WO2022079532A1

WO2022079532A1 - Catalysts for n-butane dehydrogenation and method for their preparation

Info

Publication number: WO2022079532A1
Application number: PCT/IB2021/058831
Authority: WO
Inventors: Waleed K. ALDAHLOUS; Hamad Mohammed MUDIJ; AbdulAziz I. ALZAHRANI; Zeeshan NAWAZ; Khalid Ali Al-Majnouni; Ahmed S. AL-ZENAIDI; Muhammad A. Daous; Arshid M. ALI; Seetharamulu Podila; Abdulrahim Ahmad AL-ZAHRANI; Lachezar A. Petrov
Original assignee: Sabic Global Technologies B.V.
Priority date: 2020-10-16
Filing date: 2021-09-28
Publication date: 2022-04-21

Abstract

Catalysts and methods for producing the catalysts used for hydrocarbon dehydrogenation have been disclosed. The catalyst includes platinum (Pt) and/or palladium (Pd), a transition metal, a post transition metal, and an alkaline earth metal. The catalyst is in an active cluster configuration. The method of producing the catalyst includes depositing via sequential and/or simultaneous wet impregnation the metal components on a support material to produce a dry impregnated material, and calcining the dry impregnated material to produce the catalyst.

Description

CATALYSTS FOR N-BUTANE DEHYDROGENATION AND METHOD FOR THEIR PREPARATION CROSS REFERENCE TO RELATED APPLICATIONS [0001] This application claims the benefit of priority of U.S. Provisional Patent Application No.63/093,079, filed October 16, 2020, which is hereby incorporated by reference in its entirety. FIELD OF INVENTION [0002] The present invention generally relates to catalysts for dehydrogenation of hydrocarbons. More specifically, the present invention relates to a platinum based catalyst for dehydrogenation of hydrocarbons. BACKGROUND OF THE INVENTION [0003] Alkenes are important petrochemical products with continuously growing demand. Light alkenes, such as ethylene and propylene, are usually produced by steam cracking of petroleum-based feedstocks, or catalytic dehydrogenation of alkanes. [0004] Dehydrogenation of alkanes containing 2 to 6 carbon atoms is an endothermic process. Thus, a high degree of conversion is favored at high reaction temperature and low partial pressure of the reactants. Conventionally, the catalytic dehydrogenation of alkanes is conducted using a chromium based catalyst. As chromium is detrimental to human health and the environment, more and more chemical plants have avoided the use of chromium based catalysts. Various non-chromium based catalysts comprising metal supported on different carriers have been tested and used in hydrocarbon dehydrogenation processes. However, the conversion rate of alkanes using the currently available dehydrogenation catalysts is limited. Additionally, these catalysts have a fast deactivation rate resulting in short working duration. Thus, overall production efficiency of alkenes using conventional dehydrogenation catalysts are relatively low. [0005] Overall, while catalysts for dehydrogenation of alkanes for producing alkenes exist, the need for improvements in this field persists in light of at least the aforementioned drawbacks of conventional and/or other currently available catalyst for hydrocarbon dehydrogenation. BRIEF SUMMARY OF THE INVENTION [0006] A solution to at least some of the above-mentioned problems associated with the catalyst for dehydrogenation of hydrocarbons has been discovered. The solution resides in a platinum and/or palladium based catalyst with a transition metal, a post transition metal, and an alkaline earth metal. This can be beneficial for at least avoiding the use of toxic heavy metal chromium, thereby reducing negative impact of the catalyst on human health and the environment. Additionally, the catalyst can include calcium and zinc, which have a synergistic effect to significantly increase activity and selectivity of the platinum-tin (Pt-Sn) system and platinum-tin-indium (Pt-Sn-In) system, resulting in increased activity and selectivity over other non-chromium based catalysts. Furthermore, the method of preparing the disclosed catalyst includes sequential and/or simultaneous impregnation of a supporting material, which is capable of (1) facilitating formation of proper active centers, maximal dispersion of Pt nanoparticles and (2) ensuring optimal surface acidity of the catalyst. Moreover, the method of preparing the disclosed catalyst is capable of facilitating the formation of the active cluster configuration of the catalyst, leading to the formation of a strong physical and chemical interaction between the carrier and active metal components and improved thermal and mechanical stability of the catalysts, compared to conventional dehydrogenation catalysts. Therefore, the catalyst of the present invention provides a technical achievement over the conventional catalysts for dehydrogenating hydrocarbons. [0007] Embodiments of the invention include a catalyst. The catalyst includes platinum (Pt) and/or palladium (Pd), a transition metal, a post transition metal, and an alkaline earth metal. The catalyst is in an active cluster configuration. [0008] Embodiments of the invention include a catalyst. The catalyst comprises active clusters comprising platinum (Pt), zinc (Zn), tin (Sn), indium (In), and calcium (Ca) supported on Al₂O₃. The platinum in the active clusters has a particle size of 0.01 to 0.6 nm. [0009] Embodiments of the invention include a catalyst for non-oxidative dehydrogenation of n-butane. The catalyst includes 0.1 – 3 wt.% platinum (Pt), 0.1 – 3 wt.% indium (In), 0.1 – 3 wt.% tin (Sn), 0.1 – 3 wt.% zinc (Zn) and 0.1 – 3 wt.% calcium (Ca) supported on γ-alumina (γ-Al₂O₃). [0010] Embodiments of the invention include a method of producing the aforementioned catalyst of the present invention. The method includes depositing via sequential and/or simultaneous wet impregnation of Pt, In, Sn, Zn, and Ca on the catalyst support on γ-Al₂O₃ to produce an impregnated material. The method includes calcining the impregnated material to produce the catalyst. [0011] Embodiments of the invention include a method of producing the aforementioned catalyst of the present invention. The method includes contacting a γ-Al₂O₃ support with a solution comprising soluble salts of Pt, In, Sn, Zn, and Ca to form a first mixture. The method further comprises evaporating solvent of the first mixture to obtain a dry impregnated material. The method comprises drying the modified slurry to produce a powder. The method comprises calcining the powder to obtain the catalyst. [0012] The following includes definitions of various terms and phrases used throughout this specification. [0013] The terms “about” or “approximately” are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment the terms are defined to be within 10%, preferably, within 5%, more preferably, within 1%, and most preferably, within 0.5%. [0014] The terms “wt.%”, “vol.%” or “mol.%” refer to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume, or the total moles of material that includes the component. In a non-limiting example, 10 moles of component in 100 moles of the material is 10 mol.% of component. [0015] The term “substantially” and its variations are defined to include ranges within 10%, within 5%, within 1%, or within 0.5%. [0016] The terms “inhibiting” or “reducing” or “preventing” or “avoiding” or any variation of these terms, when used in the claims and/or the specification, include any measurable decrease or complete inhibition to achieve a desired result. [0017] The term “effective,” as that term is used in the specification and/or claims, means adequate to accomplish a desired, expected, or intended result. [0018] The use of the words “a” or “an” when used in conjunction with the term “comprising,” “including,” “containing,” or “having” in the claims or the specification may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.” [0019] The words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps. [0020] The process of the present invention can “comprise,” “consist essentially of,” or “consist of” particular ingredients, components, compositions, etc., disclosed throughout the specification. [0021] The term “primarily,” as that term is used in the specification and/or claims, means greater than any of 50 wt.%, 50 mol.%, and 50 vol.%. For example, “primarily” may include 50.1 wt.% to 100 wt.% and all values and ranges there between, 50.1 mol.% to 100 mol.% and all values and ranges there between, or 50.1 vol.% to 100 vol.% and all values and ranges there between. [0022] Other objects, features and advantages of the present invention will become apparent from the following figures, detailed description, and examples. It should be understood, however, that the figures, detailed description, and examples, while indicating specific embodiments of the invention, are given by way of illustration only and are not meant to be limiting. Additionally, it is contemplated that changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. In further embodiments, features from specific embodiments may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any of the other embodiments. In further embodiments, additional features may be added to the specific embodiments described herein. BRIEF DESCRIPTION OF THE DRAWINGS [0023] For a more complete understanding, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which: [0024] THE FIGURE shows a schematic flowchart for a method of producing a catalyst, according to embodiments of the invention. DETAILED DESCRIPTION OF THE INVENTION [0025] Currently, catalysts for dehydrogenating hydrocarbons suffer several drawbacks that prevent these catalysts to be effectively and/or safely used in industrial chemical processes for producing alkenes. First, the conventional catalysts for dehydrogenating hydrocarbons include chromium, which is highly detrimental to humans and the environment. Second, currently available non-chromium based catalysts generally show limited activity and selectivity. The present invention provides a solution to at least some of these problems. The solution is premised on a catalyst that includes platinum and/or palladium, a transition metal, a post transition metal, and an alkaline earth metal. The alkaline earth metal can include calcium and the transition metal can include zinc, resulting in a synergistic effect between Ca and Zn for significantly increasing activity and selectivity. Additionally, the disclosed catalyst has a long catalyst life and is easily regenerated with a low rate of coking during the dehydrogenation process. Furthermore, the disclosed catalyst can be prepared via sequential and/or simultaneous impregnation of a support material with active metals, which leads to proper active centers, optimal dispersion of Pt nanoparticles, and optimal surface acidity of the catalyst. Moreover, the calcining step of the method of preparing the disclosed catalyst is capable of facilitating formation of an active cluster configuration, and a strong physical and chemical interaction between the support material and active metals. These and other non- limiting aspects of the present invention are discussed in further detail in the following sections. A. Catalyst of dehydrogenating hydrocarbon [0026] In embodiments of the invention, the non-chromium based catalyst described herein is configured to have high activity and selectivity for dehydrogenating hydrocarbons, and slow coking rate, compared to conventional catalyst for hydrocarbon dehydrogenation. According to embodiments of the invention, a catalyst for dehydrogenating hydrocarbons is provided. The catalyst can include platinum (Pt) and/or palladium (Pd). In embodiments of the invention, the catalyst includes a transition metal. The transition metal can include zinc (Zn) and/or zirconium (Zr). In embodiments of the invention, the catalyst includes a post transition metal. The post transition metal can include tin (Sn), indium (In), gallium (Ga), or combinations thereof. According to embodiments of the invention, the catalyst can further include an alkaline earth metal. The alkaline earth metal can include calcium (Ca). In embodiments of the invention, the transition metals, the post transition metals, and the alkaline earth metal in the catalyst are configured to promote the catalytic effect of Pt and/or Pd. [0027] According to embodiments of invention, the catalyst is supported on a support material. The exemplary support material can include a refractory oxide. The refractory oxide can include γ-Al₂O₃, ZSM-5, SAPOs, MCM-41, SiO₂ or other silicoaluminates, and combinations thereof. The γ-Al₂O₃ may have a Brunauer-Emmett-Teller (BET) surface area of 80 to 350 m²/g and all ranges and values there between, including ranges of 80 to 110 m²/g, 110 to 140 m²/g, 140 to 170 m²/g, 170 to 200 m²/g, 200 to 230 m²/g, 230 to 260 m²/g, 260 to 290 m²/g, 290 to 320 m²/g, and 320 to 350 m²/g. [0028] In embodiments of the invention, the catalyst is a non-chromium based catalyst. The catalyst may contain substantially no chromium or no chromium. According to embodiments of the invention, the Pt and/or Pd of the catalyst are in the form of nanoparticles dispersed throughout the support material. The Pt and/or Pd may have a particle size in a range of 0.01 to 0.6 nm. In embodiments of the invention, the catalyst is in a cluster configuration. In embodiments of the invention, active centers of the catalyst are in clusters comprising Pt and/or Pd, the transition metals, the post transition metal, the alkaline earth metal, and the support material. The active centers are formed with physical and chemical bonds. [0029] In embodiments of the invention, the catalyst has a higher catalytic activity compared to a conventional catalyst. A conventional catalyst can comprise 0.1 Pt-Zn silicate/Al₂O₃ (Philips STAR industrial catalyst), which has a conversion rate of 30% and selectivity to olefins (including butadiene) of 76.4% at reaction conditions at reaction temperature of 538 °C and demonstrated conversion rate of 8% and selectivity to olefins (including butadiene) of 95% (disclosed in Applied Catalysis A Gen; vol.470 (2014) pp.208- 214). The catalyst has a higher selectivity for alkenes compared to 1% Pt 1% Sn 0.5% Zn/Al₂O₃ at temperature of 550 °C, shows conversion rate of 74% and selectivity to olefins (including butadiene) of 68.3% (disclosed in Catalysis Communication, vol.47 (2014), pp.22- 27). In embodiments of the invention, the catalyst is configured to have a slower coke rate during dehydrogenation of hydrocarbons compared to a conventional catalyst. The conventional catalyst can include 3% Pt 1 Sn/SBA-15 at a reaction temperature of 550 °C, which shows conversion of 35.5% and selectivity to olefins (including butadiene = 73.2% (disclosed in Catal. Sci. Technol., vol.9 (2019) pp.947-956) catalyst. In embodiments of the invention, the surface acidity of the catalyst is 120-180 µmol/g. [0030] According to embodiments of the invention, the catalyst can contain 0.1 to 3 wt.% Pt, preferably 0.3 to 2 wt.% Pt, more preferably 1 wt.% Pt. The catalyst can contain 0.1 to 3 wt.% Sn, preferably 0.3 to 2 wt.% Sn, more preferably 1 wt.% Sn. The catalyst can contain 0.1 to 3 wt.% Zn, preferably 0.3 to 2 wt.% Zn, more preferably 1 wt.% Zn. The catalyst can contain 0.1 to 3 wt.% Ca, preferably 0.3 to 2 wt.% Ca, more preferably 1 wt.% Ca. The catalyst can contain 0.1 to 3 wt.% In, preferably 0.3 to 2 wt.% In, more preferably 1 wt.% In. In embodiments of the invention, the catalyst is characterized by a strong synergetic effect between Ca and Zn, which is configured to increase and/or enhance the activity and selectivity of Pt-Sn-In system. In embodiments of the invention, the catalyst is configured to have a catalyst life span of 2 years to 5 years and all ranges and values there between including ranges of 2 to 2.5 year, 2.5 to 3 years, 3 to 3.5 years, 3.5 to 4 years, 4 to 4.5 years, and 4.5 to 5 years. [0031] In embodiments of the invention, the catalyst is configured to catalyze non- oxidative dehydrogenation of n-butane. The non-oxidative dehydrogenation of n-butane can be conducted at a reaction temperature of 500 to 650 ℃, preferably 550 to 600 ℃, more preferably about 575 ℃. B. Method of preparing dehydrogenation catalyst [0032] Embodiments of the invention include a method of preparing the aforementioned catalyst. The method is at least partially configured to achieve the properties of the catalyst described above including strong physical and chemical bonds between active metal components and the support material, synergetic effect between Ca and Zn, low coking rate of the catalyst during dehydrogenation process, and high catalytic activity and high selectivity. [0033] With reference to THE FIGURE, a schematic flow chart is shown of method 100 for preparing the catalyst for dehydrogenating hydrocarbons. According to embodiments of the invention, as shown in block 101, method 100 includes depositing via sequential and/or simultaneous wet impregnation of Pt and/or Pd, the transition metal, the post transition metal, the alkaline earth metal in the support material to produce a dry impregnated material. The sequential and/or simultaneous wet impregnation includes step wise (sequential) and/or simultaneous mixing solutions of promoters and active metals. In embodiments of the invention, as shown in block 102, depositing at block 101 includes contacting a support material with a solution comprising soluble salts of the transition metal, the post transition metal, the alkaline earth metal to form a first mixture. The transition metal can include Zn. The post transition metal can include Sn and In. The alkaline earth metal can include Ca. The support material can include γ-Al₂O₃. [0034] According to embodiments of the invention, as shown in block 105, method 100 includes calcining the dry impregnated material produced at block 101 to produce the catalyst. In embodiments of the invention, the calcining is conducted at a temperature of 550 to 650 ℃ and all ranges and values there between including ranges of 550 to 560 ℃, 560 to 570 ℃, 570 to 580 ℃, 580 to 590 ℃, 590 to 600 ℃, 600 to 610 °C, 610 to 620 ℃, 620 to 630 ℃, 630 to 640 ℃, and 640 to 650 ℃. The calcining duration at block 105 can be 5.5 to 6.5 hours. The calcining step at block 105 is capable of facilitating the formation of the active cluster configuration of the catalyst. In embodiments of the invention, the calcining step at block 105 is capable of facilitating the formation of strong physical and chemical bonds and/or interaction between the support material and active metal components (Pt and/or Pd, the transition metal, the post transition metal, the alkaline earth metal), and an improved thermal and mechanical stability of the catalyst compared to conventional catalysts (e.g., catalysts disclosed in Journal of Industrial and Engineering Chemistry vol.16, no.5, pp.774-784). [0035] Although embodiments of the present invention have been described with reference to blocks of THE FIGURE, it should be appreciated that operation of the present invention is not limited to the particular blocks and/or the particular order of the blocks illustrated in THE FIGURE. Accordingly, embodiments of the invention may provide functionality as described herein using various blocks in a sequence different than that of THE FIGURE. [0036] The systems and processes described herein can also include various equipment that is not shown and is known to one of skill in the art of chemical processing. For example, some controllers, piping, computers, valves, pumps, heaters, thermocouples, pressure indicators, mixers, heat exchangers, and the like may not be shown. [0037] As part of the disclosure of the present invention, specific examples are included below. The examples are for illustrative purposes only and are not intended to limit the invention. Those of ordinary skill in the art will readily recognize parameters that can be changed or modified to yield essentially the same results. Example 1. Testing of catalyst activity in the non-oxidative dehydrogenation reaction of n-butane [0038] The catalytic activity of all catalysts prepared according to the method described in examples below in a non-oxidative dehydrogenation reaction of n-butane were measured in a quartz flow reactor with inner diameter (i.d.) = 12 mm containing 0.5 g catalyst. Pre- and post- catalyst bed regions were filled with commercially available α-Al₂O₃. The reaction temperature was varied in the range of 500 – 650 °C and measured by a thermocouple located in the catalyst bed. A reacting gas mixture containing n-C4H8, H2 and N2 at three different volume ratios, as shown below were used:

[0039] The Gas Hourly Space Velocity (GHSV) of the reacting gas was varied between 3040 to 9120 h^-1. The flow rates of the gases at reactor inlet were controlled by mass flow controllers. Before use, the catalyst was reduced by a hydrogen flow in the reactor at 575 ℃ for 5 hours. The n-butane conversion was checked every 30 minutes. The activity data presented in tables are for a 5 hour run of the reactor, if no other time interval is mentioned. The inlet and outlet compositions of the reaction gases were analyzed by a gas chromatograph with Flame Ionization Detector (FID) and Thermal Conductivity Detector (TCD) detectors. The carrier gas for the gas chromatograph analysis was nitrogen. Example 2. Preparation of the Pt-Sn-In-Ca-Zn/γ-Al₂O₃ catalyst [0040] The catalyst of 1%Pt1%Sn1%In1%Zn1%Ca/γ-Al₂O₃ was prepared using the sequential and/or simultaneous wet impregnation method. In a typical procedure, for 10.0 g catalyst preparation, 9.5 g of calcined γ-Al₂O₃ support was put in a round bottom flask. At the initial stage, 27.7 ml of a 1.0 % solution of CaCl₂ (0.2769 g) and 20.7 ml of a 1.0 % solution of ZnCl₂ (0.207 g) were impregnated on a γ-Al₂O₃ support in a rotary evaporator and represented as ZnCa/γ-Al₂O₃. 8.65 ml of the 1.0 % solution of PtCl₄ (0.0865 g) and 19 ml of the 1.0 % solution of SnCl₂ (0.190 g) were mixed together in a beaker and stirred for 30 min at 60 °C represented as Pt+Sn solution. Similarly, 8.65 ml of the 1.0 % solution of PtCl₄ (0.0865 g) and 19.3 ml of the 1% solution of InCl3 (0.190 g) solution were mixed in another beaker and stirred for 30 min at 60 °C represented as Pt+In solution. Next, the Pt+In and Pt+Sn solutions were impregnated to ZnCa/γ-Al₂O₃ in a rotary evaporator. [0041] The temperature of the water bath in rotary evaporator was set to 65 °C. When the temperature became stable at 65 °C, the flask containing metal salts solutions and the support was kept on rotation at 65 °C for 1 hour. The solution was then evaporated under vacuum until only solid slurry was left. After finishing the complete impregnation process, the catalyst was dried in an oven at 110 °C overnight. The dry impregnated material was calcined at 600 °C for 6 hours in a furnace. Example 3. Testing the catalytic activity of Pt-Sn-In-Ca-Zn/γ-Al₂O₃ catalyst [0042] The catalyst prepared according to Example 2 was tested by procedure according to Example 1. Table 1 shows results of testing of catalytic activity of Pt-Sn-In-Ca- Zn/γ-Al₂O₃ in reaction of non-oxidative n-butane dehydrogenation. Table 1: Results of catalytic activity test of Pt-Sn-In-Ca-Zn/γ-Al₂O₃ catalyst /

Example 4. Preparation of the Pt-Sn-X%In-Ca-Zn/γ-Al₂O₃ catalyst [0043] The catalyst 1%Pt1%SnX%In1%Zn1%Ca/γ-Al₂O₃ was prepared using the sequential and/or simultaneous wet impregnation method. The preparation method followed the same step as described in Example 1 except the In concentration was varied from 0.5 to 4.0 wt.% by maintaining other active metal components concentrations each as 1.0 wt.%. Example 5. Testing the catalytic activity of Pt-Sn-X% In-Ca-Zn/γ-Al₂O₃ catalyst

[0044] The catalyst prepared according to Example 4 was tested by the procedure according to Example 1. Table 2 shows the results of testing of catalytic activity of Pt-Sn- X%In-Ca-Zn/γ-Al₂O₃ in reaction of non-oxidative n-butane dehydrogenation.

Table 2: Results of catalytic activity test of Pt-Sn-X%In-Ca-Zn/γ-Al₂O₃ catalyst

Example 6. Testing the catalytic activity of Pt-Sn-2%In-Ca-Zn/γ-Al₂O₃ catalyst for long run

[0045] The catalyst prepared according to Example 4 was tested by the procedure according to Example 1. Table 3 shows results of long run testing of catalytic activity of Pt- Sn-2%In-Ca-Zn/γ-Al₂O₃ in reaction of non-oxidative n-butane dehydrogenation. Table 3: Results of catalytic activity of long run test of Pt-Sn-2%In-Ca-Zn/γ-Al₂O₃ catalyst

Example 7. Testing the catalytic activity of Pt-Sn-2%In-Ca-Zn/γ-Al₂O₃ catalyst under different H₂ : n-butane ratios

[0046] The catalyst prepared according to Example 4 was tested by the procedure according to Example 1. Table 4 shows results of testing of catalytic activity of Pt-Sn-2%In- Ca-Zn/γ-Al₂O₃ in reaction of non-oxidative n-butane dehydrogenation under different H₂:n- butane ratios.

Table 4: Results of catalytic activity of long run test of Pt-Sn-2%In-Ca-Zn/γ-Al₂O₃ catalyst under different H₂ : n-butane ratios

Example 8. Testing the catalytic activity of Pt-Sn-2%In-Ca-Zn/γ-Al₂O₃ catalyst under different GHSV

[0047] The catalyst prepared according to Example 4 was tested by the procedure according to Example 1. Table 5 shows results of testing of catalytic activity of Pt-Sn-2%In- Ca-Zn/γ-Al₂O₃ in reaction of non-oxidative n-butane dehydrogenation under different GHSV levels.

Table 5: Results of catalytic activity test of Pt-Sn-2%In-Ca-Zn/γ-Al₂O₃ catalyst under different GHSV

Example 9. Preparation of the Pt-Sn-Ca-Zn/γ-Al₂O₃ catalyst

[0048] The catalyst 1%Pt1%Sn1%Ca1%Zn/γ-Al₂O₃ was prepared using the sequential and/or simultaneous wet impregnation method. In a typical procedure, for 10.0 g of 1%Pt1%Sn1%Ca1%Zn/γ-Al₂O₃ catalyst preparation, 9.6 g of calcined γ-Al₂O₃ support was taken in a round bottom flask. At initial stage, 27.7 ml of 1.0 % solution of CaCl₂ (0.2769 g) and 20.7 ml of 1.0 % solution of ZnCl₂ (0.207 g) were impregnated on a γ-Al₂O₃ support in a rotary evaporator represented as ZnCa/γ-Al₂O₃. On the other side, 17.3 ml of 1.0 % solution of PtCh (0.1730 g) and 19 ml of 1.0 % solution of SnCl₂ (0.190 g) solution were mixed and stirred for 30 min at 60 °C represented as Pt+Sn solution. The mixture solution of Pt+Sn was impregnated on ZnCa/ γ-Al₂O₃. The temperature of the water bath in rotary evaporator was set to 65 °C. When the temperature became stable at 65 °C, the flask containing metal salts solutions and the support was kept on rotation at this temperature for 1 hour. The solution was then evaporated under vacuum until only solid slurry was left. After finishing the complete impregnation process, the impregnated material was dried in an oven at 110 °C for overnight.

The dry impregnated material was calcined at 600 °C for 6 h in a furnace to produce the catalyst.

Example 10. Testing of catalytic activity test of Pt-Sn-Ca-Zn/γ-Al₂O₃ catalyst [0049] The catalyst prepared according to Example 9 was tested by procedure according to Example 1. Table 6 shows results of testing of catalytic activity of Pt-Sn-Ca- Zn/γ-Al₂O₃ in reaction of non-oxidative n-butane dehydrogenation. Table 6: Results of catalytic activity test of the Pt-Sn-Ca-Zn/γ-Al₂O₃ catalyst

Example 11. Preparation of the Pt-Sn/γ-Al₂O₃ catalyst [0050] The catalyst 1%Pt1%Sn / γ-Al₂O₃ was prepared using wet impregnation method. For 10.0 g of catalyst preparation, 9.8 g of calcined γ-Al₂O₃ support was taken in a round bottom flask. At initial stage, 17.3 ml of 1.0 % solution of PtCl₄ (0.1730 g) and 19 ml of 1.0 % solution of SnCl₂ (0.190 g) solution were mixed in a small beaker and stirred for 30 min at 60 °C represented as Pt+Sn solution. Next, the mixture solution of Pt+Sn was added to the support γ-Al₂O₃ in a rotary evaporator flask. The temperature of the water bath in rotary evaporator was set to 65 °C. When the temperature became stable at 65 °C, the flask containing metal salts solutions and the support was kept on rotation at this temperature for 1 hour. Then the solution was evaporated under vacuum until only solid slurry was left. After finishing the complete impregnation process, the impregnated material was dried in an oven at 110 °C overnight. Next, the dry impregnated material was calcined at 600 °C for 6 h in a furnace to produce the catalyst. Example 12. Testing of catalytic activity test of Pt-Sn/γ-Al₂O₃ catalyst [0051] The catalyst prepared according to Example 11 was tested by the procedure according to Example 1. Table 7 shows the results of testing of catalytic activity of Pt-Sn/γ-Al₂O₃ in reaction of non-oxidative n-butane dehydrogenation. Table 7: Results of catalytic activity test of Pt-Sn/γ-Al₂O₃ catalyst

Example 13. Preparation of the Pt-Sn-Zn-La/γ-Al₂O₃ catalyst [0052] The catalyst 1%Pt1%Sn1%Zn1%La/γ-Al₂O₃ was prepared using the simultaneous wet impregnation method. For 10.0 g of catalyst preparation, 9.6 g of calcined γ-Al₂O₃ was taken in a round bottom flask. At initial stage, 17.3 ml of 1% solution of PtCl₄ (0.1730 g), 19 ml of 1% solution of SnCl₂ (0.190 g ), 20.7 ml of 1% solution of ZnCl₂ (0.207 g) and 31.2 ml of 1.0 % solution of La(NO₃)₃ ∙6 H₂O (0.3118 g) were mixed together and stirred for 30 min in a beaker at room temperature. [0053] All the metal salts solutions were added to the flask containing the γ-Al₂O₃ support. Next, the metal solution with support was kept on rotation at 60 °C for 1 hour. The solution was then evaporated under vacuum until only solid slurry was left. After impregnation, the impregnated material was dried in oven at 110 °C overnight. The dry impregnated material was calcined at 600 °C for 6 h in static air to produce the catalyst. Example 14. Testing of catalytic activity test of Pt-Sn-Zn-La/γ-Al₂O₃ [0054] The catalyst prepared according to Example 13 was tested by the procedure according to Example 1. Table 8 shows the results testing of catalytic activity of Pt-Sn-Zn- La/γ-Al₂O₃ in reaction of non-oxidative n-butane dehydrogenation. P

Example 15. Preparation of the Pt-Pd-Sn-Zn-Ca/γ-Al₂O₃ catalyst [0055] The catalyst 1%Pt1%Pd1%Sn1%Zn1%Ca/γ-Al₂O₃ was prepared using the simultaneous wet impregnation method. For 10.0 g of catalyst preparation, 9.5 g of calcined γ-Al₂O₃ was taken in a round bottom flask. At initial stage, 17.3 ml of 1% solution of PtCl₄ (0.1730 g), 16.6 ml of 1.0 % solution of PdCl₂ (0.1660 g), 19 ml of 1% solution of SnCl₂ (0.190 g), 20.7 ml of 1.0 % solution of ZnCl₂ (0.207 g) and 27.7 ml of 1.0 % solution of CaCl₂ (0.2769 g) were mixed together and stirred for 30 min in a beaker at room temperature. [0056] All the metal salts solutions were added to the flask containing the γ-Al₂O₃ support. Next, the metal solution with support kept on rotation at 60 °C for 1 hour. The solution was then evaporated under vacuum until only solid slurry was left. After impregnation, the impregnated material was dried in oven at 110 °C overnight. The dry impregnated material was calcined at 600 °C for 6 h in static air. Example 16. Testing of catalytic activity test of Pt-Pd-Sn-Zn-Ca/γ-Al₂O₃ catalyst [0057] The catalyst prepared according to Example 15 was tested by the procedure according to Example 1. Table 9 shows results of testing of catalytic activity of Pt-Pd-Sn-Zn- Ca/γ-Al₂O₃ in reaction of non-oxidative n-butane dehydrogenation. Table 9: Results of catalytic activity test of Pt-Pd-Sn-Zn-Ca/γ-Al₂O₃ catalyst

Example 17. Preparation of the Pt-Ga-Zn-Ca/γ-Al₂O₃ catalyst [0058] The catalyst 1%Pt1%Ga1%Zn1%Ca/γ-Al₂O₃ was prepared using the simultaneous wet impregnation method. For 10.0 g of catalyst preparation, 9.6 g of calcined γ-Al₂O₃ was taken in a round bottom flask. At initial stage, 17.3 ml of 1% solution of PtCl₄ (0.1730 g), 25.2 ml of 1.0 % solution of GaCl₃ (0.252 g), 20.7 ml of 1.0 % solution of ZnCl₂ (0.207 g), and 27.7 ml of 1.0 % solution of CaCl₂ (0.2769 g) were mixed together and stirred for 30 min in a beaker at room temperature. [0059] All the metal salts solutions were added to the flask containing the γ-Al₂O₃ support. Next, the metal solution with support kept on rotation at 60 °C temperature for 1 hour. The solution was then evaporated under vacuum until only solid slurry was left. After impregnation, the impregnated material was dried in oven at 110 °C overnight. The dry impregnated material was calcined at 600 °C for 6 h in static air to obtain the catalyst. Example 18. Testing of catalytic activity test of Pt-Ga-Zn-Ca/γ-Al₂O₃ catalyst [0060] The catalyst prepared according to Example 17 was tested by the procedure according to Example 1. Table 10 shows results of testing of catalytic activity of Pt-Ga-Zn- Ca/γ-Al₂O₃ in reaction of non-oxidative n-butane dehydrogenation. Table 10: Results of catalytic activity test of Pt-Ga-Zn-Ca/γ-Al₂O₃ catalyst

Example 19. Preparation of the Pt-Zr-Zn-Ca/γ-Al₂O₃ catalyst [0061] The catalyst 1%Pt1%Zr1%Zn1%Ca/γ-Al₂O₃ was prepared using the simultaneous wet impregnation method. For 10.0 g of catalyst preparation, 9.6 g of calcined γ-Al₂O₃ was taken in a round bottom flask. At initial stage, 17.3 ml of 1.0 % solution of PtCl₄ (0.1730 g), 35.3 ml of 1% solution of ZrCl₂ (0.3530 g), 20.7 ml of 1% solution of ZnCl₂ (0.207 g) and 27.7 ml of 1.0 % solution of CaCl₂ (0.2769 g) were mixed together and stirred for 30 min in a beaker at room temperature. [0062] All the metal salts solutions were added to the flask containing the γ-Al₂O₃ support. Next, the metal solution with support was kept on rotation at 60 °C for 1 hour. The solution was then evaporated under vacuum until only solid slurry was left. After impregnation, the catalyst was dried in oven at 110 °C overnight. The dried catalyst was calcined at 600 °C for 6 h in static air. Example 20. Testing of catalytic activity test of Pt-Zr-Zn-Ca/γ-Al₂O₃ catalyst [0063] The catalyst prepared according to Example 19 was tested by the procedure according to Example 1. Table 11 shows results of testing of catalytic activity of Pt-Sn-Mg- Zn/γ-Al₂O₃ in reaction of non-oxidative n-butane dehydrogenation. Table 11: Results of catalytic activity test of Pt-Zr-Zn-Ca/γ-Al₂O₃ catalyst

[0064] In the context of the present invention, at least the following 16 embodiments are described. Embodiment 1 is a catalyst. The catalyst includes platinum (Pt) and/or palladium (Pd), a transition metal, a post transition metal, and an alkaline earth metal, wherein the catalyst is in an active cluster configuration. Embodiment 2 is the catalyst of embodiment 1, wherein the transition metal includes zinc (Zn) and/or zirconium (Zr). Embodiment 3 is the catalyst of either of embodiments 1 or 2, wherein the post transition metal is selected from the group consisting of tin (Sn), indium (In), gallium (Ga,) and combinations thereof. Embodiment 4 is the catalyst of any of embodiments 1 to 3, wherein the alkaline earth metal includes calcium (Ca). Embodiment 5 is the catalyst of any of embodiments 1 to 4, wherein the catalyst includes Pt, Zn, Sn, In, and Ca supported on alumina. Embodiment 6 is the catalyst of embodiment 5, wherein the Ca and Zn in the catalyst have a synergistic effect configured to enhance activity and selectivity of Pt-Sn and Pt-Sn-In systems. Embodiment 7 is the catalyst of either of embodiments 5 or 6, wherein the alumina includes γ-Al₂O₃. Embodiment 8 is the catalyst of embodiment 7, wherein the γ-Al₂O₃ has a Brunauer-Emmett-Teller (BET) surface area of 80- 350 m²/g. Embodiment 9 is the catalyst of any of embodiments 1 to 8, wherein the catalyst contains 0.1-3 wt.% platinum (Pt), 0.1-3 wt.% indium (In), 0.1-3 wt.% tin (Sn), 0.1-3 wt.% zinc (Zn) and 0.1-3 wt.% calcium (Ca) supported on γ-alumina (γ-Al₂O₃). Embodiment 10 is the catalyst of any of embodiments 1 to 9, wherein the catalyst contains 0.3 to 2 wt.% Pt, preferably 1 wt.% Pt, 0.3 to 2 wt.% Sn, preferably 1 wt.% Sn, 0.3 to 2 wt.% Zn, preferably 1 wt.% Zn, 0.3 to 2 wt.% Ca, preferably 1 wt.% Ca, 0.3 to 2 wt.% In, preferably 1 wt.% In, or combinations thereof. [0065] Embodiment 11 is a catalyst for dehydrogenation of a hydrocarbon. The catalyst includes active clusters containing platinum (Pt), zinc (Zn), tin (Sn), indium (In), and calcium (Ca) supported on Al₂O₃, wherein the platinum in the active clusters has a particle size of 0.01 to 0.6 nm. Embodiment 12 is the catalyst of any of embodiments 1 to 11, wherein the catalyst is configured to catalyze a non-oxidative dehydrogenation of a hydrocarbon. Embodiment 13 is the catalyst of embodiment 12, wherein the catalyst is configured to catalyze a non-oxidative dehydrogenation of n-butane at an optimal reaction temperature of 500 to 650 ℃, preferably 550 to 600 ℃, more preferably about 575 ℃. [0066] Embodiment 14 is a method of producing a catalyst of any of embodiments 1 to 13. The method includes depositing via sequential and/or simultaneous wet impregnation of Pt, In, Sn, Zn, and Ca on the catalyst support of γ-Al₂O₃ to produce a dry impregnated material. The method further includes calcining the dry impregnated material to produce the catalyst. [0067] Embodiment 15 is a method of producing a catalyst of any of embodiments 1 to 13. The method includes contacting a γ-Al₂O₃ support with a solution containing soluble salts of Pt, In, Sn, Zn, and Ca to form a first mixture. The method further includes evaporating solvent of the first mixture to obtain an impregnated material. The method still further includes drying the impregnated material to produce a dry impregnated material. In addition, the method includes calcining the dry impregnated material to obtain the catalyst. Embodiment 16 is the method of either of embodiments 14 or 15, wherein the calcining is conducted at a temperature of 600 °C for 6 hours in a furnace. [0068] Although embodiments of the present application and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the embodiments as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the above disclosure, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.

Claims

CLAIMS 1. A catalyst comprising: platinum (Pt) and/or palladium (Pd); a transition metal; a post transition metal; and an alkaline earth metal; wherein the catalyst is in an active cluster configuration.

2. The catalyst of claim 1, wherein the transition metal comprises zinc (Zn) and/or zirconium (Zr).

3. The catalyst of any of claims 1 and 2, wherein the post transition metal is selected from the group consisting of tin (Sn), indium (In), gallium (Ga,) and combinations thereof.

4. The catalyst of any of claims 1 and 2, wherein the alkaline earth metal comprises calcium (Ca).

5. The catalyst of any of claims 1 and 2, wherein the catalyst comprises Pt, Zn, Sn, In, and Ca supported on alumina.

6. The catalyst of claim 5, wherein the Ca and Zn in the catalyst have a synergistic effect configured to enhance activity and selectivity of Pt-Sn and Pt-Sn-In systems.

7. The catalyst of claim 5, wherein the alumina includes γ-Al₂O₃.

8. The catalyst of claim 7, wherein the γ-Al₂O₃ has a Brunauer-Emmett-Teller (BET) surface area of 80-350 m²/g.

9. The catalyst of any of claims 1 and 2, wherein the catalyst comprises 0.1-3 wt.% platinum (Pt), 0.1-3 wt.% indium (In), 0.1-3 wt.% tin (Sn), 0.1-3 wt.% zinc (Zn) and 0.1-3 wt.% calcium (Ca) supported on γ-alumina (γ-Al₂O₃).

10. The catalyst of any of claims 1 and 2, wherein the catalyst comprises 0.3 to 2 wt.% Pt, preferably 1 wt.% Pt, 0.3 to 2 wt.% Sn, preferably 1 wt.% Sn, 0.3 to 2 wt.% Zn, preferably 1 wt.% Zn, 0.3 to 2 wt.% Ca, preferably 1 wt.% Ca, 0.3 to 2 wt.% In, preferably 1 wt.% In, or combinations thereof.

11. A catalyst for dehydrogenation of a hydrocarbon, the catalyst comprising: active clusters comprising platinum (Pt), zinc (Zn), tin (Sn), indium (In), and calcium (Ca) supported on Al₂O₃, wherein the platinum in the active clusters has a particle size of 0.01 to 0.6 nm.

12. The catalyst of any of claims 1 and 2, wherein the catalyst is configured to catalyze a non-oxidative dehydrogenation of a hydrocarbon.

13. The catalyst of claim 12, wherein the catalyst is configured to catalyze a non- oxidative dehydrogenation of n-butane at an optimal reaction temperature of 500 to 650 ℃, preferably 550 to 600 ℃, more preferably about 575 ℃.

14. A method of producing a catalyst of any of claims 1 and 2, the method comprising: depositing via sequential and/or simultaneous wet impregnation of Pt, In, Sn, Zn, and Ca on the catalyst support of γ-Al₂O₃ to produce a dry impregnated material; and calcining the dry impregnated material to produce the catalyst.

15. A method of producing a catalyst of any of claims 1 and 2, the method comprising: contacting a γ-Al₂O₃ support with a solution comprising soluble salts of Pt, In, Sn, Zn, and Ca to form a first mixture; evaporating solvent of the first mixture to obtain an impregnated material; drying the impregnated material to produce a dry impregnated material; and calcining the dry impregnated material to obtain the catalyst.

16. The method of claim 14, wherein the calcining is conducted at a temperature of 600 °C for 6 hours in a furnace.