.5. Examples of such zeolites include X2.0 or LSX. Above all preferred is LiLSX with a Li content> 95%. The preferred zeolites X as described above are particularly selective for N2 adsorption and generally have weaker infrastructure than those zeolites with high SiO2 / Al2O3 ratios, such as those with SiO2 / Al2O3 ratios greater than 20 that are commonly used as structures of the catalyst materials or catalyst support. Thus, these active materials must be prepared using techniques that strengthen, or at least do not weaken, the infrastructure. For this reason, strengthening the support structure of the zeolite, and finally of the agglomerated particles, is critical and it was observed that the use of binding agents dispersed or charged in organic solvents should be avoided.
[0024] The active material has an average particle size greater than 1 micron and preferably greater than 4 microns to produce the particle agglomerated with the pore characteristics described in this invention. Particles with an average size of 1 micron or less cannot be made in the agglomerated particles with a median pore diameter greater than or equal to 0.47 μo and with 10% or less of macropores and mesopores less than or equal to 0.1 micron . It is also preferred that the final agglomerated adsorption composition (active material and binding agent) has an average particle size ranging from 0.4 mm to 5.0 mm and more preferably 0.6 to 1.8 mm. Zeolites X are particularly suitable as the active component, since the manufacturing process can employ heat treatments at temperatures from 400 ° C to about 700 ° C without degradation, still allowing the conversion of silicones into the form that acts as the Link. In general, adsorbents that have been agglomerated using traditional clay binders or other molecular silica binders, including colloidal silica binders, can be agglomerated using the silicones of the present invention.
[0025] In the manner described, silicones are used as the precursors of binder that, during the course of preparation of the adsorbent, change to a form or species that becomes the binding agent in the final agglomerated particles. Silicones are synthetic compounds comprised of polymerized or oligomerized silicon units together with predominantly carbon, hydrogen and oxygen atoms. Silicones, also commonly known as siloxanes or polysiloxanes, are considered a hybrid of both organic and inorganic compounds since they contain organic side chains in an inorganic -Si-O-Si-O- backbone. Their structures can include linear, branched, reticulated and cage-like variants.
[0026] Silicones have the general formula [R2SiO] n, where R is one or more organic side groups selected from organic compounds C1 to C8, preferably organic compounds C1 to C4, including linear, branched and cyclic compounds or mixtures thereof and where polymeric or oligomeric silicones are typically terminated by hydroxy, methoxy, ethoxy groups or mixtures thereof. The silicones of interest generally have molecular weights ranging from about 100 to more than 500. The side group R can also represent other organic groups such as vinyl or trifluorpropyl and it is believed that a wide range of silicones is used in this invention. Examples of silicones include, but are not limited to, polydimethylsiloxanes and polydiphenylsiloxanes such as those identified by Chemical Abstracts Service (CAS) registration numbers 63148-62-9 and 63148-59-4 and those with dimethyl groups in polymeric forms with methyl, octyl silsesquioxanes such as CAS registration number 897393-56-5 (from Dow Corning with the designation IE 2404); methyl silsesquioxanes such as CAS number 68554-66-5; and (2,4,4-trimethylpentyl) triethoxysilane such as CAS number 35435-21-3. Preferred silicones are selected from hydroxy, methoxy, or finished ethoxy polymeric dimethylsiloxane or mixtures of these with methyl silsesquioxanes, octyl silsesquioxanes, methyl octyl silsesquioxanes, or mixtures thereof.
[0027] Silicones of more than one type can be used, and silicones can be used with other organic or inorganic compounds. Additional common components include water, copolymer stabilizing agents, emulsifying agents and surfactants and emulsions, and silicone suspensions can be employed as the silicone binder precursors. These additional components are often present to stabilize the particular shape of the silicone that is typically used in the form of an emulsion, solution, or resin.
[0028] In one embodiment, the silicone binder is used together with a clay bonding agent to form a double bonding agent system, in which the clay binder is present in a concentration of no more than 1 part of binder of clay to 5 parts of silicone derived binder and preferably no more than 1 part of clay to 10 parts of silicone derived agent, when measured based on the final product in dry weight. The total amount of clay binder should not exceed 3%, preferably 2%, based on the final dry weight product of the agglomerated adsorption composition. The use of small amounts of clay as a binder is particularly advantageous for microglobule formation processes to increase the manufacturing yield and / or to increase the manufacturing volume. In such cases, it is preferred that the clay be used initially to form seeds or nuclei of the adsorbent composition to stimulate the agglomeration process and then the silicone-derived binding agent is used to complete the agglomeration process. Typically, seeds or kernels are formed from clay and the active adsorbent material and comprise from about 0.5 to 25% by volume of the agglomerated particle and in which the percentage of the general bonding agent which is clay is not more than 18% by weight, with the balance being silicone-derived binding agent.
[0029] The typical manufacturing process for making adsorbents requires a heat treatment step generally known as calcination. Calcination is a heat treatment designed to perform one or more of; thermal decomposition, phase transition, or removal of volatile fractions (partial or complete) depending on the final material and its intended use. The calcination process is normally conducted in the presence of air and occurs at temperatures below the melting point of the active component (s). The adsorbent compositions of this invention are prepared with a suitable heat treatment process that is effective for removing substantially all of the volatile matter associated with the silicone derived binders and any temporary binders used as a processing aid.
[0030] During the heating process, the precursor of silicone binder becomes a species that becomes the binding agent for the adsorbent particles that form the agglomerate and does not interfere with the desired pore architecture. Fc ocpgktc cswk wucfc. “CigpVg fg nkic>“ q fgtkxcfq fg uükeqpg ”aims to describe the type of silicone that has undergone heat treatment or sufficient heat to have substantially volatilized all of the organic side groups associated with the starting silicone binder precursor and leaving a residue of binder containing silicon. Silicones are believed to be transformed by heat treatment into a new species containing silicon with a modified chemical composition that is extremely effective as binding agents for adsorbent particles, especially compositions containing zeolite, and provides sufficient strength for agglomerates at concentrations of 10 % or less, preferably 7% or less, and more preferably 5% or less, calculated on the basis of the final product in dry weight. It is believed that substantially all of the organic side groups are lost while the backbone of the residual Si and O inorganic atom is retained serving as the core of the binding agent for the adsorbent particles. This silicone-derived bonding agent is capable of producing agglomerated particles with crushing strengths greater than or equal to 0.408 kgF (0.9 lbF) measured in the 1.0 mm medium sized particles using the individual microglobe smash resistance method . It was observed that the use of silicone derived bonding agents provides the specific pore architecture to obtain adsorbents with high rates of N2 adsorption, N2 pore diffusivities (Dp) greater than or equal to 4.0 x10- 6 m2 / s, and N2 adsorption capacities greater than or equal to 26 ml / ga 1 atm and 27 ° C, preferably greater than 26.0 ml / ga 1 atm and 27 ° C.
[0031] For the purposes of this invention, the expression average particle size is that which is determined from a standard classification analysis, using USA standard mesh sieves with the weight of the sample retained in each determined sieve and corrected back to a dry weight base using an Ignition Loss (LOI) measurement or other suitable means. The term "mesh" should be understood as a standard USA mesh. For crush resistance measurements, a sample of 1.0 mm average particle size can be prepared by combining fractions of equal weight (dry weight basis) of particles with size 16x18 mesh and 18x20 mesh. In this designation of 16x18 mesh or 18x20 mesh, it is understood that the particles pass through the first sieve and are retained in the second sieve (that is, for 16x18 mesh the particles pass through the 16 mesh sieve and are retained in the 18 mesh sieve. ). All crush resistance measurements are both measured here on the 1.0 mm average size particles prepared using the classification method described above, and the particle size measurements other than 1.0 mm average size are compared as a function of of the value obtained, in equivalent average particle size, calculated by the formula y = 1.2x-0.3 (where y = the crush strength in kgF (lbF) and x is the average particle size in mm) that was derived for take into account the dependence of crush strength on the average particle size (see below). Preferred adsorbents of the present invention will have crushing strengths below the limiting value, for any given particle size, calculated from the previous formula. Adsorbents with these silicone-derived binding agents also show exceptional resistance to friction in these low concentrations of binders (after calcination) that reduce both loss of active material and equipment malfunction / cleanliness.
[0032] Agglomerated adsorbent particles produced with silicone derived binders result in pore structure characteristics that differ from those found in adsorbents produced with standard colloidal silicas and conventional clay binders and such conventional binders are commercially used in concentrations above 10 percent in weight to provide acceptable crushing strengths for gas separation processes. For example, adsorbents produced using colloidal silica bonding agents continue to have a measurable amount of small undesirable pores (ie, pores smaller than 0.1 μo + which are generally absent in adsorbents produced with silicone derived bonding agents. moreover, the crushing and frictional strength of adsorbents prepared with silicone-derived binding agents are significantly improved compared to similarly produced agglomerated adsorbent particles produced with other binders in similar concentrations and the adsorption capacity is very high and comparable with adsorbents produced without binder using the most complex caustic digestion methods of manufacture.Finally, due to the refined pore structure obtained from the use of silicone-based binding agents in aqueous solvent, the adsorption kinetics are surprisingly enhanced versus traditional adsorbents bonded with clay binders in concentrations above 3% by weight or produced with other solvents.
[0033] A method of preparing the adsorbents of the present invention is as follows. A granulation seed is prepared by combining an active adsorbent material with a clay material, such as atapulgite, sepiolite, haloisite, purified versions of these and their mixtures in the approximate ratio (dry basis) of 80-90 parts of active component at 10 to 20 clay pieces. The clay / zeolite seed forms the core of the agglomerated particle with the seed particle comprising from 0.1 to 25% (by volume) of the agglomerated particle. The agglomerated seed particles produced from silicone alone used to initiate the agglomeration step as the zeolite / silicone binder mixture are not as effective in producing the controlled particle growth that is required for commercial manufacturing processes, resulting in a low yield and time consuming, inefficient and financially unattractive production processes. This process follows the conventional preparation steps, but includes mixing the seed material comprising the active materials and clay binder with the mixture of active material and silicone bonding agent. The mixture of seed material and active material with binding agent derived from silicon is dried, calcined and optionally rehydrated, treated with a metal salt to perform ion exchange, dried again and activated in the manner understood by those skilled in the art.
[0034] In another embodiment, a mixture is prepared comprising an active component and a silicone binder and a processing aid. In some cases, in order to obtain a particle with temporary particle resistance (green resistance), a plasticizer, such as, but not limited to, methyl cellulose, can be employed. Resistance of the temporary particle is critical in commercial manufacturing to provide the particle with green resistance to be converted into a unitary operation after another without excessive loss of the agglomerated particles. However, it has been observed that plasticizers, such as methyl cellulose, pore builders and / or temporary binders adversely affect the final pore structure for some applications, resulting in pore architectures outside the preferred ranges. Furthermore, it has been observed that the use of plasticizers, in some cases, reduces the manufacturing yield due to their binding very strongly at temperatures below or equal to 300 ° C, leading to the clogging of microglobe and calcination equipment . In demonstrative production tests, product yields were lower by as much as 40% relative to formulations that did not use methyl cellulose. This was especially true when comparing example 4 (without methocel) and example 5 (with methocel). It was also observed that the presence of methylcellulose produces microglobules with factors of low sphericity and / or shape that are undesirable from the point of view of increasing the pressure drop in packaged bed adsorption processes, compared with microglobules of equivalent size with high sphericities and form factors close to the unit. Such temporary binders are typically not employed in commercial manufacturing processes and the preferred adsorbents of this invention are prepared in the absence of methyl cellulose and other process aids.
[0035] The mixing of the adsorbent components must be complete, in such a way that the final product is consistent in terms of appearance and other properties, such as loss on ignition and viscosity. High intensity or high shear mixing equipment is particularly preferred from the point of view of obtaining a mixed product with a high level of consistency and homogeneity and to densify the mixture. However, other mixing equipment that is capable of combining the components of the agglomerate formulation with one another can be used in such a way that they are passable for subsequent stages of manufacture and ultimately result in products with the required physical and performance characteristics.
[0036] The binder concentration of the adsorbent material is determined by the standard McBain test (see eg, Bolton, A0R0. "Oqlecular Sieve Zeolites." In Experimental Methods in Catalytic Research, Vol. II, ed. RB Anderson and PT Dawson, Academic Press, New York, 1976) using O2 adsorption, on activated adsorbent samples, at 77K and 9.33 kPa (70 Torr) by reference to an analog powder of the active component itself, (ie, in a “No binder” not agglomerated). The McBain test product is the fractional amount of active component of which the binder content is defined as the difference in% by weight of O2 adsorbed between the reference powder analogue and the final product relative to the reference powder analogue ( that is, (% by weight of adsorbed O2 (powder analog) -% by weight of O2 (final product)) /% by weight of O2 (powder analog) represents the fractional binder content. Multiplication of this fractional binder content per 100 results in the weight% of binders.
[0037] For purposes of the present invention, the procedure for performing the McBain test is as follows: The sample is air dried prior to the McBain test. It is then placed in the McBain apparatus and slowly dehydrated and activated under evacuation throughout the night, that is, at a pressure of about 1 x 10-4 torr. The temperature is raised from the room to about 400 ° C in eight hours and then maintained at this value for another eight hours. The sample is then cooled to the temperature of liquid N2 (77K) and ultra high purity O2 is introduced and maintained at a pressure of 9.33 kPa (70 torr) until equilibrium is reached. The amount of O2 adsorbed (% by weight) is determined gravimetrically by means of an accurate measurement of the change in length of a calibrated helical spring. The measurement is repeated in the same way for the reference sample of the powder analog and the binder content in% by weight is calculated as previously described.
[0038] For clarification, the binder content of previous clay-bound adsorbents, which are used here for comparative purposes, is commonly reported as the fractional amount of clay contained in the mixture of adsorbent powder and clay binder based on dry weight . However, depending on whether steps of making compositional change (ie, ion exchange) are used after agglomeration, the reported dry weight binder content may or may not be based on the final dry weight product. This usual practice is retained for the purpose of comparisons produced with the invention. Due to potential compositional changes after the agglomeration step, the binder content reported for samples containing clay binder may be different from that measured by the McBain standard method described above.
[0039] After the components have been mixed together, they are ready for agglomeration into the particles, which are preferred for packaged bed type applications like the processes described here. Examples of suitable forms of adsorbent include microglobules, precipitates, tablets, extrudates and granules. Modeled bodies such as honeycomb structures typically used in various catalytic processes and prescribed in US 7,582,583 are not well suited for use in cyclic gas separation processes by volume due to their low cell densities which translate to low fraction of active material for a given fixed volume of adsorbent bed and are avoided. In addition, loading the honeycomb structures comprising very hydrophilic active materials into an adsorbent bed for use in PSA, VSA or VPSA systems is difficult and there is no high temperature process to recondition the adsorbent if it gets wet during the operation. loading, unlike most catalytic processes that are operated at elevated temperatures.
[0040] These and other problems are avoided if the adsorbent components are modeled in a fluid form (ie microglobe or extruded) required for such adsorption / separation processes and an appropriate piece of equipment is used as it is known. For microglobe-type products that are required for most packaged bed adsorption processes, accretion wheels, mixers, and rotating containers are all acceptable devices for agglomeration. The purpose of the agglomeration step is to manufacture agglomerates with sizes that meet the needs of the application (typically about 0.4 to 5 mm for most adsorption processes) and have sufficient strength, often called green strength, to survive any one of the additional processing steps required, such as sorting, as well as transportation to the next manufacturing operation. The agglomeration method and equipment can be any one that achieves the goal of obtaining agglomerate products with physical and performance characteristics that satisfy the criteria described here.
[0041] After the target particle size agglomerates have been obtained from the agglomeration step, it is necessary to conduct the heat treatment / calcination as described above to remove any removable component including volatile organic components, especially hydrocarbon groups, from the silicone binder precursor and converting the silicone binder precursor into the form that binds and increases the strength of the agglomerated particles. Calcination is typically conducted at temperatures above 300 ° C to about 700 ° C. Preferably, the heat treatment is carried out by scaling the temperature rise of the surrounding environment to more than 400 ° C in the presence of a suitable purge gas, such as dry air. The type of purge gas is not considered limiting and any purge gas that completes the heat treatment objectives can be used. The thermal process removes any removable species, conditions the adsorbent for use (for example, it lowers the residual moisture content to values 0 3% by weight, measured by a suitable technique such as the Karl Fischer titration method (see US patent No. 6.171.370)) in the final process and systems, and reinforces the agglomerated particles to meet the crush resistance specification. Any type of oven, type of furnace or type of greenhouse can be used.
[0042] This basic manufacturing method for adsorbents can be increased by additional stages or stages dictated by the type of adsorbent and the intended application. Examples of additional common processing steps include, but are not limited to, ion exchange processes for zeolites and aging steps for aluminas and silicas.
[0043] The products obtained from the previous manufacturing process are adsorbent particles agglomerated with particle diameters in the size range of 0.4 to 5.0 mm. The resulting fluid agglomerated particles have high adsorption capacities and fast adsorption rates that surpass previous adsorbents. Adsorbent compositions produced from these particles will have a selectivity of Henry's law of N2 / O2 greater than 15.8, more preferably greater than 15.9. Low concentrations of silicone derived bonding agent of 10% by weight or less, preferably 7% by weight, and more preferably 5% by weight or less can be used with the final adsorbent particles, further exhibiting the requirements of superior crush resistance and resistance to friction. A content of final silicone derived binding agent of 10% by weight or less, 7% by weight or less, and 5% by weight or less results in a fraction of the active component of at least 90% by weight or more, preferably 93% by weight or more and above all preferably 95% by weight or more in the agglomerated adsorbent. The fraction of the most active component in the adsorbent, with the correct adsorption characteristics and acceptable crush resistance, will result in a higher rate material. Products linked to traditional clay using similar manufacturing processes generally require concentrations of binders above 10% by weight and, more commonly at least 15% by weight, to obtain crush resistance and sufficient friction resistance resulting in lower concentrations of active component in the final composition.
[0044] Figures 1a-d are a set of 4 Scanning Electron Microscope images, each showing a cross section of a LiLSX adsorbent microglobule produced using both a clay binding agent (a) and (b) and one silicone derived bonding agent of the present invention (c) and (d) the 4,500x magnification. SEM images are “true” cross sections of the agglomerated particles and pores larger than about 0.07 μo can be seen in this magnification. The consistent “no binder” nature of the macropores is apparent to the sample of silicone derived binder.
[0045] In Figure 1 (a), the clay binder is clearly visible as a fibrous particulate, disposed between the crystallites of the adsorbent, and it can be clearly seen that it results in a region of low porosity due to the bonding agent clay fill the pores that result from the stacking of the adsorbent crystallites. In Figure 1 (b), a different area of the microglobule is shown, still showing the binding agent filling the pores, resulting from the stacking of the adsorbent crystallites, although to a lesser extent. Without attaching to any theory, it is believed that these regions emptied of “fgpuc” clay binder , lower adsorption kinetics.
[0046] In the case of adsorbent bound with silicone derived binding agents shown in Figures 1 (c) and 1 (d), the location of the binding agent is not clearly identifiable, suggesting that new silicone derived species formed during the heat treatment that is binding the particles are of small particle size. Again, without attaching to any theory, it is believed that the silicone-derived species forms clusters or coatings (partial-porous) on the crystallite surfaces of the adsorbent forming points of contact for the bonding of one crystallite to another. Since the pores of the inventive adsorbent are predominantly free of binding agent, improvements in the pore structure are observed, expressed in the median pore diameter, percentage of small pores and pore connectivity characteristics.
[0047] Three parameters are used to provide a more detailed view of the pore structure of the adsorbent of the inventive adsorbents; namely, the median pore diameter, the fraction of pores that are 00.1 μm and a hysteresis parameter representing pore connectivity. These parameters are all measured and obtained by standard Hg porosimetry techniques. The median pore diameter is known for the pore support structures with improved characteristics (for example, see US patent No. 6,425,940 B1). The second parameter is the fraction of small pores, denoted F (see Equation 2), and is a measure of the amount or mass transfer rate that limits small macropores and mesopores present in the agglomerated adsorbent particles, which are determinable by the Hg porosimetry technique. . With reference to Equation 2, I (413.6 mPa) (60,000 psia) is the cumulative intrusion volume at 413.6 mPa (60,000 psia), I (0.013 mPa) (2 psia), is the cumulative intrusion volume at 0.013 mPa (2 psia) and I (13.1 mPa) (1,900 psia) is the cumulative intrusion volume at 13.1 mPa (1,900 psia). As defined here, F is a measure of the pore fraction of 0 0.1 μm pore size and has also been used in the prior art to indicate the innovation of a particleboard structure (for example, see US patent application. 2011104494 and US Patent No. 6,171,370 B1 where the detrimental impact of large fractions of these small macroporous and mesoporous transport pores is prescribed). The third parameter is the jkuVgtgug “T” factor swg hqk fgfípkfq by the standard Hg porosimetry data shown in equation 1, where: I (413.6 mPa) (60,000 psia) is the cumulative intrusion volume at 413.6 mPa (60,000 psia) of the intrusion curve, I (0.344 mPa) (50 psia) is the cumulative intrusion volume at 0.344 mPa (50 psia) of the intrusion curve and E (0.344 mPa) (50 psia) is the volume of cumulative intrusion at 0.344 mPa (50 psia) of the extrusion curve.
agglomerated adsorbents are as follows: the median pore diameter greater than or equal to 0.45 μm, 10% or less of the macropores / mesopores are less than or equal to 0.1 μm, and the hysteresis factor
[0048] The pore structure characteristics of the present agglomerated adsorbents are as follows: the poromedian diameter greater than or equal to 0.45 µm, 10% or less of the macropores / mesopores are less than or equal to 0.1 µm, and the hysteresis factor is greater than or equal to 0.6. The use of Hg porosimetry intrusion and extrusion data to determine pore structure and connectivity information, such as the presence or absence of ink bottle pores, is well known and described in textbooks on this subject (see Chapter 4 in Analytical Methods in Fine Particle Technology, Paul A. Webb & Clyde Orr, Published by Micromeritics Instruments Corp., 1997 ISBN0-9656783-0-X). From the perspective of a preferred pore structure and connectivity, the higher the hysteresis factor R for a cluster close to a maximum of 1, the better, since this equates to a more homogeneous pore architecture without ink bottles and other less desirable pore morphologies. From the point of view of defining the pore structure of the agglomerated adsorbents described here, a high value for the median pore diameter, a low fraction (F) of pores less than or equal to 0.1 μm and a high hysteresis factor (R ) are preferred. In terms of measuring the adsorption capacity, volumetric and gravimetric adsorption systems can be used. The adsorption capacities reported here were determined at a pressure of 1 atm and a temperature of 27 ° C. The adsorbents of the present invention offer adsorption capabilities that are superior to compositions prepared using only clay binding agents, after taking into account the binder content of the product. This surprising result is believed to be due to the use of the silicone-derived bonding agent and the minimization of the amount of clay present in the fluid agglomerated particles.
[0049] Finally, the preferred fluid agglomerated adsorbent particles of the present invention will have crush resistance values, measured by the single microglobe method, greater than or equal to 0.408 kgF (0.9 lbF) at 1.0 mm average particle size and a friction rate below 1%, preferably 0.75%. A simple equation is established to take into account the dependence of the crush resistance value on the average particle size of the microglobe or agglomerated particle. According to this equation, the agglomerated particles will have a crush resistance value greater than that obtained from the value determined by the relationship of y = 1.2x - 0.3 where y is the average crush resistance in kgF (lbF) and x is the average particle size in mm. Percentage friction is determined as the amount of product that passes through a USA standard 25 mesh sieve after 60 minutes of stirring using 100 g of calcined material pre-classified to greater than 25 mesh on a model Ro-tap® sieve shaker RX-29 equipped with sieves with a diameter of: ”.
[0050] Table 1 shows characteristics for representative LiLSX zeolite adsorbents produced using traditional clay binders and the silicone derived binders of the present invention. A representative binder without representative binder is also provided for comparison prepared by the caustic digestion method prescribed in US Patent No. 6,425,940 B1. The pore diffusivity (Dp) determined using the method and equipment described in US patent No. 6.00.234 B1 and US patent No. 6.790.260 B2 is also given in table 1. Table 1. Porosimetry parameters of and Diffusion of Nitrogen Pore (Dp) to LiLSX Produced with Clay and Silicone Derivative Bonding Agents

[0051] From the data in table 1, it is evident that the zeolite adsorbent LiLSX with the silicone derived bonding agent has the best combination of a high median pore diameter, a smaller percentage of pores 0 0.1 μm and a better hysteresis factor compared to the other samples. The median pore diameter for the sample without binder is the highest of the three samples, yet the pore diffusivity of N2 is lower than the sample derived from silicone, indicating a lower adsorption rate. The hysteresis factor is also lower for the sample without a binder, indicating a less effective pore architecture. The three parameters of Hg porosimetry measurement defined in combination represent a more complete view of the real pore architecture and are good predictors of the adsorption rate, compared to any of the parameters used in isolation. The adsorbents with the silicon derived bonding agents clearly present a superior pore architecture for gas separation processes.
[0052] Finally, adsorbents produced using silicone derived binding agents have high adsorption rates measured by nitrogen pore diffusivity (Dp, a measure of adsorption rate). The agglomerated adsorbent particles of this invention have a Dp greater than 4.0 x 10-6 m2 / s. This compares adsorbent particles bound with conventional clay binders with a Dp of less than 3.0 x 10-6 m2 / s and adsorbent particles without binder with a Dp of 3.9 x 10-6 m2 / s. The following examples demonstrate the differentiated features of the inventive adsorbents from the adsorbents produced from conventional binders including clays and colloidal silica bonded products. The examples are provided at 7% by weight of silicone-derived binding agent and less. Used adsorbents can be prepared at higher concentrations of binders, including 10% by weight of silicone-derived binding agent. Experienced in the technique, they will realize that the increase in the binder concentration will provide improved physical characteristics, especially the crushing resistance. At a binder concentration of up to 10% by weight, the improvements in Dp, median pore diameter, pore percentage 00.1 μm and hysteresis factor described here, will be obtained versus the traditional clay and colloidal silica binding agents described previous technology. At 10% by weight of binding agent, the 90% active phase concentration is still high versus many traditional prior art compositions. The concentration of binder greater than 10% by weight, the benefit of high concentrations of active phase, offered by the present invention, decreases. Example 1. Zeolite adsorbent NaKLSX with 7% by weight of silicone derived bonding agent
[0053] 2,000.0 g of NaKLSX zeolite powder based on dry weight (2,684.6 g in wet weight) were mixed with Methocel F4M 60 g in a Hobart mixer for 10 minutes. Then, with the mixer still stirring, 467.5 g of IE-2404 (a silicone resin emulsion containing silicone from Dow Corning) was pumped at a rate of 15 mL / minute. After the addition of IE-2404 was complete, mixing continued for an additional 1 hour, before the now mixed products were transferred to a Nauta mixer with an internal volume ~ 0.028 m3 (1 ft3) and agitated in it at a speed of 9 rpm . The Nauta mixture continued, gradually adding deionized water at the same time to form microglobules with porosity in the range of 35 to 40%, measured after calcination using a Hg Micromeritics Autopore IV porosimeter. At the end of the mixing time, microglobules including those in the target 12 x 16 mesh size range formed. The product's microglobules were air dried overnight before calcination using a shallow pan method at temperatures up to 593 ° C. The shallow pan calcination method used a General Signal Company Blue M Electric equipped with a dry air purge. The adsorbents were spread on stainless steel mesh trays to provide a thin layer less than 0.5 inch deep. A 200 SCFH dry air purge was fed into the furnace during calcination. The temperature was set at 90 ° C followed by a 360 minute stop time. The temperature was then increased to 200 ° C gradually over a period of 360 minutes (approximate rate of increase = 0.31 ° C / min), and then further increased to 300 ° C over a period of 120 minutes (rate of approximate increase = 0.83 ° C / minute) and finally increased to 593 ° C for a period of 180 minutes (approximate rate of increase = 1.63 ° C / minute) and held there for 4 minutes before cooling. The calcined microglobules were subjected to a classification operation to determine the yield and to collect those particles in the 12 x 16 mesh size range. Example A (Comparative). Zeolite adsorbent NaKLSX with 7% by weight of colloidal silica bonding agent
[0054] 2,000.0 g of NaKLSX zeolite powder based on dry weight (2,684.6 g in wet weight) were mixed with Methocel F4M 60 g in a Hobart mixer for 10 minutes. Then, with the mixer still stirring, 376.4 g of colloidal silica Ludox HS-40 (from Dow Chemical) was pumped at a rate of 17 mL / minute. After the addition of colloidal silica was complete, mixing continued for an additional 1 hour, before the now mixed products were transferred to a Nauta mixer with an internal volume ~ 0.028 m3 (1 ft3) and agitated in it at a speed of 9 rpm. The Nauta mixture continued, gradually adding deionized water at the same time to form microglobules with porosity in the range 35 to 40%, measured after calcination using a Hg Micromeritics Autopore IV porosimeter. At the end of the mixing time, microglobules including those in the target 12 x 16 mesh size range formed. The product microglobules were air dried overnight before calcination using the shallow pan method at temperatures up to 593 ° C, as described in example 1. The calcined microglobules were subjected to a grading operation to determine yield and harvest those particles in the 12 x 16 mesh size range. Example B (Comparative). Zeolite adsorbent NaKLSX with 7% by weight of clay bonding agent
[0055] 2,000.0 g of NaKLSX zeolite powder based on dry weight (2,684.6 g in wet weight) were mixed with 150.5 g of Actigel 208 based on dry weight (195.5 g in wet weight) and Methocel F4M 60.0 g in a Hobart mixer for 1 hour and 35 minutes. The Hobart product was transferred to a Nauta mixer with an internal volume ~ 0.028 m3 (1 ft3) and stirred in it at a speed of 9 rpm. The Nauta mixture continued, gradually adding deionized water at the same time to form microglobules with porosity in the range 35-40%, measured after calcination using a Hg Micromeritics Autopore IV porosimeter. At the end of the mixing time, microglobules including those in the target 12 x 16 mesh size range formed. The product microglobules were air dried overnight before calcination using the shallow pan method at temperatures up to 593 ° C, as described in example 1. The calcined microglobules were subjected to a grading operation to determine production and harvesting of those particles in the 12 x 16 mesh size range. Table 2. Pore structure parameters by Examples 1, A and B
1 Average particle size is determined using a standard classification analysis method using 100 g of calcined material on a Ro-tap® model RX-29 sieve shaker equipped with USA standard mesh sieves of: ”in diameter using 15 minutes of agitation .2 Porosity, median pore diameter (MPD),% of pores 0 0.1 μm and hysteresis factor are determined as previously described from the Hg porosimetry data.3 Crush resistance is measured in calcined products by the single microglobe method , using 40 microglobules from which the average crush resistance is calculated. All crush resistance measurements used a Dr. Schleuniger Pharmatron Tablet 8M tester equipped with a 50 N.4 load cell. Percentage attrition is determined as the amount of product that passes through a standard 25 USA mesh sieve after 60 minutes of agitation using 100 g of calcined material pre-classified in mesh greater than 25 in a Ro-tap® sieve shaker model RX-29 equipped with a sieve fg: ”fg fkâogVtq.
[0056] A side-by-side comparison of the characteristics of the adsorbents of Example 1, an adsorbent with a silicone-derived binding agent, Comparative Example A, a colloidal silica binding agent, and Comparative Example B, a traditional clay binder, is shown in table 2. The three adsorbents had an equivalent particle size and binder content. The adsorbent with the silicone-derived bonding agent produced a 400% improvement in crushing resistance compared to the other samples. The results of crush strength by example 1 and Comparative Examples A and B are plotted together in Figure 2 and show exceeding the crush strength limit requirement.
[0057] Similarly, resistance to friction, a measure of the amount of dust formed by agglomerate-particle particle contact, has also been significantly improved with the silicone-derived bonding agent, being over 300% better than the more comparative example. next, the adsorbent with the clay binder. Regarding the structure of pore differences, samples using colloidal silica bonding agents and clay bonding agents are characterized by a larger pore fraction (about 200% more) with a diameter less than or equal to 0.1 μo , suggesting lower adsorption kinetics. The pore structure information derived from the Hg porosimetry measurements confirms that the pore architecture of the macropores and mesopores of the silicone-derived adsorbent (Example 1) is clearly differentiated from comparative samples of colloidal silica and clay (A and B). The adsorbent of this invention has a median pore diameter greater than or equal to 0.45 μm; less than 10%, preferably less than 8%, of its pores being less than or equal to 0.1 μo = and a hysteresis factor R greater than or equal to 0.5. Example 2 Zeolite LiLSX adsorbent with 5% by weight of silicone-derived binding agent, laboratory preparation with Methocel F4M
[0058] 27.17 kg (59.90 lb) of dry weight NaKLSX zeolite powder (34.67 kg (76.45 lb) in wet weight) were mixed with 0.27 kg (0.60 lb) Methocel F4M in a Littleford LS-150 shear mixer for 1 minute. Then, with the mixer still stirring, 4.44 kg (9.8 lb) of IE-2404 (a silicone resin emulsion containing silicone from Dow Corning) was pumped at a rate of 0.45 kg / minute (1 lb / minute). After the addition of IE-2404 was complete, 4.98 kg (11.0 lb) of water was added at a rate of 0.45 kg / minute (1 lb / minute) under constant agitation in the shear mixer. At the end of the addition of water, the shear mixture continued for an additional 5 minutes. The powder product mixed with shear labeled after "the formulation" was transferred to an inclined rotary drum mixer with an internal operating volume of ~ 75 L and agitated in it at a speed of 24 rpm. Mixing of the formulation continued during the addition of deionized water gradually to form microglobules. A recycling operation was carried out, involving crushing and reforming the microglobules until the microglobules had a porosity, measured using a Hg Micromeritics Autopore IV porosimeter in the calcined product, in the range 35 to 40% were formed. The product's microglobules were air dried overnight before calcination using the shallow pan method at temperatures up to 593 ° C, described in example 1.
[0059] The calcined microglobules were subjected to a grading operation to determine the yield and harvest of those particles in the 16 20 mesh size range for further processing known in the art including hydration steps, Li ion exchange and activation up to 593 ° C under purging of dry air. Li exchange of the samples (for a Li exchange level of at least 96% Li on an equivalent basis) was obtained using the following procedure: a column ion exchange process was used where the samples are packaged inside a column glass (dimensions: 3-inch id) placed in contact with lithium chloride solution (1.0 M) at 90 ° C at a flow rate of 15 mL / minute. A preheat zone before the packed adsorbent column ensures that the temperature of the solution reaches the target value before putting the zeolite samples in contact. A 12-fold excess of solution was placed in contact with the samples to produce products with Li contents of at least 96% exchange, or more. After the required amount of solution is pumped through the column containing the samples, the feed is switched to deionized water to remove excess LiCl from the samples. A volume of water of 50 L, a flow rate of 80 mL / minute and a temperature of 90 ° C were used. An AgNO3 test, familiar to those skilled in the art, was used to verify that the effluent was essentially chloride free at the end of the washing stage. The wet samples were dried and activated under a dry air purge (200 SCFH flow rate) using the same procedure as the shallow pan calcination method described in example 1 in a General Singal Company Blue M Electric oven. Example 3 Zeolite LiLSX adsorbent with 5% by weight of silicone-derived binding agent, laboratory preparation without Methocel
[0060] The sample was prepared following the procedure in example 2 with the exception that no OgVjqegn H6O was added “in the formulation” Example 4 Zeolite Na, KLSX adsorbent with 5% by weight of Silicone Derived Bonding Agent without Methocel, Semi Commercial Preparation
[0061] 319.7 kg (705 lb) of dry weight NaKLSX zeolite powder (399.8 kg (881.6 lb) wet weight) were mixed without any Methocel F4M in a Littleford FKM-2000-D mixer Ploughshare® for 4 minutes. Then, with the mixer still stirring, 50.98 kg (112.4 lb) of IE-2404 (a silicone resin emulsion containing silicone from Dow Corning) was pumped at a rate of 2.26 kg / minute (4 , 9 lb / minute). The mixed powder product labeled after "the formulation" was transferred to a rotating container granulation wheel. To start the granulation process a small fraction of seed material was used zeolite clay to promote microglobe formation. The amount of zeolite clay seed used represented approximately 25% (by volume) of the total granulation wheel load and the NaKLSX clay / zeolite seed content was 12% clay, zeolite balance. The formulation was added to the clay-zeolite seeds under constant rotation of the container granulation wheel. During this time, water was added through a spray nozzle to promote particle agglomeration. The addition of the formulation and addition of water continued under constant rotation of the granulation wheel of the container until the microglobules including those in the target 10 x 20 mesh size range formed. A representative sample of the product's microglobules was air dried overnight before calcination using the shallow pan method at temperatures up to 593 ° C, as described in example 1. The calcined microglobules were subjected to a grading operation to determine the production and harvest of those particles in the 10 x 20 mesh size. Example C (Comparative) Zeolite adsorbent LiLSX with 7% by weight of Clay bonding agent without Methocel, Semi Commercial Preparation
[0062] 1,270 kg (2,800 lb) of dry weight NaKLSX zeolite powder (1,587.5 kg (3,500 lb) in wet weight) were mixed with 95.7 kg (211 lb) of Actigel 208 clay based on weight dry (119.7 kg (264 lb) wet weight) and Nauta mixer. The mixed powder product Nauta labeled after “the formulation” was transferred to a rotating container granulation wheel. To start the granulation process, a small fraction of zeolite clay seed material was used to promote microglobe formation. The amount of zeolite clay seed used represented approximately 25% (by volume) of the total load for the granulation wheel and the NaKLSX clay / zeolite content in seed was 12% clay, zeolite balance. The formulation was added to the zeolite clay seeds under constant rotation of the container granulation wheel. During this time, water was added through a spray nozzle to promote particle agglomeration. The addition of the formulation and addition of water continued under constant rotation of the granulation wheel of the container until the microglobules including those in the target 16 x 20 mesh size range formed. A representative sample of the product's microglobules was air-dried overnight before calcination using the shallow pan method at temperatures up to 593 ° C, as described in example 1. The calcined microglobules were subjected to a grading operation to determine the production and harvesting of those particles in the 16 x 20 mesh size range for further processing for Li ion exchange and activated form as described in example 2. Example 5. Zeolite LiLSX adsorbent with 5% by weight of silicone derived bonding agent, commercial scale preparation with Methocel F4M
[0063] 1,016 kg (2,240 lb) of dry weight NaKLSX zeolite powder (1,270 kg (2,800 lb) in wet weight) were mixed with 9.97 kg (22 lb) of Methocel F4M in a Littleford Ploughshare® mixer with an internal volume of 4,200 liters for approximately 1 minute. Then, with the mixer still stirring, 162.8 kg (359 lb) IE-2404 (a silicone resin emulsion containing silicone from Dow Corning) diluted with 45.35 kg (100 lb) of water was pumped at a rate 13.6 kg / minute (30 lb / minute). The mixed powder product labeled after "the formulation" was transferred to a rotating container granulation wheel. To start the granulation process, a small fraction of zeolite clay seed material was used to promote microglobe formation. The amount of zeolite clay seed used represented approximately 25% (by volume) of the total load for the granulation wheel and the NaKLSX clay / zeolite seed content was 12% clay, zeolite balance. The formulation was added to the zeolite clay seeds under constant rotation of the container granulation wheel. During this time, water was added through a spray nozzle to promote particle agglomeration. The addition of the formulation and addition of water continued under constant rotation of the granulation wheel of the container until the microglobules including those in the target 16 x 20 mesh size range formed. The microglobules with the target size of 16 x 20 mesh were collected by a sorting process and sent to a storage hopper. The products in the storage hopper were then sent to a dryer and calciner in which the temperature was scaled from room temperature to 600 ° C over a period of approximately 4 hours to remove any removable component and convert the silicone-derived bonding agent into its form of final binding agent. The products of the calcination step were rehydrated, Li ion exchange and activated by methods described in the technique. The level of final Li ion exchange was greater than 98% on an equivalent basis and the residual moisture content of the final product was reduced below 0.3% by weight by the activation process, measured by the Karl Fischer titration method . Example D (Comparative) Zeolite LiLSX adsorbent with 12% by weight of clay bonding agent, commercial scale preparation
[0064] A product of the commercial LiLSX adsorbent was obtained from Zeochem LLC, in an average microglobe size of 1.5 mm. The product contains 12% by weight of a clay binding agent and was subjected to ion exchange with Li greater than 96%. Example E (Comparative) Zeolite LiLSX adsorbent with 7% by weight of clay bonding agent, commercial scale preparation
[0065] A commercial LiLSX product from the adsorbent was obtained from Zeochem LLC, in an average microglobe size of 1.5 mm. The product contains 7% by weight of a clay binding agent and was subjected to ion exchange with Li greater than 98%. Example F (Comparative) Zeolite LiLSX adsorbent with 7% by weight of silicone derived bonding agent using dibasic ester solvent
[0066] 2,000.0 g of NaKLSX zeolite powder based on dry weight (2,535.2 g in wet weight) were mixed with Methocel F4M 60.0 g in a Hobart mixer for 1 hour. Then, with the mixer still stirring, 289.4 g of Flake 233 resin (a silicone containing silicone resin from Dow Corning) dissolved in 434.1 g of dibasic ester (DBE) were pumped at a rate of 14 mL / minute. After the addition was complete, mixing continued for 4 minutes. The mixed formulation was then transferred to a Nauta mixer with an internal volume of about 0.028 m3 (1 ft3) and stirred at a speed of 9 rpm. The Nauta mixture continued to gradually add deionized water at the same time to form microglobules with porosity in the range 35 to 40%, measured after calcination using a Hg Micromeritics Autopore IV porosimeter. At the end of the mixing time, microglobules including those in the target 16 x 20 mesh size range formed. The modeled microglobules were dried and calcined to develop resistance in the modeled adsorbent, according to the precepts of the US patent 5,633,217.
[0067] The product microglobules were air dried overnight before calcination using the shallow pan method at temperatures up to 593 ° C, as described in example 1. The calcined microglobules were subjected to a grading operation to determine the production and harvesting of those particles in the 16 x 20 mesh size range for further processing for Li subjected to ion exchange and activated form as described in example 2. Example G. (Comparative) LiLSX adsorbent with 5% by weight of Silicone Derived Bonding Agent and Methocel F4M with Low Calcination Temperature
[0068] 5.13 kg (11.31 lb) of the mixed powder formulation Ploughshare® of Example 4 were mixed with 0.63 kg (1.41 lb) of Methocel F4M in a Simpson mixer-crusher for 30 minutes after 1.36 kg (3.0 lb) of water was added at a rate of 0.045 kg / minute (0.1 lb / minute) under constant mixing. At the end of the addition of water, the mixing continued for another 5 minutes. The mixed powder product labeled after “the formulation” was transferred to a Nauta mixer with an internal volume ~ 0.028 m3 (1 ft3) and stirred in it at a speed of 9 rpm. The Nauta mixture continued to gradually add 1.36 kg (3.0 lb) of deionized water at the same time at a rate of 0.045 kg / minute (0.1 lb / minute). The formulation became paste-like and the mixing continued for 18 hours, which helped to densify the paste to bring the porosity below 40%, in line with inventive comparisons. The formulation was transferred to an LCI low pressure extruder (Model No. MG-55) equipped with a 1.5 mm die and extruded in axial geometry. The extruded products of 1.5 mm in diameter were then dried and calcined according to the precepts of US patent 6,458,187. The shallow pan method in example 1 was used with the maximum temperature set at 210 ° C.
[0069] The products of inventive examples 2 to 5 and comparative examples CG were characterized by Hg porosimetry to measure in each case the median pore diameter, percentage of pores 0 0.1 μm and the hysteresis factor (see Table 3) . The results show that only the inventive examples meet all the Hg porosimetry criteria of the present, these having a median pore diameter greater than or equal to 0.45 μm, 10% or less of the macropores and mesopores are less than or equal to 0, 1 μm and a hysteresis factor greater than or equal to 0.6 of the invention. For comparative examples, at least one, and in some cases, all of these criteria are not met. In particular, for comparative example G, prepared following the precepts of US patent 6,458,187, Hg porosimetry data shows that this sample has a very undesirable median pore diameter, pore fraction less than or equal to 0.1 μm and hysteresis factor compared to the inventive examples.
[0070] It was observed that crushing strengths for the inventive examples were also measured and met or exceeded the relationship y = 1.2 x -0.3, where y is the crushing resistance in kgF (lbF) and x is the average particle diameter in mm. Crush strengths were measured using the method and equipment described in table 2. In addition, N2 capacity and N2 pore diffusivities were obtained for representative samples to show that the adsorbents described here are high performance products for applications such as non-cryogenic air separation (Table 4). The N2 capacity is determined at 101.3 kPa (760 Torr) and 27 ° C using a Micromeritics ASAP2050 extended pressure sorption unit. N2 pore diffusivity (Dp) is calculated using the method and equipment described in Ackley et al US patent No. 6,500,234 B1 and US patent No. 6,790,260 B2. The N2 / O2 selectivity of Henry's law is obtained by obtaining Henry's law constant for oxygen (KHO2) and nitrogen (KHN2) from isothermal data measured at 27 ° C using a Micromeritics ASAP2050 extended pressure sorption unit and dividing the KHN2 by KHO2 to obtain selectivity). Table 3. Hg Porosimetry Results and Crush Resistance by Examples 2-5 and CG
1 Average particle size is determined using a standard classification analysis method using 100 g of calcined material on a Ro-tap® model RX-29 sieve shaker equipped with 8 ”diameter USA standard mesh sieves using 15 minutes of agitation.2 Porosity, median pore diameter (MPD),% of pores 0 0.1 μm and hysteresis factor are determined as previously described from Hg.3 porosimetry data. Crush resistance is measured in calcined products by the single microglobe method, using 40 microglobules, from which the average crush resistance is calculated. All crush resistance measurements used a Dr. Schleuniger Pharmatron Tablet 8M tester equipped with a 50 N load cell. Table 4. N2 capacity (27 ° C, 101.3 kPa (760 Torr)), Selectivity of N2 / O2 from Henry's law (27 ° C) and N2 pore diffusivity (Dp) by Examples 2-5 and CF

[0071] A prerequisite for the use of silicone-derived bonding agents is to ensure that the adsorbent is not damaged as a result of the bonding agent and / or any component or solvent that are used with the bonding agent. From the data in table 4, it is clear that the inventive samples prepared with silicone-based binding agents have superior capacities and selectivities for samples prepared with traditional clay binding agents. These improvements are manifested both in laboratory scales and in commercial production. Comparison of the laboratory samples of inventive examples 2 and 3 with a comparative example C prepared semi-commercially shows that the nitrogen capacities and selectivity of N2 / O2 are superior for the inventive samples. Similarly, comparison of the results for inventive example 5 which was produced on commercial production scales with high-tech samples manufactured with clay binding agents, also prepared on commercial production scales (Comparative Examples D and E), again shows that the inventive samples have superior N2 capacities and selectivities. A similar comparison of laboratory scale with laboratory scale and commercially produced with commercially produced shows that the inventive samples have similarly higher N2 pore diffusivities, versus traditional clay-based adsorbents.
[0072] Comparison of the inventive examples with a sample prepared following the precept of US patent 5,633,217 (Comparative example F in table 4) shows that the N2 capacities and N2 / O2 selectivity are inferior for this formulation of the prior technology prepared using dibasic ester as a solvent. A standard X-ray diffraction from comparative example F was recorded and compared to example 1. From the comparison of standard X-ray diffraction, it is clear that the intensities of all peaks were decreased for comparative example F compared to example 1. This loss of intensity is a characteristic of structure damage or loss of crystallinity, suggesting that the low silica zeolite adsorbent sustained structural damage when compared to example 1. Since both adsorbent compositions used training, processing equipment and identical thermal set points, structural damage and loss of crystallinity were caused by the use of the dibasic ester solvent. In hydrothermal conditions, such as those present during drying and calcination of the adsorbent compositions, it is believed that dibasic ester compounds can decompose and form acidic species that can be harmful to low silica zeolites, such as those with lower SiO2 / Al2O3 ratios 15, which have low resistance to acids.
[0073] One of the advantages of using the silicone derived bonding agent formulations described here is the ability to obtain products with good crush resistance at very low binder contents, such as 5% by weight. The benefits associated with such low-binder silicone derived binder formulations have been described with reference to Table 4 above. In order to show that some of the performance advantages of these new inventive formulations are not entirely due to the low binder content, we normalized the capacity data presented in table 4 to the binder content in table 5. Normalization is performed by multiplying the nitrogen capacity by 95 / (100-7) for the samples in table 4 with a binder content of 7% by weight and by 95 / (100-12) for samples with a binder content of 12% by weight, where the numerator is the percentage of active adsorbent in the inventive samples and the denominator is the percentage of active adsorbent in the comparative samples. Table 5. N2 Capacity Adjusted by Binder by Examples 2-5 and CF
1Where N2 capacity adjusted by the binder is the N2 capacity measured at 27 ° C, 101.3 kPa (760 Torr) after normalization to binder content where for samples with 7% by weight, the measured N2 capacity (see Table 4) is multiplied by 95 / (100-7) and for samples with 12% by weight binder content, the measured N2 capacity (see Table 4) is multiplied by 95 / (100-12).
[0074] In table 5 and Figure 4, comparing the samples made in the laboratory from the inventive examples 2 and 3 with a comparative example C semi commercially prepared, it shows that the nitrogen capacities adjusted by binder, are superior for the inventive samples. Similarly, comparing the nitrogen capacities adjusted by binder for inventive example 5, which was produced on commercial production scales, with samples of cutting edge technology manufactured with clay binding agents, also prepared on commercial production scales (Comparative Examples D and E), again shows that the inventive samples have N2 capacities adjusted by the upper binders. This is surprising, since the differences in the binder content accounted for normalization and suggest that these nitrogen capacities greater than expected are a feature of the inventive formulations of the adsorbent.
[0075] It should be apparent to those skilled in the art that the present invention is not limited by the examples provided here, which were provided merely to demonstrate the operability of the present invention. The selection of appropriate adsorbent components and processes for use can be determined from the specification without departing from the spirit of the invention disclosed and described herein. The scope of this invention includes modalities, modifications and equivalent variations that are in the scope of the appended claims.

权利要求:
Claims (19)
[0001]
1. Heat-treated adsorbent composition, characterized by the fact that it comprises a mixture of at least one active material comprising one or more zeolites and a silicone-derived bonding agent formed as agglomerated particles comprised of 90% or more of at least one active material calculated based on the final product in dry weight and with: a median pore diameter greater than or equal to 0.45 μm, 10% or less of macropores and mesopores are less than or equal to 0.1 μm, a greater hysteresis factor or equal to 0.6, and a crush resistance value greater than or equal to that obtained from the value determined by the relationship y = 1.2x - 0.3 where y is the average crush resistance in kgF (lbF) and x is the average particle size in mm, and in which the silicone binder precursor is selected from the group consisting of polymeric dimethylsiloxane terminated in hydroxy, methoxy, or ethoxy, or mixtures thereof, with methyl silsesquioxanes, octyl silsesquioxanes , methyl octyl silsesquioxanes, or mixtures thereof.
[0002]
2. Composition according to claim 1, characterized by the fact that at least one active zeolite material has an average particle size greater than 1 micron.
[0003]
Composition according to claim 1, characterized by the fact that at least one active zeolite material comprises one or more zeolites with a SiO2 / Al2O3 molar ratio less than 15.
[0004]
Composition according to claim 3, characterized in that one or more zeolites include a zeolite with a SiO2 / Al2O3 molar ratio less than or equal to 2.5.
[0005]
5. Composition according to claim 4, characterized by the fact that the zeolite is LiLSX or LiX.
[0006]
6. Composition according to claim 1, characterized by the fact that the silicone binder precursor is a dimethylsiloxane with CAS registration number of 897393-56-5.
[0007]
7. Composition according to claim 1, characterized by the fact that the mixture additionally comprises a clay binder selected from atapulgite, sepiolite, haloisite, purified versions of these and their mixtures, in a concentration of no more than 1 part of binder of clay for 5 parts of silicon derived bonding agent.
[0008]
8. Composition according to claim 1, characterized by the fact that the capacity of N2 is greater than or equal to 26 mL / g at 1 atm and 27 ° C.
[0009]
9. Composition according to claim 1, characterized by the fact that the agglomerated particles are selected from the group of forms consisting of microglobules, precipitates, tablets, extrudates and granules.
[0010]
10. Composition according to claim 1, characterized by the fact that the agglomerated particles have an average particle size ranging from 0.4 mm to 5.0 mm and the composition exhibits a greater selectivity of Henry's law of N2 / O2 greater that 15.8.
[0011]
11. Adsorption process to separate N2 from a gas mixture containing N2 and at least one less strongly adsorbable component, characterized by the fact that it comprises bringing the mixture into contact with the adsorbent composition as defined in claim 1.
[0012]
Adsorption process according to claim 11, characterized in that the process comprises a cyclic adsorption process for the separation of gases.
[0013]
13. Adsorption process according to claim 12, characterized by the fact that the process is selected from a vacuum oscillation adsorption process (VSA), temperature oscillation adsorption (TSA), pressure oscillation adsorption (PSA ), adsorption with vacuum pressure oscillation (VPSA) and combinations of these.
[0014]
14. Adsorption process according to claim 11, characterized by the fact that the adsorbent composition exhibits a selectivity of Henry's law of N2 / O2 greater than 15.8.
[0015]
15. Composition according to claim 1, characterized by the fact that the average particle size of the agglomerated particles is 0.6 to 1.8 mm.
[0016]
16. Adsorbent composition used in gas adsorption and separation processes, characterized by the fact that it comprises one or more crystalline aluminosilicate particles with an average particle size greater than 1 micron and with a SiO2 / Al2O3 molar ratio less than 2.5 and produced by a method comprising mixing the particles in an aqueous solution containing 10% or less of a silicone binder precursor and a clay binder in concentrations of no more than 1 part of clay binder for 5 parts of derivative binding agent silica to form a mixture, agglomerate the mixture to form agglomerated crystalline particles and calcinate the mixture at temperatures above 400 ° C to 700 ° C for a period sufficient to remove substantially all volatile organic components associated with the silicone binder precursor .
[0017]
17. Method for making an agglomerated adsorbent composition, as defined in any one of claims 1 to 10 or 15, characterized in that it comprises: (a) preparing a mixture comprising one or more activated zeolite materials and a derivative binding agent (b) mixing seed material comprising one or more of the activated zeolite materials and a clay binder with the mixture and water to form agglomerated adsorbent particles, (c) drying the agglomerated adsorbent particles, and (d) calcining the dry agglomerated adsorbent particles at temperatures from above 400 ° C to 700 ° C for a period sufficient to substantially remove all volatile organic components associated with the silicone binder precursor to form a calcined agglomerated adsorbent composition.
[0018]
18. Method according to claim 17, characterized in that the method for making the agglomerated adsorbent composition includes, after the calcination step, the steps of: (e) rehydrating the calcined composition to form rehydrated agglomerated adsorbent particles, ( f) treat the rehydrated agglomerated adsorbent particles with a metal salt solution to perform an ion exchange of cations to form agglomerated adsorbent particles subjected to ion exchange, (g) dry and activate the particles subjected to ion exchange by heating under dry purge gas the agglomerated particles subjected to ion exchange to form the agglomerated adsorbent composition.
[0019]
19. Method according to claim 17, characterized in that the seed material comprises the silicone-derived binding agent and the clay binder in a concentration of no more than 1 part of clay binder for 5 parts of agent silicone bonding.

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法律状态:
2018-12-04| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-07-30| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-08-04| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

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2021-02-02| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-02-23| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 20/06/2013, OBSERVADAS AS CONDICOES LEGAIS. |

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