DESC:FIELD
The present disclosure relates to a shaped catalyst composite for reducing the olefin content of hydrocarbons.
DEFINITIONS
As used in the present disclosure, the following terms are generally intended to have the meaning as set forth below, except to the extent that the context in which they are used indicate otherwise.
Pugging: the term “pugging” refers to working a material into a soft, plastic condition suitable for making different objects, without air pockets.
Compositing material: the term “compositing material” refers to the oxides of elements from group IIIA and group VA, or combinations thereof.
BACKGROUND
Production of para-xylene by the adsorption process requires the C8 aromatics feed to be free from olefinic impurities, so as to safeguard the high priced adsorbent. Hence, these olefinic impurities are removed from up-streams of the adsorption unit using specialty clay. However, clay has a short life and cannot be regenerated, thus necessitating frequent changeover, resulting in generation of huge volumes of solid waste.
Therefore, development of a new composite for application as a catalyst and for the hydrocarbon conversion process in the area of refining and petrochemicals is of commercial interest.
Therefore, there is felt a need to provide a catalyst composite that mitigates the drawbacks mentioned hereinabove.
OBJECTS
Some of the objects of the present disclosure, which at least one embodiment herein satisfies, are as follows:
An object of the present disclosure is to ameliorate one or more problems of the prior art or to at least provide a useful alternative.
Another object of the present disclosure is to provide a shaped catalyst composite.
Still another object of the present disclosure is to provide a shaped catalyst composite for reducing the olefin content of hydrocarbons containing olefinic impurities.
Other objects and advantages of the present disclosure will be more apparent from the following description, which is not intended to limit the scope of the present disclosure.

SUMMARY
In one aspect, the present disclosure provides a shaped catalyst composite comprising at least one zeolite selected from the group consisting of MWW type zeolite and hetero-atom incorporated MWW type zeolite; and at least one compositing agent selected from the group consisting of oxides of elements from group IIIA, oxides of elements from group VA, aluminium phosphate and complex oxides of combination of aluminium and phosphorous.
In accordance with an embodiment of the present disclosure, the hetero-atom in the hetero-atom incorporated MWW type zeolite is cerium and the amount of cerium in the hetero-atom incorporated MWW type zeolite is in the range of 0.01 weight% to 5 weight %, preferably in the range of 0.5 weight% to 1.5 weight%. The hetero-atom incorporated MWW type zeolite is at least one zeolite selected from the group consisting of Ce-MCM-49, Ce-MCM-36, Ce-MCM-22 and Ce-MCM-56.
In accordance with an embodiment of the present disclosure, the hetero-atom incorporated MWW type zeolite is Ce-MCM-22.
The oxide of element from group IIIA is at least one selected from the group consisting of alumina, and gallium oxide.
The oxide of element from group VA is phosphorous pentoxide.
The weight proportion of the zeolite to the compositing agent is in the range of 95:5 to 5:95, preferably in the range of 60:40 to 80:20.
The shape of the shaped catalyst composite is at least one selected from the group consisting of spherical, cylindrical, tri-lobe, tetra-lobe, star, ring, tablets, pellets, and honeycomb structure.
The shaped catalyst composite has a diameter in the range of 0.2 millimeters to 5 millimeters, and length in the range of 0.2 millimeters to 20 millimeters.
In a second aspect, the present disclosure provides a process for preparing the shaped catalyst composite. The process comprises the following steps:
at least one zeolite selected from the group consisting of MWW type zeolite and hetero-atom incorporated MWW type zeolite is provided. At least one compositing agent selected from the group consisting of oxides of elements from group IIIA, oxides of elements from group VA, aluminium phosphate and complex oxides of combination of aluminium and phosphorous is provided. A homogenous mixture comprising the zeolite and the compositing agent is prepared. The homogeneous mixture is pugged to obtain an extrudable mass. The extrudable mass is extruded to obtain formed bodies. The formed bodies are dried to obtain dried formed bodies. The dried formed bodies are calcined to obtain the shaped catalyst composite.
The homogeneous mixture further comprises an extrusion aid.
In accordance with an embodiment of the present disclosure, the step of preparing the homogenous mixture involves mixing the zeolite and the compositing agent, and pulverizing the resultant mixture, and adding water to the pulverized mixture to obtain the homogeneous mixture.
In accordance with another embodiment of the present disclosure, the compositing agent is aluminium phosphate, and the step of preparing the homogenous mixture involves the following sub-steps. Alumina and water are mixed to obtain a suspension and orthophosphoric acid is added to the suspension to obtain a reaction mixture. Alumina and orthophosphoric acid are reacted to obtain aluminum phosphate. Aluminum phosphate is admixed with the zeolite to obtain the homogeneous mixture.
In a third aspect, the present disclosure provides a process for reducing the olefin content of hydrocarbons. The process comprises the following steps. Hydrocarbons comprising olefins is provided; and the hydrocarbon is contacted with the shaped catalyst composite of the present disclosure, in a reactor, at a temperature in the range of 100 °C to 500 °C, preferably at a temperature in the range of 150 °C to 250 °C, for a time period in the range of 30 minutes to 300 minutes, preferably for a time period in the range of 150 minutes to 200 minutes, to obtain treated hydrocarbon with reduced olefin content.
The olefin content of the hydrocarbon is reduced by 10 weight% to 70 weight %.

DETAILED DESCRIPTION
Production of para-xylene by the adsorption process requires the C8 aromatics feed to be free from olefinic impurities, so as to safeguard the high priced adsorbent. Hence, these olefinic impurities are removed from up-streams of the adsorption unit using specialty clay. However, clay has a short life and cannot be regenerated, thus necessitating frequent changeover, resulting in generation of huge volumes of solid waste.
The present disclosure envisages a shaped catalyst composite comprising an environment friendly material that can replace the existing short-lived, non-regenerable clays. The shaped catalyst composite of the present disclosure has enhanced efficacy and service life, and enhanced process reliability and can be reused.
In one aspect, the present disclosure provides a shaped catalyst composite comprising at least one zeolite selected from the group consisting of MWW type zeolite and hetero-atom incorporated MWW type zeolite; and at least one compositing agent selected from the group consisting of oxides of elements from group IIIA, oxides of elements from group VA, aluminum phosphate and complex oxides of combination of aluminum and phosphorous.
Clays can be employed as compositing agent for preparing shaped catalyst composites comprising zeolite. However, clays have certain inherent properties, such as the high acid strength of surface hydroxyl group, which adversely affect the performance of zeolites.
The compositing materials used in the process of the present disclosure do not adversely affect the performance of zeolite. In some cases, it is observed that the performance of zeolite in relation to removal of olefins has been enhanced due to use of the compositing agent of the present disclosure. Surprisingly, it is observed that the use of aluminum phosphate as a compositing agent improved performance of the shaped catalyst composite by at least 20%.
In accordance with an embodiment of the present disclosure, the hetero-atom in the hetero-atom incorporated MWW type zeolite is cerium and the amount of cerium in the hetero-atom incorporated MWW type zeolite is in the range of 0.01 weight% to 5 weight %, preferably in the range of 0.5 weight% to 1.5 weight%. The hetero-atom incorporated MWW type zeolite is at least one zeolite selected from the group consisting of Ce-MCM-49, Ce-MCM-36, Ce-MCM-22 and Ce-MCM-56.
In accordance with an embodiment of the present disclosure, the hetero-atom incorporated MWW type zeolite is Ce-MCM-22.
The oxide of element from group IIIA is at least one selected from the group consisting of alumina, and gallium oxide.
In accordance with an embodiment of the present disclosure, the oxide of element from group IIIA is alumina.
The oxide of element from group VA is phosphorous pentoxide.
In an exemplary embodiment of the present disclosure, the compositing agent is aluminium phosphate. Typically, aluminum phosphate used as compositing agent comprises compounds having phosphorous to aluminum molar ratio in the range of 0.5:1 to 3:1.
The weight proportion of the zeolite to the compositing agent in the shaped catalyst composite is in the range of 95:5 to 5:95, preferably in the range of 60:40 to 80:20.
In accordance with an embodiment of the present disclosure, the weight proportion of zeolite in the shaped catalyst composite is 70 weight%.
The shape of the shaped catalyst composite is at least one selected from the group consisting of spherical, cylindrical, tri-lobe, tetra-lobe, star, ring, tablets, pellets, and honeycomb structure.
The shaped catalyst composite has diameter in the range of 0.2 millimeters to 5 millimeters, and length in the range of 0.2 millimeters to 20 millimeters.
In a second aspect, the present disclosure provides a process for preparing the shaped catalyst composite. The process comprises the following steps. At least one zeolite selected from the group consisting of MWW type zeolite and hetero-atom incorporated MWW type zeolite is provided. At least one compositing agent selected from the group consisting of oxides of elements from group IIIA, oxides of elements from group VA, aluminium phosphate and complex oxides of combination of aluminium and phosphorous is provided. A homogenous mixture comprising the zeolite and the compositing agent is prepared. The homogeneous mixture is pugged to obtain an extrudable mass. The extrudable mass is extruded to obtain formed bodies. The formed bodies are dried to obtain dried formed bodies. The dried formed bodies are calcined to obtain the shaped catalyst composite.
The homogeneous mixture further comprises an extrusion aid.
In accordance with an embodiment of the present disclosure, the extrusion aid is hydroxypropylmethylcellulose.
In accordance with an embodiment of the present disclosure, the step of obtaining the homogenous mixture involves mixing the zeolite and the compositing agent, and pulverizing the resultant mixture, followed by adding water to the pulverized mixture to obtain the homogeneous mixture.
In accordance with another embodiment of the present disclosure, the compositing agent is aluminium phosphate, and the step of preparing the homogenous mixture involves the following sub-steps. Alumina and water are mixed to obtain a suspension. Orthophosphoric acid is added to the suspension to obtain a reaction mixture. Alumina and orthophosphoric acid are reacted to obtain aluminum phosphate. Aluminum phosphate is admixed with the zeolite to obtain the homogeneous mixture.
Alumina and orthrophosphoric acid can be reacted by stirring the reaction mixture. In accordance with one embodiment, alumina and orthrophosphoric acid are reacted by stirring the reaction mixture while heating.
In a third aspect, the present disclosure provides a process for reducing the olefin content of hydrocarbon. The process comprises the following steps. Hydrocarbon comprising olefins is provided; and the hydrocarbon is contacted with the shaped catalyst composite of the present disclosure, in a reactor, at a temperature in the range of 100 °C to 500 °C, preferably at a temperature in the range of 150 °C to 250 °C, for a time period in the range of 30 minutes to 300 minutes, preferably for a time period in the range of 150 minutes to 200 minutes, to obtain treated hydrocarbon with reduced olefin content.
The olefin content of the hydrocarbon is reduced by 10 weight% to 70 weight %.
The shaped catalyst composite of the present disclosure can be regenerated by calcination at a temperature in the range of 450 °C to 600 °C, for a time period in the range of 1 hour to 10 hours in an oxidizing atmosphere.
In accordance with one embodiment of the present disclosure, the shaped catalyst composite of the present disclosure was regenerated four times without loss of the activity for removal of olefins from hydrocarbon.
The shaped catalyst composite of the present disclosure can be used for the effective removal of olefinic impurities from hydrocarbon. The shaped catalyst composite exhibits a higher catalytic performance than that of the conventional catalyst and hence lower amounts of the catalyst composite is required for the olefin reduction of hydrocarbon.
It is observed that catalytic activity of the shaped catalyst composite of the present disclosure for the removal of olefinic impurities from hydrocarbon is higher than the activity of clay. Specifically, the shaped catalyst composite containing Ce-MWW zeolite and aluminium phosphate showed catalytic activity twice the activity of clay.
The higher performance of the catalyst composite could be possibly due to highly disordered nature of the Ce-MWW layered material, thus providing much lower diffusional resistance to the reactant molecules.
It is observed that the compositing agent used for the preparation of the shaped catalyst composite plays a significant role in catalytic activity for the removal of olefins from hydrocarbons. Typically, aluminum phosphate containing catalyst composites showed high catalytic activity.
The shaped catalyst composite of the present disclosure has higher stability and longer life. Therefore, the frequency of change-over for loading the catalyst is reduced. Since, the catalyst composite can be regenerated; the generation of solid waste is avoided.
The present disclosure is further described in light of the following laboratory scale experiments which are set forth for illustration purpose only and not to be construed for limiting the scope of the disclosure. These laboratory scale experiments can be scaled up to industrial/commercial scale and the results obtained can be extrapolated to industrial/commercial scale.
Experimental Details
Experiments 1 and 2: Preparation of MWW-zeolite and Ce-incorporated MWW zeolite
Calculation of molar composition of zeolite:
The zeolite material obtained after crystallization step always contains the occluded templating agent. The templating agent is usually decomposed during the calcining step. Therefore, for any formulation purpose, the actual material content needs to be considered on loss on ignition (LOI) basis.
Similarly, the compositing material was also examined for extent of loss on ignition. To achieve the desired final composition of the composite material, initial quantities of corresponding zeolites and compositing materials, were corrected for LOI, and the final composition of the zeolite are reported on LOI basis.
Experiment 1: Preparation of MWW zeolite
A mixture of 61 g of sodium aluminate and 1400 ml water in a 5000 ml beaker was placed under an overhead mechanical stirrer. The mixture was stirred at 300 rpm for 10 minutes and a clear solution was obtained. 17 g of NaOH was dissolved in 1000 ml water separately, and the solution was added to the solution of sodium aluminate. Stirring was continued for another 30 minutes.
Subsequently, 194 g of hexamethyleneimine (HMI) was added to the above solution, and the resultant mixture was stirred further for 30 minutes at room temperature. Finally, to this resulting mixture, 620 g of precipitated silica was added slowly and stirred further for 1h.
The gel was treated hydrothermally at 170 °C for 30 h in an autoclave with continuous stirring.
After the crystallization process, the solid product was separated and washed thoroughly with water, till free from alkali. Finally, the material was dried at 120 °C overnight in oven.
The composition (on molar basis) and conditions for preparation of MWW zeolite along with those without any hetero-atom incorporation is shown in Table 1.
Experiment 2: Preparation of Ce-incorporated MWW zeolite (Ce-MWW)
To a mixture containing 100 g H2O, 2.08 g NaOH, 3.71 g NaAlO2 was slowly added cerium nitrate solution (35.35 g H2O and 2.17 g cerium nitrate), and the resultant mixture was stirred vigorously. To the vigorously stirred mixture, was gently added 19.83 g HMI, followed by the addition of 113 g colloidal silica to obtain a mixture. The mixture was stirred continuously at room temperature for 2 h to obtain a hydrogel. The resulting hydrogel was transferred into an autoclave, wherein the hydrogel was subjected to a hydrothermal treatment at 170 °C under stirring at a speed of 250 rpm for 48 hours to obtain crystalline material. The solid product was recovered and washed to make free from alkali. Finally, the material was dried at 120 °C overnight in oven.
The composition and conditions for preparation of Ce-incorporated MWW zeolite along with those without any hetero-atom incorporation is shown in Table 1.
Table 1: Compositions and conditions for synthesis of MWW zeolites
S. No. Experiment 1 2
1. Silica Source Precipitated Silica Colloidal silica
Molar composition
2. SiO2/(Al2O3+CeO2) - 30
3. SiO2/Al2O3 30 43
4. SiO2/CeO2 - 100
5. H2O/SiO2 15 15
6. Na/SiO2 1.5 1.5
7. HMI/SiO2 0.2 0.3
Crystallization Conditions
8. Temperature, °C 170 170
9. Stirring speed, rpm 250 250
10. Time, h 30 48
Characteristic Properties
11. Crystalline Phase MCM-22 Ce-MCM-22
12. BET Surface Area, /m2g-1 422 400

Experiment 3: Preparation of shaped catalyst composite with MWW zeolite and alumina
61.6 g Condia alumina (having LOI 27 wt%) and 130.4 g MWW zeolite from the stock as prepared in experiment 1 were mixed thoroughly in a mortar-pastel. 227.8 g aqueous solution of 3.7% acetic acid was added to the powder mixture to obtain a homogeneous mixture. The homogeneous mixture was pugged thoroughly till an extrudable mass was obtained. Extrusion was done using a 1.5 mm die. Extrudate were dried at room temperature for 1 h followed by drying at 120 °C for 6 h in an air oven. Dried sample was calcined at 540 °C for 6 h under flowing air. Zeolite content in the final composite (on loss free basis) was 70% by weight.
Experiment 4: Preparation of shaped catalyst composite with MWW zeolite and precipitated aluminium phosphate
Aluminium Phosphate powder preparation: 24 g of flash calcined activated alumina powder (obtained from a commercial supplier, having LOI 9.07 wt%) was dispersed in 100 g of demineralized (DM) water. 142 g of orthophosphoric acid (H3PO4) was added drop wise to above mixture with continuous stirring. After addition of H3PO4, the temperature was raised to 85 °C and maintained for 1h. The final mixture was cooled down to room temperature. Sodium aluminate solution (90 g sodium aluminate in 500 g water) was added drop wise to complete the formation of aluminum phosphate. This was washed with water and was dried at 120 °C overnight.
28 g precipitated aluminum phosphate powder (having LOI 27.82 wt%) was mixed with 43.8 g MWW zeolite and 0.65 g hydroxypropyl methyl cellulose (HPMC). 81 g DM water was added and pugged thoroughly till a smooth dough was formed. Extrusion was done using 1.5 mm die. Extrudate was dried at room temperature for 1 h, followed by drying at 120 °C for 6 h. Dried sample was calcined at 540 °C for 6 h. Zeolite content in final composite was 70% by weight.
Experiment 5: Preparation of shaped catalyst composite with MWW zeolite, alumina and phosphoric acid
6.8 g Condia alumina, 35.4 g MWW zeolite and 0.38 g hydroxy-propyl-methyl cellulose was thoroughly mixed in a mortar-pastel. A solution of H3PO4 (11.36 g) in 64.08 g of DM water was prepared. This solution was added to powder mixture to obtain homogeneous mixture and the homogeneous mixture pugged thoroughly to get the desired dough. Extrusion was done using 1.5 mm die. Extrudate was dried at room temperature for 1 h followed by at 120 °C for 6 h. Dried sample was calcined at 540 °C for 6 h. Zeolite content in final composite was 70% by weight.
Experiment 6: Preparation of shaped catalyst composite with MWW zeolite and aluminium phosphate hydrogel
16.9 g Condia alumina was taken in a Teflon beaker and 49.1 g DM water was added to it and stirred with magnetic bar for 10 min. 28.4 g H3PO4 was added drop wise to above slurry and it transformed to a thick and smooth hydrogel. 49.3 g DM water was added in to the gel and stirred for another 10 min. This gel was added to 87.6 g of MWW zeolite powder (from the stock as prepared in experiment 1) to obtain a homogeneous mixture and the homogeneous mixture was pugged thoroughly with added extra 18 g DM water. It was pugged for 10 min and extruded using 1.5 mm die. Extrudate was dried at room temperature for 1 h followed by at 120 °C for 6 h. Dried sample was calcined at 540 °C for 6 h under flowing air. Zeolite content in final composite was 70% by weight.
Experiment 7: Preparation of shaped catalyst composite with MWW zeolite and aluminum phosphate hydrogel
16.9 g Condia alumina was taken in a beaker and 49.1 g DM water was added to it and stirred with a magnetic bar for 10 min to make a slurry. 22.9 g H3PO4 was added drop wise to above slurry. A smooth and thick gel was formed. 19.2 g DM water was added to the gel and stirred for another 10 min. The smooth and thinner hydrogel was added to 87.6 g of MWW zeolite powder (from the stock as prepared in experiment 1) to obtain a homogeneous mixture and the homogeneous mixture was pugged thoroughly. 105.9 g DM water was added to the mixture and pugged for 10 min and extruded using 1.5 mm die. Extrudate was dried at room temperature for 1 h followed by at 120 °C for 6 h. Dried sample was calcined at 540 °C for 6 h under flowing air. Zeolite content in final composite was 70% by weight.
Experiment 8: Preparation of shaped catalyst composite with MWW zeolite and aluminium phosphate hydrogel
16.9 g Condia alumina was taken in a Teflon beaker and 14.9 g DM water was added to it and stirred with magnetic bar for 10 min. 34 g H3PO4 was added drop wise to above slurry. A thick and smooth gel was formed and stirred for another 10 min. This hydrogel was added to 87.6 g of MWW zeolite powder (from the stock as prepared in experiment 1) to obtain a homogeneous mixture and the homogeneous mixture was pugged thoroughly with additional 110.4 g DM water. Pugged for 10 min and extruded using 1.5 mm die. Extrudate was dried at room temperature for 1 h followed by at 120 °C for 6 h. Dried sample was calcined at 540 °C for 6 h under flowing air. Zeolite content in final composite was 70% by weight.
Experiment 9: Preparation of shaped catalyst composite with Ce-incorporated MWW zeolite and aluminium phosphate gel
12 g Condia alumina was taken in a Teflon beaker and 11 g DM water was added to it and stirred with magnetic bar for 10 min. 19.8 g H3PO4 was added drop wise to above slurry. A thick and smooth gel was formed and stirred for another 10 min. This hydrogel was added to 60.6 g of Ce incorporated MCM-22, MWW zeolite powder (from the stock as prepared in experiment 2) to obtain a homogeneous mixture and the homogeneous mixture was pugged thoroughly with added extra 81.4 g DM water. Pugged for 10 min and extruded using 1.5 mm die. Extrudate was dried at room temperature for 1 h followed by at 120 °C for 6 h. Dried sample was calcined at 540 °C for 6 h under flowing air. Zeolite content in final composite was 70% by weight.
Experiment 10-16
Catalytic performance of the samples was evaluated for reduction of olefin content from a commercial C8+ aromatic hydrocarbon. Composition of the Deheptanizer bottom hydrocarbon, as employed for the olefin removal experiments is shown below in Table 2.
Table 2: Composition of Deheptanizer Column Bottom hydrocarbon
Component wt%
Non-aromatics 1.3
Toluene 1.56
Ethyl benzene 8.31
Xylenes 44.51
C9Aromatics 36.23
C10A + Heavy Aromatics 8.09

5 g of extrudates were added to 35 g of commercial deheptanizer column bottom hydrocarbon in a stainless steel autoclave of 70 ml capacity. The reactor was purged with nitrogen to remove air and was closed. The autoclave reactor was heated at predetermined temperature and duration mentioned in Table 3. After this, the reactor was cooled to ambient conditions. The hydrocarbon liquid was separated from the solid catalyst, and was examined for level of olefinic impurity. Olefin concentration of the feed and product samples was analyzed using Bromine Index (BI) by standard test method ASTM D-1491. The results are presented in Table 3.
Table 3: Performance of the shaped catalyst composites of the present disclosure towards reducing olefin content of hydrocarbon
Experiment No Catalyst Details from Reaction Conditions Results % Bromine Index (BI) Reduction (Olefin Conv.)
Temp., °C Time, h Feed BI Prod. BI
Experiment 10 Experiment 3 180 3 608 371 39
Experiment 11 Experiment 4 180 3 603 338 44
Experiment 12 Experiment 5 180 3 609 313 49
Experiment 13 Experiment 6 180 3 611 343 44
Experiment 14 Experiment 7 180 3 613 348 43
Experiment 15 Experiment 8 180 3 597 299 51
Experiment 16 Experiment 9 180 3 614 225 63

It is evident from Table-3 that the shaped catalyst composite of the present disclosure efficiently reduce olefins from the Deheptanizer Column Bottom hydrocarbon (C8+ aromatics hydrocarbon).
Further, it is observed that the catalyst composite containing Ce-MWW zeolite and aluminium phosphate (Experiment 16) has higher performance towards reducing olefins from the Deheptanizer Column Bottom hydrocarbon (C8+ aromatics hydrocarbon) as compared to the MWW zeolite and aluminium phosphate (Example 15).
Experiment 17: Comparative experiment using clay
Catalytic performance of the clay was evaluated for reduction of olefin content from a commercial C8+ aromatic hydrocarbon.
5 g of Clay was added to 35 g of commercial deheptanizer column bottom hydrocarbon in a stainless steel autoclave of 70 ml capacity. The reactor was purged with nitrogen to remove air and was closed. The autoclave reactor was heated at predetermined temperature and duration mentioned in Table 4. After this, the reactor was cooled to ambient conditions. The hydrocarbon liquid was separated from the clay, and was examined for the level of olefinic impurity. Olefin concentration of the feed and product samples was analyzed using Bromine Index (BI) by standard test method ASTM D-1491. The results are presented in Table 4.
Table 4: Performance of clay towards reducing olefin content of hydrocarbon
Experiment No Reaction Conditions Results % Bromine Index (BI) Reduction (Olefin Conv.)
Temp., °C Time, h Feed BI Prod. BI
Experiment 17 180 3 610 432 29

It is evident from Tables 3 and 4 that the catalytic activity of the shaped catalyst composite of the present disclosure for the removal of olefinic impurities from hydrocarbon is higher than the activity of clay. Specifically, the shaped catalyst composite containing Ce-MWW zeolite and aluminium phosphate (Table 3, experiment 16) showed catalytic activity twice the activity of clay.

Experiment 18-21: Regeneration of spent catalyst
The catalyst composite of present disclosure is said to be spent catalyst composite when the olefin removal efficiency of the catalyst composite drops to less than 50% (due to continuous usage), with respect to that at the beginning of the process.
Experiment 18: First regeneration of spent catalyst
A fresh batch of catalyst composite (30 g) was prepared according to the procedure given in experiment 9. 25 g of this fresh catalyst was subjected to accelerated aging conditions. After 9 days of continuous operation, olefin removal efficiency of the catalyst composite decreased to 44% with respect to that of the fresh catalyst at the beginning of run, indicating that the zeolitic catalyst composite is deactivated and was in spent form.
The spent catalyst composite was separated and, was dried in an oven at 120 °C for two hours. The dried spent catalyst composite was then calcined in air at 540 °C for 6 h. The calcined zeolitic composite was cooled to ambient temperature to obtain regenerated zeolitic catalyst composite.
The extrudates were clean white after the regeneration process. The regenerated zeolitic composite catalyst, thus obtained, was the first regenerated zeolite catalyst composite.
The first regenerated zeolitic composite catalyst (5 g) was employed for reduction of olefins from a fresh feed of commercial de-heptanizer bottom hydrocarbon following the procedure as described in Experiment 16. Reaction conditions and results are provided in Table 5.
Experiment 19: Second regeneration of spent catalyst
The first regenerated composite catalyst (19.0 g) was subjected to accelerated aging conditions. After 9 days of continuous operation, olefin removal efficiency of the catalyst composite decreased to 43% olefin reduction with respect to the olefin removal efficacy of the first regenerated catalyst composite at the beginning of the run, indicating that the first regenerated zeolitic composite catalyst spent.
The spent first regenerated zeolitic composite was separated, and was regenerated using the process mentioned hereinabove. This sample was the second regenerated zeolitic composite catalyst.
The second regenerated zeolitic composite catalyst (5 g) was employed for reduction of olefins from a fresh feed of commercial de-heptanizer bottom hydrocarbon following the procedure as described in Experiment 16. Reaction conditions and results of the test are given in Table 5.
Experiment 20: Third regeneration of spent catalyst
The second regenerated zeolitic composite catalyst (13.0 g) was subjected to accelerated aging conditions. After 8 days of continuous operation, olefin conversion efficiency of the catalyst composite decreased to 47% olefin reduction as compared to that of the second regenerated catalyst composite at the beginning of the run, indicating that the second regenerated zeolitic composite catalyst spent.
The spent second regenerated zeolitic composite catalyst was separated, and was regenerated using the process mentioned hereinabove. This sample was the third regenerated zeolitic composite catalyst.
The third regenerated zeolitic composite catalyst (5 g) was employed for reduction of olefins from a fresh feed of commercial de-heptanizer bottom hydrocarbon following the procedure as described in Experiment 16. Reaction conditions and results of the test are given in Table 5.
Experiment 21: Fourth regeneration of spent catalyst
The third regenerated zeolitic composite catalyst (7.0 g) was subjected to accelerated aging conditions. After 10 days of continuous operation, olefin removal efficiency of the catalyst composite decreased to 39% olefin reduction as compared to that of the third regenerated catalyst composite at the beginning of the run, indicating that the first regenerated zeolitic composite catalyst spent.
The spent third regenerated zeolitic composite catalyst was separated and, was regenerated using the process mentioned hereinabove. This sample was the fourth regenerated zeolitic composite catalyst.
The fourth regenerated zeolitic composite catalyst (5 g) was employed for the reduction of olefins from a fresh feed of commercial de-heptanizer bottom hydrocarbon following the procedure as described in Experiment 16. Reaction conditions and results of the test are given in Table 5.
Table 5: Regenerability of the catalyst composite
Experiment No Type of catalyst (Fresh/regenerated) Reaction Conditions Results % Bromine Index (BI) Reduction (Olefin Conv.)
Temp., °C Time, h Feed BI Prod. BI
Experiment 16 Fresh 180 3 601 220 63
Experiment 18 First regenerated catalyst 180 3 605 230 62
Experiment 19 Second regenerated catalyst 180 3 592 218 63
Experiment 20 Third regenerated catalyst 180 3 619 235 62
Experiment 21 Fourth regenerated catalyst 180 3 609 238 61

Clearly, it is seen from Table-5 that the catalyst composite of the present disclosure is regenerable on calcination in an oxidizing atmosphere.
Experiment 22: Amount of benzene and toluene formation
This experiment provides the extent of benzene and toluene formation during removal of olefins from commercial C8 aromatics hydrocarbon while employing the catalyst composite of the present disclosure.
5 g of extrudates (as prepared in experiment 9) was added to 35 g of commercial deheptanizer column bottom hydrocarbon in a Teflon lined stainless steel bomb of 100 ml capacity. The reactor was purged with nitrogen to remove air and was closed. The bomb reactor was heated at 180 °C for 3 h. After this, the reactor was cooled to ambient conditions. The hydrocarbon liquid was separated from the solid catalyst, and was examined for level of olefinic impurity. The results are shown in Table-6.

Table 6: GC Analysis of Feed and Product
Feed Product (weight %)
Lighters 0.35 0.32
Benzene 0.00 0.00
Toluene 0.23 0.25
C8 Aromatics 52.85 52.67
C9 Aromatics 39.65 39.71
C10 Aromatics and heavies 6.92 7.05

Analysis of the feed and product by gas chromatograph showed that benzene formation was nil, while toluene formation was only 200 ppm.
TECHNICAL ADVANCEMENTS
The present disclosure described herein above has several technical advantages including, but not limited to, the realization of:
- a shaped catalyst composite for reducing olefins from hydrocarbon;
- the shaped catalyst composite for removal of olefins in the range of 10 to 70 weight% from hydrocarbon;
- a shaped catalyst composite having higher stability and longer life and hence reducing the frequency of change-over for loading the catalyst; and
- a shaped catalyst composite that can be regenerated, thus avoids solid waste generation.
Throughout this specification the word “comprise”, or variations such as “comprises” or “comprising”, will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.
The use of the expression “at least” or “at least one” suggests the use of one or more elements or ingredients or quantities, as the use may be in the embodiment of the invention to achieve one or more of the desired objects or results. While certain embodiments of the inventions have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the inventions. Variations or modifications to the formulation of this invention, within the scope of the invention, may occur to those skilled in the art upon reviewing the disclosure herein. Such variations or modifications are well within the spirit of this invention.
The numerical values given for various physical parameters, dimensions and quantities are only approximate values and it is envisaged that the values higher than the numerical value assigned to the physical parameters, dimensions and quantities fall within the scope of the invention unless there is a statement in the specification to the contrary.
While considerable emphasis has been placed herein on the specific features of the preferred embodiment, it will be appreciated that many additional features can be added and that many changes can be made in the preferred embodiment without departing from the principles of the disclosure. These and other changes in the preferred embodiment of the disclosure will be apparent to those skilled in the art from the disclosure herein, whereby it is to be distinctly understood that the foregoing descriptive matter is to be interpreted merely as illustrative of the disclosure and not as a limitation.
,CLAIMS:WE CLAIM
1. A shaped catalyst composite comprising:
• at least one zeolite selected from the group consisting of MWW type zeolite and hetero-atom incorporated MWW type zeolite; and
• at least one compositing agent selected from the group consisting of oxides of elements from group IIIA, oxides of elements from group VA, aluminium phosphate and complex oxides of combination of aluminium and phosphorous.
2. The shaped catalyst composite as claimed in claim 1, wherein said hetero-atom in said hetero-atom incorporated MWW type zeolite is cerium and the amount of cerium in said hetero-atom incorporated MWW type zeolite is in the range of 0.01 weight% to 5 weight %, preferably in the range of 0.5 weight% to 1.5 weight%.
3. The shaped catalyst composite as claimed in any of claims 1 or 2, wherein said hetero-atom incorporated MWW type zeolite is at least one zeolite selected from the group consisting of Ce-MCM-49, Ce-MCM-36, Ce-MCM-22 and Ce-MCM-56.
4. The shaped catalyst composite as claimed in any of claims 1 or 2, wherein said hetero-atom incorporated MWW type zeolite is Ce-MCM-22.
5. The shaped catalyst composite as claimed in claim 1, wherein said oxide of element from group IIIA is at least one selected from the group consisting of alumina, and gallium oxide.
6. The shaped catalyst composite as claimed in claim 1, wherein said oxide of element from group VA is phosphorous pentoxide.
7. The shaped catalyst composite as claimed in claim 1, wherein the weight proportion of said zeolite to said compositing agent is in the range of 95:5 to 5:95, preferably in the range of 60:40 to 80:20.
8. The shaped catalyst composite as claimed in claim 1, wherein the shape of said shaped catalyst composite is at least one selected from the group consisting of spherical, cylindrical, tri-lobe, tetra-lobe, star, ring, tablets, pellets, and honey comb structure.
9. The shaped catalyst composite as claimed in claim 1, wherein the diameter of said shaped catalyst composite is in the range of 0.2 millimeters to 5 millimeters, and length is in the range of 0.2 millimeters to 20 millimeters.
10. A process for preparing the shaped catalyst composite, said process comprising the following steps:
a. providing at least one zeolite selected from the group consisting of MWW type zeolite and hetero-atom incorporated MWW type zeolite;
b. providing at least one compositing agent selected from the group consisting of oxides of elements from group IIIA, oxides of elements from group VA, aluminium phosphate and complex oxides of combination of aluminium and phosphorous;
c. preparing a homogenous mixture comprising said zeolite and said compositing agent, and pugging said homogeneous mixture to obtain an extrudable mass;
d. extruding said extrudable mass to obtain formed bodies;
e. drying said formed bodies to obtain dried formed bodies; and
f. calcining said dried formed bodies to obtain said shaped catalyst composite.
11. The process as claimed in claim 10, wherein the homogeneous mixture further comprises an extrusion aid.
12. The process as claimed in claim 10, wherein the step of preparing said homogenous mixture involves mixing said zeolite and said compositing agent, and pulverizing the resultant mixture, and adding water to said pulverized mixture to obtain said homogeneous mixture.
13. The process as claimed in claim 10, wherein the compositing agent is aluminium phosphate, and the step of obtaining said homogenous mixture involves the following sub-steps:
a. mixing alumina and water to obtain a suspension and adding orthophosphoric acid to said suspension to obtain a reaction mixture;
b. reacting alumina and orthophosphoric acid to obtain aluminum phosphate; and
c. admixing aluminum phosphate with said zeolite to obtain said homogeneous mixture.
14. A process for reducing the olefin content of hydrocarbon, comprising
• providing hydrocarbon comprising olefins; and
• contacting said hydrocarbon with said shaped catalyst composite as claimed in claim 1, in a reactor, at a temperature in the range of 100 °C to 500 °C, preferably at a temperature in the range of 150 °C to 250 °C, for a time period in the range of 30 minutes to 300 minutes, preferably for a time period in the range of 150 minutes to 200 minutes, to obtain treated hydrocarbon with reduced olefin content,
wherein the olefin content of the hydrocarbon is reduced by 10 weight% to 70 weight %.