Patent Application
20190336954
This disclosure relates to an alumina silicate zeolite-type material for use as a catalyst in Selective Catalytic Reduction (SCR) reactions and a process of forming said catalyst.
The statements in this section merely provide background information related to the present disclosure and may not constitute prior art.
A zeolite is a crystalline aluminosilicate having a framework based on an extensive three dimensional network of oxygen ions. The fundamental building block of all zeolites is a tetrahedron of four oxygen anions surrounding a small silicon or aluminum ion. These tetrahedra are arranged so that each of the four oxygen anions is shared in turn with another silica or alumina tetrahedron. The crystal lattice extends in three-dimension, and the −2 charge, i.e., oxidation state, of each oxygen anion is accounted for. Each silicon ion has its +4 charge, balanced by the four tetrahedral oxygen anions, and the silica tetrahedral are therefore electrically neutral. Each aluminum tetrahedron has a −1 residual charge since the trivalent aluminum is bonded to four oxygen anions. This is balanced by cations that occupy non-framework positions and act as strong, acid-donating Brønsted sites as further described in the schematic below.
High-silica containing zeolites or molecular sieves are typically prepared from an aqueous reaction mixture containing sources of an alkaline metal or an alkaline earth metal oxide; sources of an oxide of silicon; optionally sources of aluminum oxide; and a cation derived from 1-Adamantamine, its derivative N,N,N-trimethyl-1-adamantamonium hydroxide, and mixtures thereof. Fumed silica is used as the typical source of silicon oxide, while aluminum hydroxide is used as the typical source of aluminum oxide. The “as synthesized” crystalline zeolite formed by crystallization may then be subjected to further treatment. For example, the structure directing agent (SDA) can be removed by thermal treatment (i.e. calcination). Such further treatments include the removal of the metal cation by ion-exchange using known methods such as using a diluted acid solution or ammonium nitrate solutions.
U.S. Pat. No. 4,544,538, discloses a method of preparing the SSZ-13 molecular sieve in the presence of N,N,N-trimethyl-1-adamantamonium cation, which is known as the organic template and acts as the structure directing agent (SDA). The strongly directing template species control the course of the reaction by serving primarily to establish the pH conditions of the reaction mixture. The N,N,N-trimethyl-1-adamantamonium cation has been known to crystallize different zeolite structures in the presence of various amount of the inorganic metal.
Y. Nakagawa et al. in Microporous and Mesoporous Materials, 22, (1998) p. 69-85 have computationally determined five different zeolites that can be made using the N,N,N-trimethyl-1-adamantamonium cation. Their molecular modeling calculations agree with their experimental data. They have reported that this template crystallizes SSZ-13, SSZ-23, SSZ-24, SSZ-25, and SSZ-31 type of zeolites. They show the crystallization field boundaries for the five zeolites commonly made by two SDA's. N,N,N-trimethyl-1-adamantamonium SDA molecule crystallizes chabazite phase at SAR 10-40, while STT phase at SAR 50-70.
The drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure in any way.
The following description is merely exemplary in nature and is in no way intended to limit the present disclosure or its application or uses. It should be understood that throughout the description, corresponding reference numerals indicate like or corresponding parts and features.
The present disclosure generally provides a core-shell hybrid Chabazite (CHA) material that exhibits catalytic activity for Selective Catalytic Reduction (SCR) reactions. This zeolite-type material as prepared according to the synthesis conditions described herein exhibits high catalytic activity initially equivalent to Chabazite (CHA) catalysts that have a silicon to aluminum ratio (SAR) on the order of about 25-30 and after hydrothermal aging a level of activity that is equivalent to or higher than existing Chabazite zeolites having an SAR between 12 to 14, as demonstrated by ammonia and N-propylamine temperature desorption studies.
The following specific embodiments are given to illustrate the preparation, identification, and use of the core-shell hybrid Chabazite (CHA) materials prepared according to the teaching of the present disclosure and should not be construed to limit the scope of the disclosure. Those skilled-in-the-art, in light of the present disclosure, will appreciate that many changes can be made in the specific embodiments which are disclosed herein and still obtain alike or similar result without departing from or exceeding the spirit or scope of the disclosure. One skilled in the art will further understand that any properties reported herein represent properties that are routinely measured and can be obtained by multiple different methods. The methods described herein represent one such method and other methods may be utilized without exceeding the scope of the present disclosure.
Referring to
The shell 15 at least partially encapsulates the core 10 in the core-shell CHA material 5. Alternatively, the core 10 is entirely encapsulated by the shell 15. It is also possible to have a mixture of core-shell particles or crystallites in the core-shell CHA material 5 in which some of the cores 10 are partially encapsulated with the shell 15 and some of the cores 10 are entirely or substantially encapsulated in the shell 15. The core-shell Chabazite (CHA) material crystallizes in a triclinic crystal system which includes rhombohedral shaped particles that are pseudo-cubic in shape as shown in
Referring now to
The core-shell hybrid CHA materials formed according to the teachings of the present disclosure exhibit an ammonia (NH3) absorption that is greater than 1.25 mmol/g of material when freshly prepared; alternatively, greater than about 1.50 mmol/g of material; alternatively, greater than about that is greater than 1.75 mmol/g of material alternatively, about 1.75 mmolg/g to about 2.25 mmol/g of material; alternatively, about 2 mmol/g of material. Upon hydrothermal aging at 800° C. for 6 hours, the core-shell hybrid CHA materials retain an ammonia (NH3) absorption value that is greater than 0.3 mmol/g of material; alternatively, greater than about 0.4 mmol/g of material; alternatively, between about 0.4 mmol/g of material to about 0.6 mmol/g of material.
The shell of the core-shell hybrid CHA materials may be characterized as having Broensted acid sites that are present in a greater number than such sites in the core of the core-shell hybrid CHA materials. Although not wanting to be held to theory, the presence of these Broensted acid sites are believed to result in the core-shell hybrid CHA material exhibiting greater than a 50% increase in n-propylamine temperature desorption over an SSZ-13 zeolite after being subjected to hydrothermal aging at 800° C. for 6 hours.
Referring to
Still referring to
The amount of metal present in the metal-containing core-shell hybrid Chabazite (CHA) material ranges from about 0.1 wt. % to about 5 wt. %; alternatively, from about 0.3 wt. % to about 5 wt. %, based on the total weight of the metal-containing core-shell hybrid Chabazite (CHA) material. The lattice structure or framework core-shell hybrid CHA material exhibits a pore size or diameter that is typically less than about 10 nanometers; alternatively, less than about 6 nanometers.
Metals may be introduced into the zeolite by replacing some of the existing cations with metal cations via standard ion exchange techniques, such as those described in U.S. Pat. Nos. 3,140,249, 3,140,251, and 3,140,253, the contents of which are hereby incorporated by reference. Typical cation replacement may include the use of metal cations that are selected from the groups 1 through 12 of the Periodic Table, and mixtures thereof, with a preference toward the elements of the group 1, 2 and 8 of the Periodic Table. Alternatively, the metal is as one from the group of Copper (Cu), iron (Fe), cobalt (Co), zirconium (Zr), titantium (Ti), or a mixture thereof.
Zeolites with transition metals incorporated within the framework exhibit different and very often valuable catalytic properties. For example, cobalt-containing zeolites have been the subject of much interest over the last years, largely because of their catalytic performance in the selective catalytic reduction (SCR) of nitrogen oxides with methane. This reaction is important because methane is expected to replace ammonia as a reductant of NO emitted from stationary sources. U.S. Publication No. 2008/0226545A1 discloses the use of copper exchanged zeolites in the control of NOx emissions from gaseous media over a broad temperature range using selective catalytic reduction of nitrogen monoxide by ammonia.
A significant factor that affects the catalytic activity of zeolite catalysts is the preparation route selected for the catalyst. For example, Janas et al. in Applied Catalysis B: Environmental, 91, (2009), p. 217, describes the effect of copper content on the catalytic activity of a Copper beta zeolite (CuSiBEA) in the selective catalytic reduction (SCR) of NOx. It is possible to control the incorporation of copper into the framework of the beta zeolite by a two-step post-synthesis method to obtain the CuSIBEA catalyst.
The process of the present disclosure provides a method for preparing a core-shell hybrid Chabazite (CHA) material with different silicon to alumina ratios (SAR) exhibited by the core of hybrid material and the shell of the hybrid material. The method may optionally comprise the step of heating the core-shell hybrid Chabazite (CHA) material after impregnation with the aqueous metal salt solution to a temperature of at least 150° C., alternatively about 160° C. The zeolite framework has a pore size that is typically less than 10 nanometers; alternatively less than 6 nanometers; alternatively, between about 1 nanometer and 4 nanometers.
The metal-containing core-shell hybrid Chabazite (CHA) materials prepared according to the teachings of the present disclosure may be used as catalysts, such as in SCR applications. The metal-containing core-shell hybrid CHA material comprises a sufficient amount of a metal to maintain NOx conversion performance in an exhaust gas stream containing nitrogen oxides. The NOx conversion performance of a fresh catalyst at about 500° C. is about 70%. The NOx conversion performance of the hydrothermally aged catalyst at about 200° C. is about 30%.
The acid strength of the synthesized zeolite materials is monitored by measuring the temperature that molecules with basic character (e.g., ammonia and N-propylammine) are desorbed (temperature programmed desorption measurements). The acidity of the samples are measured by ammonia temperature-programmed desorption, and N-propylamine-TPD techniques. Optionally, the metal-containing core-shell hybrid Chabazite (CHA) materials may be deposited onto a honeycomb structure, including but not limited to a wall flow substrate; a metal substrate, or a formed extrudate.
The replacement of aluminum within the structure of the core-shell hybrid Chabazite (CHA) with Cu, Fe, Co, Zr, Ti, or a mixture thereof increases the SCR activity of the catalyst. The core-shell hybrid Chabazite (CHA) with a metal in the framework lattice is capable of storing less ammonia. This metal substitution process reduces the amount of BrOnsted Acid sites present in the catalyst and replaces such sites with Lewis Acid sites. Overall the metal replacement reduces the NOx slip that occurs in ammonia SCR catalysts.
A core-shell hybrid Chabazite (CHA) material (R-1) was prepared according to the method defined above and described in
The X-ray diffraction pattern of the core-shell hybrid CHA material (R-1) is shown in
Temperature-programmed desorption of basic molecules NH3 and N-propyalamine are applied to study the overall nature and distribution of the acid sites on the existing SSZ-13, and the PIDC zeolite-type materials prepared herein. TPD spectra are recorded on 2920 Micromeritic instrument connected with a thermal conductivity detector (TCD) in MKS Cirrus Mass Spec equipment.
Typically for NH3-TPD, 0.1 g catalyst is pretreated at 500° C. for 30 minutes at a rate of 20° C./min in helium flowing at 25 mL min−1 and then cooled to adsorption temperature of 100° C. The catalyst is saturated with diluted ammonia (10% Ammonia/90% Argon) at 100° C. for 30 minutes. After saturation the sample is purged with helium at 25 mL min−1, for 20 minutes to remove the weakly adsorbed ammonia on the surface of the zeolite. The temperature of the sample is then raised at a heating rate of 20° C./min from 100° C. to 650° C., with the flow helium maintained at 25 mL min−1, and then finally held at 650° C. for 40 minutes. A mass spectrometer is used to monitor desorbed NH3.
The amounts of ammonia desorbed from the cone-shell hybrid CHA material both after being freshly prepared (R-1 FRESH) and after be hydrothermally aged (R-1 AGED) determined from their measured TPD peak areas. Two NH3 desorption peaks are observed in the measured ammonia desorption profile as shown in
Within this specification embodiments have been described in a way which enables a clear and concise specification to be written, but it is intended and will be appreciated that embodiments may be variously combined or separated without parting from the invention. For example, it will be appreciated that all preferred features described herein are applicable to all aspects of the invention described herein.
The foregoing description of various forms of the invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Numerous modifications or variations are possible in light of the above teachings. The forms discussed were chosen and described to provide the best illustration of the principles of the invention and its practical application to thereby enable one of ordinary skill in the art to utilize the invention in various forms and with various modifications as are suited to the particular use contemplated. All such modifications and variations are within the scope of the invention as determined by the appended claims when interpreted in accordance with the breadth to which they are fairly, legally, and equitably entitled.
