The present disclosure relates to a catalyst comprising support matrix, active metal, promoter metal and halide, wherein the support matrix is additionally subjected to a modifier to obtain a modified support matrix. The catalyst of the present disclosure exhibits increased activity, selectivity and stability when used for reforming process. Besides that it enhances the reformate yield with reduced coke formation when compared to the available catalyst for reforming process, production of aromatics and improving the quality of reformate. The disclosure further relates to the process for preparing the catalyst of the present disclosure. The catalyst of the present disclosure derived from the process described herein, displays lower deactivation rate during reactions demonstrating reduced regeneration frequency, thereby making the catalyst economically feasible.
Catalytic reforming is a well-established industrial process applied by the petroleum industry for improving the octane quality of naphtha and production of aromatics. In catalytic reforming, a functional catalyst is employed which contains metal function, to govern reactions such as dehydrogenation and hydrogenation of naphthenes. During the reaction the catalyst deactivates continuously due to coking, and as the coke builds up on the catalyst surface, the reaction temperature has to be increased gradually to offset the loss of catalyst activity. Over a period of time it is no longer feasible economically to continue operations. There are numbers of catalysts available, which are being used for catalytic naphtha reforming process, wherein platinum alone or with combination of metals such as rhenium, iridium, tin and germanium is employed on a support matrix. In reforming catalysts, a certain level of catalyst acidity is required to initiate essential isomerization reactions; whereas presence of acidity more than required level leads to both yield loss and catalyst deactivation. Although, these catalysts exists, there still is a need for further improvement, especially with regard to catalyst activity, selectivity, stable performance and importantly reducing the laydown of coke due to formation of undesirable heavier products, which is affecting the activity of the catalyst. In view of the above said, there is a need for developing a better catalyst and a process for developing such catalyst to overcome the limitations observed with respect to the catalysts known in the art.
The present disclosure relates to a catalyst comprising components including but not limiting to a support matrix subjected to a modifier to obtain a modified support matrix, active metal, promoter metal and halide.
In an exemplary embodiment, the support matrix of the catalyst of the present disclosure is modified by contacting the support matrix with modifier such as chemical element including but not limiting to alkaline earth metal and lanthanide, or a combination thereof.
In a preferred embodiment, the present disclosure relates to a catalyst comprising an aluminum support matrix, modified by combination of alkaline earth metal and lanthanide.
This modified catalyst is thereafter chlorinated and impregnated with platinum and tin to obtain the final catalyst of the present disclosure.
The present disclosure further relates to a process for preparing the catalyst composition, said process comprising steps of:
In another embodiment, the present disclosure relates to a use of the catalyst composition for reducing coke formation to at least 4% to 5% per kg of a feed, wherein the catalyst composition comprises support matrix, active metal, promoter metal and halide and wherein the support matrix is a modified support matrix.
In a non-limiting embodiment, the catalyst of the present disclosure has a lower deactivation rate and increased activity, selectivity and stability, leading to reduced regeneration frequency and increased economic feasibility. The catalyst also provides for increased reformate yield, suppression of acid site cracking and reduced coke formation during catalytic reforming process.
The present disclosure relates to a composition, wherein the composition is a catalyst having a catalytic activity which provides for an increased reformate yield and reduced coke formation during the process of catalytic reforming.
In a non-limiting embodiment, the catalyst of the present disclosure has lower deactivation rate and increased activity, selectivity and stability, leading to reduced regeneration frequency and increased economic feasibility. In a preferred embodiment, the catalyst of the present disclosure is a reforming catalyst.
In an embodiment, the catalyst of the present disclosure comprises components including but not limiting to a support matrix, active metal, promoter metal and halide, wherein the support matrix is additionally subjected to a modifier to obtain a modified support matrix. The present disclosure thus provides a catalyst whose performance is improved with simultaneous optimization of acid site cracking through the use of support matrix modification with alkaline earth metals and lanthanides.
In a non-limiting embodiment, the support matrix of the catalyst is an inorganic oxide including but not limiting to alpha alumina, theta alumina, gamma alumina, delta alumina, eta alumina, silica alumina, cordierite, zirconia, titania, zeolites and non-zeolitic molecular sieves (NZMS), or any combination thereof. In an exemplary embodiment, the support matrix includes but is not limited to alpha alumina, theta alumina, gamma alumina, delta alumina, eta alumina, theta alumina and silica alumina, or any combination thereof. In a preferred embodiment, the support matrix is gamma alumina.
In an embodiment, the support matrix including but not limiting to alpha alumina, theta alumina, gamma alumina, delta alumina, eta alumina, silica alumina, cordierite, zirconia, titania, zeolites and non-zeolitic molecular sieves (NZMS), or any combination thereof, is modified by contacting said support matrix with modifier such as chemical element including but not limiting to alkaline earth metal and lanthanide, or any combination thereof.
In an exemplary embodiment, the alkaline earth metal includes but is not limited to beryllium, magnesium, calcium, strontium, and barium, or any combination thereof.
In an exemplary embodiment, the lanthanide includes but is not limited to lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium, or any combination thereof.
In a preferred embodiment, the support matrix of the catalyst is modified by the alkaline earth metal such as magnesium and barium, or a combination thereof. In an alternate preferred embodiment, the support matrix of the catalyst is modified by lanthanum.
In another preferred embodiment, the support matrix of the catalyst is modified by a combination of an alkaline earth metal such as magnesium and a lanthanide such as lanthanum. Thus, the support matrix of the catalyst may comprise a combination of magnesium and lanthanum.
In an exemplary embodiment, the active metal of the catalyst includes but is not limited to ruthenium, rhodium, palladium, osmium, iridium and platinum, or any combination thereof.
In a preferred embodiment, the active metal of the catalyst is platinum.
In an exemplary embodiment, the promoter metal of the catalyst includes but is not limited to tin, germanium, rhenium, gallium, bismuth, lead, indium, cerium and zinc, or any combination thereof.
In a preferred embodiment, the promoter metal of the catalyst is tin.
In an exemplary embodiment, the halide of the catalyst includes but is not limited to fluorine, chlorine and bromine, or any combination thereof.
In a preferred embodiment, the halide of the catalyst is either in the elemental form or in the ionic form.
In another preferred embodiment, the halide of the catalyst is in the ionic form, wherein the halide is chloride.
In a non-limiting embodiment, the modifier including but not limiting alkaline earth metal such as magnesium and barium and lanthanide such as lanthanum, independently or in combination within the catalyst, are at a concentration ranging from about 0.01 wt % to about 0.5 wt %.
In an exemplary embodiment, the magnesium and barium, independently or in combination within the catalyst are at a concentration ranging from about 0.01 wt % to about 0.5 wt %.
In yet another exemplary embodiment, the lanthanum within the catalyst is at a concentration ranging from about 0.01 wt % to about 0.5 wt %.
In a non-limiting embodiment, the active metal such as platinum within the catalyst is at a concentration ranging from about 0.01 wt % to about 0.5 wt %.
In an exemplary embodiment, the platinum within the catalyst is at a concentration ranging from about 0.01 wt % to about 0.5 wt %.
In a non-limiting embodiment, the promoter metal such as tin within the catalyst is at a concentration ranging from about 0.01 wt % to about 0.5 wt %.
In an exemplary embodiment, the tin within the catalyst is at a concentration ranging from about 0.01 wt % to about 0.5 wt %.
In a non-limiting embodiment, the halide such as chloride within the catalyst is at a concentration ranging from about 0.8 wt % to about 1.2 wt %.
In an exemplary embodiment, the chloride within the catalyst is at a concentration ranging from about 0.8 wt % to about 1.2 wt %.
In a non-limiting embodiment, the concentration of the support matrix within the catalyst is the remaining percentage with respect to cumulative percentages of the components such as active metal, promoter metal and halide, wherein the active metal is at a concentration ranging from about 0.01 wt % to about 0.5 wt %, the promoter is at a concentration ranging from about 0.01 wt % to about 0.5 wt % and the halide is at a concentration ranging from about 0.8 wt % to about 1.2 wt %. For instance, in a case when the active metal is at a concentration of about 0.01 wt %, the promoter is at a concentration of about 0.01 wt % and the halide is at a concentration of about 0.8 wt % then the concentration of the support matrix is about 99.18 wt %. Similarly when the concentration of the active metal is about 0.5 wt %, concentration of the promoter metal is about 0.5 wt % and the concentration of the halide is about 1.2 wt %, then the concentration of support matrix is about 97.8 wt %.
Thus, in a preferred embodiment, the present disclosure relates to a catalyst comprising a gamma aluminum support matrix, modified by combination of alkaline earth metal and lanthanide in the form of magnesium and lanthanum. This modified catalyst is thereafter chlorinated and impregnated with platinum and tin to obtain the final catalyst of the present disclosure, which provides for an increased reformate yield and reduced coke formation during the process of catalytic reforming.
In a non-limiting embodiment, the catalyst of the present disclosure provides stable performance towards activity and selectivity for total aromatics during naphtha reforming.
In another non-limiting embodiment, the catalyst of the present disclosure is a bi-functional catalyst having both metal function and an acidic function.
In a non-limiting embodiment, the present disclosure also relates to a process for preparing the catalyst herein comprising support matrix, active metal, promoter metal and halide, wherein the support matrix is additionally subjected to a modifier to obtain a modified support matrix.
In an exemplary embodiment, the process for preparing the catalyst of the present disclosure comprises acts of:
In an exemplary embodiment, the process for preparing the catalyst of the present disclosure comprises acts of:
In an exemplary embodiment, the process for preparing the catalyst of the present disclosure comprises acts of:
In a preferred embodiment, the process for preparing the catalyst of the present disclosure comprises acts of:
In a non-limiting embodiment, the modifier including but not limiting to alkaline earth metal such as magnesium and barium employed in the process for preparing the catalyst of the present disclosure ranges from about 0.01 wt % to about 0.5 wt %.
In another non-limiting embodiment, the modifier including but not limiting to lanthanide such as lanthanum employed in the process for preparing the catalyst of the present disclosure ranges from about 0.01 wt % to about 0.5 wt %.
In yet another non-limiting embodiment, the halide such as chloride employed in the process for preparing the catalyst of the present disclosure ranges from about 0.8 wt % to about 1.2 wt %.
In still another non-limiting embodiment, the active metal such as platinum employed in the process for preparing the catalyst of the present disclosure ranges from about 0.01 wt % to about 0.5 wt %.
In still another non-limiting embodiment, the promoter metal such as tin employed in the process for preparing the catalyst of the present disclosure ranges from about 0.01 wt % to about 0.5 wt %.
In a more preferred embodiment, the process for preparing of catalyst of the present disclosure comprises acts of:
In a non-limiting embodiment, the magnesium in the process for preparing the catalyst of the present disclosure ranges from about 0.01 wt % to about 0.5 wt %.
In yet another non-limiting embodiment, the chloride in the process for preparing the catalyst of the present disclosure ranges from about 0.8 wt % to about 1.2 wt %.
In still another non-limiting embodiment, the platinum in the process for preparing the catalyst of the present disclosure ranges from about 0.01 wt % to about 0.5 wt %.
In still another non-limiting embodiment, the tin in the process for preparing the catalyst of the present disclosure is ranging from about 0.01 wt % to about 0.5 wt %.
In an exemplary embodiment, platinum solution and tin solution are prepared by using precursors including but not limiting to hexacholoroplatinic acid (H2PtCl6. (H2O)6) and tin chloride (SnCl2), respectively, wherein the hexacholoroplatinic acid is at a concentration of about 19.03 mg/ml and tin chloride at a concentration of about 115.04 mg/ml, respectively.
The concentration of the precursors of platinum and tin are adjusted in order to have platinum and tin within the catalyst at a concentration ranging from about 0.01 wt % to about 0.5 wt %.
In another exemplary embodiment, hydrogen chloride solution is added to the solution of H2PtCl6. (H2O)6 and SnCl2 in order to avoid precipitation of metal chloride solution. To this solution, the modified alumina support of the present disclosure is added and immersed for a time period ranging from about 6 hours to about 18 hours, preferably 12 hrs, at a temperature ranging from about 15° C. to about 35° C. with intermediate gentle stirring. During impregnation in equilibrium, the solid (alumina support) to solution ratio is in the range of about 1:5. This is followed by removing the solution by subjecting it to rotary evaporation having a maximum speed of 50 rpm at a temperature ranging from about 40° C. to about 60° C.
The process for preparation of catalyst of the present disclosure reduces weak and strong acid site in the catalyst and thereby increases the activity and stability of the catalyst. Both weak acid site and strong acid site in the magnesium modified catalyst is reduced in comparison to the priorly known catalysts in the art. Further, the catalyst (catalyst-2) of the present disclosure tends to have 3 peaks, wherein first peak shall correspond to weak acid sites, second peak shall correspond to medium to strong acid sites and third peak shall correspond to very strong acid sites. This distinct difference in the acidity pattern of the catalyst of the present disclosure plays a significant role in performance and stability of the catalyst, unmodified catalyst (reference catalyst).
In a non-limiting embodiment, the process for preparing the catalyst of the present disclosure causes higher active metal dispersion of about 98% in the catalyst of the present disclosure when compared to unmodified catalyst (reference catalyst) having the active metal dispersion of about 86%. It is critical to note that higher active metal dispersion in the catalyst, indicates stronger interaction between the metal and the modified support matrix, which in turn is responsible for enhanced activity and stability of the catalyst.
In another non-limiting embodiment, pore size distribution of the catalyst of the present disclosure ranges from about 20° A to about 100° A, when compared to the unmodified catalyst (reference catalyst), wherein the pore size distribution ranges from about 30° A to about 150° A. Due to a narrower pore size distribution in the catalyst of the present disclosure, there is a higher dispersion of active metal and promoter metal, either individually or in combination, thereby leading to higher stability and increased activity of the catalyst of the present disclosure.
In a non-limiting embodiment, the catalyst of the present disclosure demonstrates a total C8 aromatics yield ranging from about 33% to about 35% at the start of the reaction (SOR) and ranging from about 21% to about 29% at the end of the reaction (EOR), when compared to the unmodified catalyst (reference catalyst) which demonstrate the total C8 aromatics yield of about 32% at the start of the reaction (SOR) and about 20% at the end of the reaction (EOR).
In another non-limiting embodiment, the catalyst of the present disclosure demonstrates a total aromatics yield ranging from about 78% to about 81% at the start of the reaction (SOR) and ranging from about 48% to about 67% at the end of the reaction (EOR), when compared to unmodified catalyst (reference catalyst) which demonstrates the total aromatics yield of about 75% at the start of the reaction (SOR) and about 44% at the end of the reaction (EOR).
In yet another non-limiting embodiment, the catalyst of the present disclosure exemplifies greater hours of stream in a catalytic reaction when compared to the unmodified reforming catalyst.
In an exemplary embodiment, the catalyst of the present disclosure demonstrates at least 60 hours of stream in a catalytic reaction when compared to the unmodified reforming catalyst.
In still another non-limiting embodiment, the catalyst of the present disclosure exemplifies reduced coke formation of about 3% when compared to the coke formation of about 6% when employing unmodified catalyst (reference catalyst) in a reaction. The reduced coke formation/deposition demonstrated by the catalyst of the present disclosure corroborates with the reduced acid site and higher metal dispersion on the catalyst of the present disclosure.
In a non-limiting embodiment, the expression ‘contact or contacting’ defined in the instant specification independently refers to impregnation, immersion and/or saturation, wherein there is a thorough interaction between the components.
In a non-limiting embodiment, the expression catalyst-2 described in the instant specification refers to the catalyst of the present disclosure having magnesium modified support matrix.
In a non-limiting embodiment, the expression catalyst-3 described in the instant specification refers to the catalyst of the present disclosure having barium modified support matrix.
In a non-limiting embodiment, the expression catalyst-4 described in the instant specification refers to the catalyst of the present disclosure having Lanthanum modified support matrix.
Additional embodiments and features of the present disclosure will be apparent to one of ordinary skill in art based upon description provided herein. The embodiments herein provide various features and advantageous details thereof in the description. Descriptions of well-known/conventional methods and techniques are omitted so as to not unnecessarily obscure the embodiments herein. The examples provided herein are intended merely to facilitate an understanding of ways in which the embodiments herein may be practiced and to further enable those of skill in the art to practice the embodiments herein. Accordingly, the following examples should not be construed as limiting the scope of the embodiments herein.
The performance evaluation of unmodified catalyst (reference catalyst) used as a reference bench mark catalyst and lab prepared catalysts were carried out under identical reaction conditions i.e. at Pressure 7.3 kg/cm2, H2/HC mol ratio 4, LHSV 1.95 h−1, and reaction temperature 510-540° C. using naphtha feed.
About 30 g of alumina support is dried at a temperature of about 120° C. for about 12 hrs to remove the surface organic impurities and moisture. The dried alumina is immersed in a container containing magnesium nitrate solution (about 0.95 g of magnesium nitrate in about 150 ml water, wherein the metal (magnesium) content is 0.3 wt %) having a pH of about 5 to about 6 for about 6 hrs. Thereafter, the solution is removed by subjecting the immersed alumina with the solution to an equilibrium-rotary evaporator at 50° C. to obtain magnesium modified alumina. Upon removal of the solvent, the magnesium modified alumina is dried at a temperature of about 120° C. for about 12 hrs to about 15 hrs in an oven and calcined at a temperature of about 540° C. for about 6 hrs.
Alternatively about 30 g of alumina support is dried at a temperature of about 120° C. for about 12 hrs to remove the surface organic impurities and moisture. The dried alumina is immersed in a container containing barium nitrate solution (about 0.171 g of barium nitrate in about 150 ml of water, wherein the metal (barium) content is 0.3 wt %) having a pH of about 5 to about 6 for about 6 hrs. Thereafter, the solution is removed by subjecting the immersed alumina with the solution to a equilibrium-rotary evaporator at 50° C. to obtain barium modified alumina. Upon removal of the solvent, the barium modified alumina is dried at a temperature of about 120° C. for about 12 hrs to about 15 hrs in an oven and calcined at a temperature of about 540° C. for about 6 hrs.
Alternatively about 30 g of alumina support is dried at a temperature of about 120° C. for about 12 hrs to remove the surface organic impurities and moisture. The dried alumina is immersed in a container containing lanthanum nitrate (about 0.28 g of lanthanum nitrate in about 150 ml of distilled water, wherein the metal (lanthanum) content is 0.3 wt %) solution having a pH of about 5 to about 6 for about 6 hrs. Thereafter, the solution is removed by subjecting the immersed alumina with the solution to a equilibrium-rotary evaporator at 50° C. to obtain lanthanum modified alumina. Upon removal of the solvent, the lanthanum modified alumina is dried at a temperature of about 120° C. for about 12 hrs to about 15 hrs in an oven and calcined at a temperature of about 540° C. for about 6 hrs.
About 30 g of calcined modified alumina support such as magnesium modified alumina, barium modified alumina and lanthanum modified alumina, respectively is immersed in about 150 ml of hydrochloride solution comprising about 0.8 ml of 35% aqueous hydrogen chloride (molarity of about 11.5) for about 12 hrs (ratio of alumina support to the volume of hydrogen chloride solution is about 1:5), followed by drying the modified alumina at a temperature of about 120° C. for about 12 hrs to about 14 hrs to obtain chlorinated magnesium-alumina support, chlorinated barium-alumina support and chlorinated lanthanum-alumina support, respectively.
About 30 g chlorinated magnesium modified alumina support, about 30 g of chlorinated barium-alumina support and about 30 g of chlorinated lanthanum-alumina support, respectively is immersed in a solution of platinum and tin solutions, which in-turn were prepared by using (H2PtCl6. (H2O)6) and SnCl2, respectively.
2.61 ml and 0.439 ml of platinum and tin solution, respectively are used in order to obtain the required 0.25 wt % of platinum and tin in the final catalyst. The ratio of the impregnating solution (solution of platinum and tin) to the chlorinated magnesium alumina support, chlorinated barium-alumina support and chlorinated lanthanum-alumina support, respectively is about 1:5 (by weight) (solid to liquid ratio). To the above solution, 0.8964 ml of 35% hydrogen chloride solution (molarity of about 11.5) is added in order to avoid the precipitation of metal chloride in the solution. To this solution, chlorinated magnesium-alumina support, chlorinated barium-alumina support and chlorinated lanthanum-alumina support, respectively is immersed for about 12 hrs to about 15 hrs at a temperature of about 27° C. to about 35° C. with intermediate stirring. The solution is removed using equilibrium-rotary evaporator, followed by drying the alumina support having metals, at a temperature of about 120° C. for about 12 hrs in an oven. The dried chlorinated magnesium-alumina support, chlorinated barium-alumina support and chlorinated lanthanum-alumina support, respectively having platinum and tin, is finally calcined at a temperature of about 540° C. for about 6 hrs to obtain the final catalyst.
In an exemplary embodiment, the above mentioned process steps are also followed to obtain catalyst including but not limiting to active metal such as ruthenium, rhodium, palladium, osmium, iridium, promoter metal such as germanium, rhenium, gallium, bismuth, lead, indium, cerium and zinc, wherein the support matrix of the catalyst is modified by alkaline earth metal such as beryllium, calcium and strontium and lanthanide such as cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
Reaction Condition:
Pressure about 7.3 Kg/cm2, Liquid Hourly Space Velocity (LHSV) of about 1.95 h-1, H2:HC mol ratio of about 4. The reaction temperature at the start of the reaction (SOR) is about 521° C. and reaction temperature at the end of the reaction (EOR) is about 540° C.
Observations of Table 1:
Observations of Table 2:
The effect of the magnesium on the nature of the acidic sites in catalyst-2 is studied by using NH3-TPD adsorption-desorption method and the chemisorption profiles are obtained by catalyst-2 and reference catalyst, as illustrated in
Temperature Programmed Reduction (TPR) is carried out on a Micrometrics Autochem II chemisorption analyser instrument using about 200 mg samples (catalyst 2 and reference catalyst, respectively) for each experiment. The catalyst (reference catalyst and catalyst-2, respectively) is loaded into a quartz tube and allowed for stabilization of TCD (thermal conductivity signal) base line in the said analyser. Thereafter, H2-TPR is started from about room temperature to about 900° C. at a heating rate of about 10° C./min in about 10 ml/min of 8% H2 in Ar. A thermal conductivity detector (TCD) is used to monitor the consumption of H2.
Further, thermal conductivity detector (TCD) signal is an indication of hydrogen consumption during TPR studies. The TCD signal obtained with the catalyst-2 is very sharp (at 320° C. and 480° C. respectively) in comparison with the reference catalyst, which exemplifies the strong metal and support interaction which is responsible for enhanced activity and stability of catalyst-2, unlike the reference catalyst.
The analysis of pore size distribution of the catalyst of the present disclosure (catalyst-2) and unmodified catalyst (reference catalyst) is carried by BJH (Barrett-Joyner-Halenda) method using Micromeritics ASAP 2020 apparatus.
Reaction Condition:
Pressure about 7.3 Kg/cm2, Liquid Hourly Space Velocity (LHSV) of about 1.95 h-1. H2:HC mol ratio of about 4. The reaction temperature at the start of the reaction (SOR) is about 521° C. and reaction temperature at the end of the reaction (EOR) is about 540° C.
Observations of Table-4:
Observations of Table 5:
The reaction subjected with the catalyst of the present disclosure (catalyst-3) illustrates the coke content (undesired product) of about 2.6%, which is much lesser than the coke content of about 6.1% illustrated by the reference catalyst. Thereby demonstrating reduced coke deposition in a reaction subjected with the catalyst of the present disclosure.
Reaction Condition:
Pressure about 7.3 Kg/cm2, Liquid Hourly Space Velocity (LHSV) of about 1.95 h-1, H2:HC mol ratio of about 4. The reaction temperature at the start of the reaction (SOR) is about 521° C. and reaction temperature at the end of the reaction (EOR) is about 540° C.
Observations of Table-6:
Observations of Table 7:
The reaction subjected with the catalyst of the present disclosure (catalyst-4) illustrates the coke content (undesired product) of about 4.5%, which is much lesser than the coke content of about 6.1% illustrated by the reference catalyst. Thereby demonstrating reduced coke deposition in a reaction subjected with the catalyst of the present disclosure.
Number | Date | Country | Kind |
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3940/MUM/2015 | Oct 2015 | IN | national |