HYDROCARBON CONVERSION PROCESSES USING METAL CARBIDE NANOMATERIAL CATALYSTS
20200246783 ยท 2020-08-06
Assignee
- China Energy Investment Corporation Limited (Beijing, CN)
- National Institute of Clean-and-Low-Carbon Energy (Beijing, CN)
Inventors
- Junjun Shan (Mountain View, CA, US)
- Hui Wang (Mountain View, CA, US)
- Lisa Nguyen (Mountain View, CA, US)
- Joshua Miles (Mountain View, CA, US)
- Jihong Cheng (Mountain View, CA, US)
Cpc classification
C07C2/76
CHEMISTRY; METALLURGY
B01J35/396
PERFORMING OPERATIONS; TRANSPORTING
B01J37/0009
PERFORMING OPERATIONS; TRANSPORTING
B01J35/393
PERFORMING OPERATIONS; TRANSPORTING
B01J35/60
PERFORMING OPERATIONS; TRANSPORTING
Y02P20/52
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B01J35/30
PERFORMING OPERATIONS; TRANSPORTING
B01J35/40
PERFORMING OPERATIONS; TRANSPORTING
C07C2529/40
CHEMISTRY; METALLURGY
C07C2/76
CHEMISTRY; METALLURGY
B01J29/40
PERFORMING OPERATIONS; TRANSPORTING
International classification
B01J35/00
PERFORMING OPERATIONS; TRANSPORTING
B01J29/40
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A catalyst that includes heterogeneous metal carbide nanomaterials and a novel preparation method to synthesize the metal carbide nanomaterials under relatively mild conditions to form an encapsulated transition metal and/or transition metal carbide nanoclusters in a support and/or binder. The catalyst may include confined platinum carbide nanoclusters. The preparation may include the treatment of encapsulated platinum nanoclusters with ethane at elevated temperatures. The catalysts may be used for catalytic hydrocarbon conversions, which include but are not limited to, ethane aromatization, and for selective hydrogenation, with negligible green oil production.
Claims
1. A catalytic process using metal carbide nanomaterials comprising the steps of: preparing a metal carbide nanomaterial comprising a support and a plurality of metal carbide nanoclusters encapsulated in a plurality of micropores of the support, performing a catalytic hydrocarbon conversion process using the metal carbide nanomaterial.
2. The catalytic process according to claim 1, wherein the support is selected from, but not limited to, inorganic oxides, silicon carbide, silicon nitride, boron nitride, carbon, and combinations thereof, preferably an aluminosilicate zeolite, more preferably ZSM-5.
3. The catalytic process according to claim 1, wherein the metal is a transition metal, preferably platinum.
4. The catalytic process according to claim 1, wherein the catalyst contains between 300-25000 ppm of platinum, and most preferably 500 ppm platinum.
5. The catalytic process according to claim 4, wherein the encapsulated platinum carbide nanoclusters have a size close to 1 nm.
6. The catalytic process according to claim 4, wherein the catalyst has a platinum dispersion greater than 90%.
7. The catalytic process according to claim 1, wherein the hydrocarbon conversion process includes but is not limted to catalytic conversion of ethane to aromatics and catalytic hydrogenation of alkynes and alkadienes to olefins.
8. The catalytic process according to claim 6, wherein the encapsulated platinum carbide nanoclusters are active and selective towards ethane aromatization.
9. The catalytic process according to claim 8, wherein the ethane aromatization is perfomed at temperatures between 300-750 C., preferably between 500-650 C., more preferably between 600-630 C.
10. The catalytic process according to claim 8, wherein the ethane aromatization is perfomed at gas hourly space velocity (GHSV) of ethane between 500-5000 hr.sup.1, preferably at GHSV of ethane at 1000 hr.sup.1.
11. The catalytic process according to claim 7, wherein the catalytic hydrocarbon conversion process includes but is not limited to selective hydrogenating of acetylene to ethylene.
12. The catalytic process according to claim 11, wherein the encapsulated metal carbide nanoclusters are platinum carbide nanoclusters that are active towards selective hydrogenating of acetylene to ethylene, with negligible green oil productivity.
13. The catalytic processes according to claim 11, wherein selective hydrogenating of acetylene to ethylene is performed at temperatures between 20-200 C., preferably between 20-90 C.
14. The catalytic processes according to claim 11, wherein selective hydrogenating of acetylene to ethylene is performed at GHSV of acetylene between 10-1000 hr.sup.1, and a H.sub.2/C.sub.2H.sub.2 ratio between 0.5 to 20, preferably between 2-6.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0025] The accompanying drawings herein are used to provide further understanding of the invention and constitute a part of the description. The accompanying drawings together with the following embodiments serve to explain the invention, but do not constitute a limitation to the invention. In the accompanying drawings:
[0026]
[0027]
[0028]
[0029]
[0030]
[0031]
[0032]
[0033]
[0034]
[0035]
[0036] In the various figures, similar elements are provided with similar reference numbers. It should be noted that the drawing figures are not necessarily drawn to scale, or proportion, but instead are drawn to provide a better understanding of the components thereof, and are not intended to be limiting in scope, but rather provide exemplary illustrations, and graphs are drawn to present the relevant data.
DETAILED DESCRIPTION OF THE INVENTION
[0037] The embodiments of the invention will be described below in detail with reference to the accompanying drawings. It should be understood that embodiments described herein are only for illustration and explanation of the invention, but not for limitation to the invention.
[0038] The present invention relates to a method for synthesizing supported catalysts, where the active phase is at the surface or within pores of the solid support, where the novel supported catalysts are capable of delivering selective hydrogenation performance with high olefin-gain selectivity and low selectivity to green oil (oligomers) and/or saturates, and to catalysts obtained from this method. In so doing, the present invention at least has the benefits of the increase in life expectancy of the catalysts and/or increased catalytic activity.
[0039] As seen in
[0040] Step 1 (S1): mixing a support and/or binder in a solution of metal precursor, preferably metal nitrate, to form a mixture;
[0041] Step 2 (S2): drying the mixture to form a dry product;
[0042] Step 3 (S3): calcinating the dry product;
[0043] Step 4 (S4): reducing the dry product;
[0044] Step 5 (S5): forming a catalyst comprising encapsulated metal nanoclusters within the support and/or binder; and
[0045] Step 6 (S6): preferably, but not necessarily, activating the catalyst in an ethane atmosphere.
[0046] Specifically, in the mixing step S1, the support and/or binder is selected from inorganic oxides, silicon carbide, silicon nitride, boron nitride, carbon, zeolites and combinations thereof, where preferably, the support is an aluminosilicate zeolite, which includes but is not limited to, ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, MOR, Ferrierite, Faujacite, Chabacite, beta zeolite (BEA), Y zeolite, X zeolite, SSZ-13, titanium silicalite-1 (TS-1), Amicite, B arrerite, Clinoptilolite, Harmotome, Laumontite, Paulingite, Pollucite, and mesoporous silica (e.g., MCM41), preferably ZSM-5, having a silica to alumina ratio of between 10:1 to 80:1, preferably between 20:1 to 45:1, and most preferably 30:1. The support and/or binder is mixed with an aqueous solution, which contains metal precursor, preferably platinum nitrate, which includes salts and complexes of platinum, where the mixture is mixed at moderate temperatures, e.g., 10-100 C., preferably 80 C., and ambient pressures, e.g., standard atmospheric pressure 101.3 kPA.
[0047] The mixture is then dried at step S2 to obtain a dry product, where the dry product is then air calcinated at elevated temperatures at step S3, for example, between 300-800 C., and preferably at 550 C., for a certain period, preferably 0.5 to 24 hours, more preferably four hours. It is appreciated that during the air calcination step S3, inert binders such as silica powder and/or alumina powder can be added before or after the air calcination step to improve the catalyst strength. After air calcination, the product is in-situ reduced in hydrogen in step S4 at elevated temperatures, for example, 300-800 C., and preferably at 630 C., for a certain period, preferably 0.5 to 24 hours, more preferably one hour, and then cooled to room temperature, e.g., between 20-25 C. in a hydrogen atmosphere, to provide the synthesized catalyst in step S5.
[0048] Optionally, after the in-situ reduction, at step S6, the product is cooled down to 100-650 C., preferably to 300-500 C., more preferably to 400 C., in the hydrogen atmosphere, which is followed by purging with an inert gas, e.g., nitrogen, at a temperature between 300-500 C., preferably 400 C., and activation in an atmosphere comprising at least one carbon-containing molecule, e.g., CO.sub.x, CS.sub.x, C.sub.xH.sub.y, C.sub.xH.sub.yCl.sub.z, C.sub.xH.sub.yF.sub.z, C.sub.xH.sub.yBr.sub.z, C.sub.xH.sub.yI.sub.z, C.sub.xH.sub.yO.sub.z, and preferably ethane, and nitrogen (e.g., 50% balanced in nitrogen) at a temperature between 100-750 C., and preferably between 300-750 C., more preferably at 400 C., for a certain period of time. After the activation, the catalyst is cooled down to between 80-150 C., preferably to 100 C., using the carbon-containing molecule atmosphere, and then further cooled down to room temperature in an inert atmosphere, e.g., in nitrogen.
[0049] The resulting hydrogenation catalyst is a heterogeneous catalyst that includes the metal nanoclusters on the support and/or binder, and more preferably platinum or platinum carbide nanoclusters on an aluminosilicate zeolite, where the metal or metal carbide nanoclusters are confined or encapsulated in micropores of the zeolite. For example, the metal or metal carbide nanoclusters have sizes close to 1 nm, e.g., +/10%, to be encapsulated in the zeolite. In one embodiment of the invention, the catalyst contains between 300-25000 ppm of platinum, and most preferably 500 ppm of platinum, where the platinum has a metal dispersion greater than 90% and preferably between 95-100%.
[0050] The inventive method and catalyst will be further illustrated with respect to specific Examples that are only intended to demonstrate the invention, but not limit it in any way.
Comparative Example 1
[0051] 5 grams of Al.sub.2O.sub.3 powder was mixed with an amount of a Pt(NO.sub.3).sub.2 containing solution. The mixture was stirred at room temperature for 1 hour and then heated to 80 C. for 1 hour in a rotary evaporator to obtain a dry product, followed by air calcination at 550 C. for 4 hours. The powder was then in-situ reduced in hydrogen at 630 C. for 1 hour, and cooled down to room temperature in a hydrogen atmosphere. The powder was then pressed and sized to 2040 mesh. The obtained product is denoted as Catalyst A, which contains 500 ppm Pt. Catalyst A was then subjected to characterization measurements to determine its features.
Example 1
[0052] 5 g of ZSM-5 powder (having a silica to alumina ratio of 30) was mixed with a certain amount of Pt(NO.sub.3).sub.2 in solution. The mixture was agitated at room temperature for 1 hour and then heated to 80 C. in a rotary evaporator to obtain a dry product, which was followed by air calcination at 550 C. for 4 hours. The powder was then in-situ reduced in hydrogen at 630 C. for 1 hour, and cooled down to room temperature (e.g., between 20-25 C.) in a hydrogen atmosphere. The powder was then pressed and sized to 2040 mesh. The obtained product is denoted as catalyst B, which contains 500 ppm Pt. Catalyst B was then subjected to characterization measurements to determine its features.
Example 2
[0053] A powder was prepared using the same procedure for Catalyst B from Example 1, but after the reduction in the hydrogen atmosphere, the powder was cooled to 400 C. in a hydrogen atmosphere, followed by a an inert gas purge at 400 C. for 10 minutes and then activated in ethane (50% balance in nitrogen) at a temperature between 300-500 C. After the ethane activation, the powder was cooled down to 100 C. under ethane flow, and further cooled to room temperature in an inert gas atmosphere, e.g., in nitrogen. The obtained product is denoted as catalyst C, which also contains 500 ppm platinum.
[0054] Catalysts A, B, and C were then characterized by testing and analyzing the catalysts for the platinum dispersion in the catalyst by dynamic CO chemisorption measurements (chemical adsorption), where the evolution of the platinum species was also studied by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and X-ray absorption near edge structure (XANES). As will be discussed below, the characterization data show for catalyst B, after reduction, the platinum forms encapsulated Pt small nanoclusters. Additionally, after ethane activation (catalyst C), these Pt nanoclusters are transformed to novel encapsulated Pt carbide nanoclusters, PtC.sub.x/ZSM-5. The data also shows that adding inert binder does not affect such transformation, in other words does not affect the formation of Pt nanoclusters to Pt carbide nanoclusters.
[0055]
[0056]
[0057] The CO-DRIFTS measurements in
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[0059] As seen in
[0060]
[0061] The XANES data in
[0062] That is, the characterizations of these catalytic materials are shown in
TABLE-US-00002 TABLE 2 Sample Pt dispersion Particle Size Catalyst B, 0.05 wt % 100% ~1 nm Pt/ZSM-5 Catalyst A, 0.05 wt % 21% 6 nm Pt/Al.sub.2O.sub.3
[0063] Such novel catalysts were found to be capable of delivering improved selective hydrogenation performance with high olefin-gain selectively and low selectivity to green oil and/or saturates during a hydrogen conversion process as known in the art. For example, hydrogen conversion processes as disclosed in U.S. Pat. Nos. 7,153,807 and 8,946,107 and U.S. publication 2018/0194701, which are incorporated herein by reference. In so doing, the benefits of the novel catalysts B and C include, but are not limited to, the extension of the lifetime performance of the catalyst and/or the extension of the operation cycle of the hydrogenation due to the reduction of green oil production.
[0064] In one embodiment of the invention, the ethane aromatization is performed at temperatures between between 300-750 C., preferably between 500-650 C., more preferably between 600-630 C. and/or at gas hourly space velocity (GHSV) of ethane between 500-5000 hr.sup.1, preferably at GHSV of ethane at 1000 hr.sup.1. Additionally, the selective hydrogenating of acetylene to ethylene is performed at temperatures between 20-200 C., preferably between 20-90 C. and/or at GHSV of acetylene between 10-1000 hr.sup.1, and a H.sub.2/C.sub.2H.sub.2 ratio between 0.5 to 20, preferably between 2-6.
[0065] The benefits of such novel catalysts B and C are discussed further below with respect to the catalytic performance of catalysts A, B, and C in hydrocarbon conversions as illustrated in the selective acetylene hydrogenation reaction, and ethane aromatization reactions, e.g., catalytic hydrogenation of alkynes and alkadienes to olefins and catalytic conversion of ethane to aromatics. Applicant notes that while discussion is made of the catalytic hydrocarbon conversion process to the selective hydrogenating of acetylene to ethylene, such conversion process is not limited to said selective hydrogenating of acetylene to ethylene, but can also include selective hydrogenation of 1,3-butadiene (C.sub.4H.sub.6) to butene (C.sub.4H.sub.8). The Pt dispersion in these catalysts were examined by dynamic CO chemisorption measurements. The active phase of these catalysts was studied by CO-DRIFTS, and XANES.
[0066]
[0067]
[0068] Based on the catalytic results shown in
[0069]
[0070]
[0071]
[0072]
[0073] The measurements also show that mixing the inert binder with Pt/ZSM-5 does not change the catalyst activity and selectivity in the case of catalyst B and catalyst C, for both acetylene hydrogenation and ethane aromatization reactions. Thus, the inert binder does not participate the catalytic reactions of hydrocarbon conversions
[0074] In conclusion, the data shows that catalyst C (Pt/ZSM-5 after ethane activation) forms novel encapsulated Pt carbide nanoclusters, which has several benefits over the previous hydrogenation catalysts. For example, while not limiting the invention, the benefits include: [0075] 1. Metal carbide material can be synthesized at ambient pressure. [0076] 2. Metal carbide material can be synthesized at temperatures between 300-650 C. [0077] 3. Pt carbide material can be synthesized by using commercially available zeolite supports and Pt precursors, preferably Pt nitrate, without using expensive diamond support and laser heating. [0078] 4. Metal carbide can be formed as nanoclusters in the support.
[0079] Accordingly, the above embodiments of the invention provided involve at least the following three approaches: [0080] 1. Preparation of catalysts with impregnation of zeolite with a metal solution, followed by calcination, reduction, and ethane activation. [0081] 2. Illustration of the high catalytic performance of prepared catalysts in catalytic hydrocarbon conversion reactions. [0082] 3. Identification of the active phase of the prepared catalysts through various in-situ characterizations.
[0083] The above description is merely the various embodiments of the present invention, where the scope of the invention is not limited thereto, and changes or substitutions within the technical scope of the invention can be easily made by those persons skilled in the art and should be considered to be within scope of the present invention. Therefore, the scope of protection of the present invention is only subject to the scope of protection of the appended claims.