Title of Invention

" A Process for the Preparation of Fluid Catalytic Cracking (FCC) Catalyst"

Abstract

A process for the preparation of fluid catalytic cracking (FCC) catalyst by preparing NH4Y Zeolite with aqueous solution of ammonium salt by known methods to achieve silica alumina ratio of 80:20 having concentration range of 1 to 3N at a temperature in the range of 70-100°C to obtain NH4Y Zeolite, heating the above said NH4Y Zeolite at a temperature of 380-820°C for a period in the range of 0.1 to 12 hrs. in presence of steam to obtain dealuminated Zeolite Y, treating the dealuminated Zeolite Y with mineral acid with concentration range of 0.1 to6N, dispersing the 30% dealuminated Zeolite Y into 40% active silica alumina matrix having silica alumina ratio of 80:20 to obtain dispersed dealuminated Zeolite Y, stirring the above said dispersed dealuminated Zeolite Y mixture and adding 20% of Kaolin, adding 10% of peptized alumina hydrate at a pH range between 6-7.5, filtering, washing, drying & calcining at temperature ranging 400 to 600°C to obtain catalyst, treating the catalyst obtained with a salt of lanthanum solution having 2-3 wt% lanthanum & drying the rare earth exchanged catalyst for 2-4 hrs at a temperature of 80 to 150°C, calcining the catalyst at temperature 400-600°C for 2 to 3 hrs. & sieving to obtain 100-200 mesh size particle catalyst.

Full Text

This invention relates to a process for the preparation of fluid catalytic cracking catalyst. In particular the invention relates to a process for the preparation of cracking catalyst using dealurainated Y-type crystalline molecular sieve (zeolite) and catalytically active silica-alumina matrix as important components. The invention more specifically relates to a process for the preparation of novel fluid catalytic cracking catalyst using Y-type zeolite dealuminated to a varying degree and cata-lytically active silica-alumina matrix which results in improved catalytic performance with respect to better middle distillate and coke selectivity. Fluid catalytic cracking (FCC) occupies an improtant place in petroleum refining industry for the conversion of heavier petroleum fractions in to valuable product like LPG gasoline and middle distillate [Total Cycle Oil (TCO)] a blending component for diesel pool. Often, it is said that FCC is the source for the production of some of the dirtiest transportation fuel, as the gasoline and middle distillate produced from FCC requires hydrotreatment to meet the specifications of transportation fuels. With the introduction of new specifications for gasoline i.e. reformulated gasoline, however, FCC is also known as the source for the production of some of the cleanest fuels. Light olefins (C , C and C ) i.e. propylene, iso butylene and iso amylene, produced from FCC is the feed stock for the production of environmentally friendly, high octane fuel like oxygenates such as methyl tertiary butyl ether (MTBE), tertiary amyl ether (TAME) and alkylates such as iso octane. The operation of Indian FCC units is some what different as compared to American or European units. To achieve the objective of maximising total cycle oil (TCO) the FCC units in India operate to limit the conversion of vacuum gas oil (VGO) on a first pass basis by controlling the reaction severity to avoid over cracking of TCO range molecules to the lighter products. + The heavy cycle oil (370 ) with potential for conversion is recycled back to the reactor to maximise total cycle oil. Table-2 summarises the major operating conditions and yield structures of FCC units in India and abroad. Table-2 Typical Operating Conditions and Product Yield (FCC) (Table Remobved) A suitable catalyst plays a major role in maximising total cycle oil since changing the operating parameters has its own limitations for a commercial unit. To meet the demand of a particular product, around 300 different varites of catalysts are commercially available world wide with more than 350 commercial FCC units processing 350 million tonnes per annum of the feed stock. In India there are nine FCC units in refineries located in different parts of the country with processing capacity of 7.3 million tonnes per annum. All these units have adopted imported catalyst and process technology. An overview of Indian FCC units are summarised in Table-1. Table-1 FCC Units in India (Table Remobved) The objective of FCC catalyst formulation for use in Indian context can be classified as better coke selectivity increased bottoms conversion i.e. decreased yield of + unconverted material (370 ) Higher middle distillate [Total cycle oil (TCO)l selectivity LPG with increased olefinicity To achieve the objective listed above, catalyst formulation requires delauminated zeolite and catalytically active matrix. One of the characte'ristics of the FCC operation is a tendency towards higher regenerator temperature and consequently more severe deactivation of catalyst. Another desirable feature of zeolite in FCC processing is coke selectivity i.e. low tendency to produce catalytic coke. This is achieved by dispersing dealuminated zeolite-Y of higher silica alumina ratio which are known as ultrastable Y-zeolite in silica alumina matrix. Dealumination of Y-zeolite results in decrease in unit cell size (UCS) and an increase in the silica to alumina ratio of the zeolite frame work which in turn affects the physico chemical properties of the zeolite and increase the thermal and hydrothermal stability. Such changes in zeolite composition and properties have a significant impact on catalytic activity, selectivity and stability. The degree of dealumination also changes the acidity pattern of the zeolite and hence the activity and coke selectivity. Because of lower concentration of active sites, hydrogen transfer reactions are suppressed and there by produce less coke and more olefinic products resulting in higher olefinicity of LPG. During hydrothermal dealumination of zeolite-Y consumption of sodalite units leads to the formation of secondary pores, such as super micropores (~30A ) and mesopores (50-200 A ). Mesopores are helpful in reduction of bottoms yield. The size and number of secondary pores increases with the degree of frame work dealumination. Acid leaching increases the effective dia of secondary pores by removing non frame work aluminium (NFAL) species and facilitate the diffusion of larger molecules in to the zeolite crystal. The catalytically active matrix serves one valuable purpose i.e., the cracking of larger molecules with increased accessibility of active sites of the matrix to the reacting molecules. The inclusion of active matrix in the catalyst therefore leads to the decrease in the yield of bottoms i.e. slurry oil boiling above 370 C. The objective of the present invention is therefore, to provide a process for the preparation of novel FCC catalyst using Y-zeolite dealuminated to varying degree and catalytically active matrix with increased bottoms conversion and better middle distillate and coke selectivity. In carrying out the present invention, as a result of extensive research carried out by us, five FCC catalysts were prepared each having the same active matrix. Each of the catalyst had the same composition, the only difference was that each catalyst had zeolite of different degree of dealumination which varied from 20 to 80%. The composition of the finished catalyst is presented in detail in Table-3. Table-3 Composition of FCC Catalysts Catalyst SiO -AlO Peptized Kaolin Zeolite Type of Zeolite-Y (Table Remobved) Accordingly, the present invention provides a process for the preparation of fluid catalytic cracking (FCC) catalyst, which comprises: a) preparing NH4Y Zeolite with aqueous solution of ammonium salt by known methods to achieve silica alumina ratio of 80:20 having concentration range of 1 to 3N at a temperature in the range of 70-100°C to obtain NH4Y Zeolite, b) heating the above said NH4Y Zeolite at a temperature of 380-820°C for a period in the range of 0.1 to 12 hrs. in presence of steam to obtain dealuminated Zeolite Y, c) treating the dealuminated Zeolite Y with mineral acid with concentration range of 0.1 to6N, d) dispersing the 30% dealuminated Zeolite Y into 40% active silica alumina matrix having silica alumina ratio of 80:20 to obtain dispersed dealuminated Zeolite Y, e) stirring the above said dispersed dealuminated Zeolite Y mixture and adding 20% of Kaolin, f) adding 10% of peptized alumina hydrate at a pH range between 6-7.5, g) filtering, washing, drying & calcining at temperature ranging 400 to 600°C to obtain catalyst, h) treating the catalyst obtained with a salt of lanthanum solution having 2-3 wt% lanthanum & drying the rare earth exchanged catalyst for 2-4 hrs at a temperature of 80 to 150°C, i) calcining the catalyst at temperature 400-600°C for 2 to 3 hrs. & sieving to obtain 100-200 mesh size particle catalyst. The source of silica may be selected from sodium silicate, polysilisic acid, the source of alumina may be selected from aluminium sulphate and aluminium nitrate. The acid used in step (ii) may be selected from sulphuric, acetic, formic, nitric and hydrochloric acid, the mineral acid used in step (vi) may be selected from hydrochloric and sulfuric acid. The process of the present invention is described in detail below : (a) Exchange of NaY zeolite to the NH4Y zeolite is affected by treatment with an aqueous solution of ammonium salt generally of 1-3N strength at a temperature in the range of 70-100°C. The salt such as that of ammonium chloride, sulphate or nitrate preferably ammonium nitrate may be used. This step as required to bring down the sodium content to less than 1%, where in the concentration of the ammonium salt solution is so adjusted to provide 2-6 equivalents of the cation per equivalent of total base exchange capacity. (b) The NH -Y zeolite formed is heated to a temperature in the range of 380-820 C over a period of 0.1 to 12 hours in presence of steam in a specified and controlled manner to achieve a degree of dealumination in the range of 20-80%. (c) The dealuminated zeolite-Y obtained from step (b) is treated with a mineral acid to further enchance the crystallinity and the pore size of the zeolite Y and reducing sodium content to less than 0.1%, which treatment is given only in cases of dealumination exceeding 60%, otherwise it is not recommended. The concentration of the acid in the range of 0.1-6N is so chosen that it does not affect the frame work aluminium. The acid used may be selected from any mono basic acid like sulphuric and nitric acid. (d) The dealuminated zeolite-Y was then dispersed into active matrix prepared by the process of the present invention. Silica-alumina gel and peptized alumina constituted the active matrix. The silica-alumina matrix prepared by the method of the present invention is catalytically active and has maximum protonic acidity at silica-alumina ratio of 80:20. This increases the catalytic activity of matrix and over all Bronsted/Lewis acidity ratio required for better coke selectivity i.e., lower yield of coke. The fresh catalyst prepared was deactivated by hydrothermal treatment. To have a meaningful purpose for the performance evaluation of FCC catalysts, these are hydrothermally deactivated. This is important because the activity of fresh catalyst is an inadequate measure of its performance. In a commercial cracking unit during operation the catalyst is deactivated by thermal and hydrothermal degradation. The determination of activity level of a catalyst is more meaningful if the fresh catalyst is artificially deactivated by hydrothermal treatment at high temperature in the presence of steam. Hydrothermal deactivation of catalysts was done at predetermined conditions of temperature, duration and steam partial pressure. Hydrothermally deactivated catalyst samples were subjected to detailed evaluation of catalytic activity and product selectivities in Micro Activity Test (MAT) unit at predetermined conditions of temperature, duration of reaction, cat/oil ratio, etc. The invention may be practised as illustrated in the following examples, which sould not be construed to limit the scope of the present invention. Example-1 This example describes a process for the preparation of FCC catalyst using 20% dealuminated zeolite-Y. In a typical procedure, sodium silicate solution was diluted to have 5% silica. To this solution, 6 N sulfuric acid was added till the PH of the gel fell down to 6.5. The gel was aged for 24 hours at 40-50 C and then calculated amount of aluminium sulphate was added to it to have a silica-alumina ratio of 80:20. The mixture was aged for 4 hours and the PH raised to 8.5 by the addition of 10% sodium hydroxide solution. The precipitated gel was aged at 40-50 C for 18 hours before other constituents of the catalysts were added to it. Kaolin clay was treated with N/10 hydrochloric acid at room temperature. The treated clay was washed free of chloride ion and then dried at 110 C. Disperal alumina hydrate was peptized by adding 1.0 ml acetic acid to 100 g alumina hydrate. 40 g silica alumina gel prepared above was taken and to it was added the slurry of 30 g of 20% dealuminated zeolite-Y. The mixture of silica alumina gel and zeolite was thoroughly stirred and then a slurry of 20g of modified Kaolin in water was added to it. The mixture was again stirred. Finally lOg of peptized alumina was mixed with it. The whole mass was vigorously stirred. The PH of the mixture was 5.5. This was raised to 6.5 by addition of sodium hydroxide solution. The slurry was aged for 2 hours at room temperature and then dried at 110 C for 16 hours. The dried mass was first washed with warm water by decantation. Water was then replaced by ammonium nitrate solution. Washing was continued till the sodium content in the water fell down 0.5 ppm. The catalyst was finally washed with water before drying at 110 C for 16 hours. The dried catalyst was calcined at 350 C for 2 hours. This was then exchanged at 85 Cfor 2 hours using Lanthanum nitrate solution. The concentration of the solution (2-2.5g/100ml water) was so chosen that not more than 3 wt% of Lanthanum would be exchanged. The exchanged mass was filtered, washed and dried at 110 C. Analysis showed that it did not contain more than 3 wt% Lanthanum. The rare earth exchanged catalyst was calcined at 500 C for 2 hours. It was then sieved to get 100-200 mesh size particles. This catalyst was designated as FCZ-1. Example-2 This example describes' a process for the preparation of FCC catalysts using 50% dealuminated zeolite-Y. In a typical procedure, sodium silicate solution was diluted to have 5% silica. To this solution, 6 N sulfuric acid was added till the PH of the gel fell down to 6.5. The gel was aged for 24 hours at o 40-50 C and then calculated amount of aluminium sulphate was added to it to have a silica-alumina ratio of 80:20. The mixture was aged for 4 hours and the PH raised to 8.5 by the addition of 10% sodium hydroxide solution. The precipitated gel was aged at 40-50 C for 18 hours before other constituents of the catalysts were added to it. Kaolin clay was treated with N/10 hydrochloric acid at room temperature. The treated clay was washed free of chloride ion and then dried at 110 C. Disperal alumina hydrate was peptized by adding 1.0 ml acetic acid to 100 g alumina hydrate. 40 g silica alumina gel prepared above was taken and to it was added the slurry of 30 g of 50% dealuminated zeolite-Y. The mixture of silica alumina gel and zeolite was thoroughly stirred and then a slurry of 20g of modified Kaolin in water was added to it. The mixture was again stirred. Finally lOg of peptized alumina was mixed with it. The whole mass was vigorously stirred. The PH of the mixture was 5.5. This was raised to 6.5 by addition of sodium hydroxide solution. The slurry was aged for 2 hours at room temperature and then dried at 110 C for 16 hours. The dried mass was first washed with warm water by decantation. Water was then replaced by ammonium nitrate solution. Washing was continued till the sodium content in the water fell down 0.5 ppm. The catalyst was finally washed with water before drying at 110 C for 16 hours. The dried catalyst was calcined at 350 C for 2 hours. This o was then exchanged at 85 Cfor 2 hours using Lanthanum nitrate solution. The concentration of the solution (2-2.5g/100ml water) was so chosen that not more than 3 wt% of Lanthanum would be exchanged. The exchanged mass was filtered, washed and dried at 110 C, Analysis showed that it did not contain more than 3 wt% Lanthanum. The rare earth exchanged catalyst was calcined at 500 C for 2 hours. It was then sieved to get 100-200 mesh size particles. This catalyst was designated as FCZ-2. Example-3 This example describes a process for the preparation of FCC catalyst using 60% dealuminated zeolite-Y. In a typical procedure, sodium silicate solution was diluted to have 5% silica. To this solution, 6 N sulfuric acid was added till the PH of the gel fell down to 6.5. The gel was aged for 24 hours at ft 40-50 C and then calculated amount of aluminium sulphate was added to it to have a silica-alumina ratio of 80:20. The mixturo uas aged lor 4 hours and the PH raised to 8.5 by the addition of 10% sodium hydroxide solution. The precipitated gel was aged at 40-50 C for 18 hours before other constituents of the catalysts were added to it. Kaolin clay was treated with N/10 hydrochloric acid at room temperature. The treated clay was washed free of chloride ion and then dried at 110 C. Disperal alumina hydrate was peptized by adding 1.0 ml acetic acid to 100 g alumina hydrate. 40 g silica alumina gel prepared above was taken and to it was added the slurry of 30 g of 60% dealuminated zeolite-Y. The mixture of silica alumina gel and zeolite was thoroughly stirred and then a slurry of 20g of modified Kaolin in water was added to it. The mixture was again stirred. Finally lOg of peptized alumina was mixed with it. The whole mass was vigorously stirred. The PH of the mixture was 5.5. This was raised to 6.5 by addition of sodium hydroxide solution. The slurry was aged for 2 hours at room temperature and then dried at 110 C for 16 hours. The dried mass was first washed with warm water by decantation. Water was then replaced by ammonium nitrate solution. Washing was continued till the sodium content in the water fell down 0.5 ppm. The catalyst was finally washed with water before drying at 110 C for 16 hours. The dried catalyst was calcined at 350 C for 2 hours. This was then exchanged at 85 Cfor 2 hours using Lanthanum nitrate solution. The concentration of the solution (2-2.5g/100ml water) was so chosen that not more than 3 wt% of Lanthanum would be exchanged. The exchanged mass was filtered, washed and dried at 110 C. Analysis showed that it did not contain more than 3 wt% Lanthanum. The rare earth exchanged catalyst was calcined at 500 C for 2 hours. It was then sieved to get 100-200 mesh size particles. This catalyst was designated as FCZ-3. Example-4 This example describes a process for the preparation of FCC catalyst using 75% dealuminated zeolite-Y after acid extraction of non frame work aluminium (NFAL) removed during dealumination. 30 gms zeolite slurried in 85 ml 1.0 NHCl was refluxed for 30 minutes, filtered and washed free of chloride ions with demineralized water and dried at HOoC for 16 hours. In a typical procedure, sodium silicate solution was diluted to have 5% silica. To this solution, 6 N sulfuric acid was added till the PH of the gel fell down to 6.5. The gel was aged for 24 hours at 40-50 C and then calculated amount of aluminium sulphate was added to it to have a silica-alumina ratio of 80:20. The mixture was aged for 4 hours and the PH raised to 8.5 by the addition of 10% sodium hydroxide solution. The precipitated gel was aged at 40-50 C for 18 hours before other constituents of the catalysts were added to it. Kaolin clay was treated with N/10 hydrochloric acid at room temperature. The treated clay was o washed free of chloride ion and then dried at 110 C. Disperal alumina hydrate was peptized by adding 1.0 ml acetic acid to 100 g alumina hydrate. 40 g silica alumina gel prepared above was taken and to it was added the slurry "of 30 g of 75% dealuroinated zeolite-Y. The mixture of silica alumina gel and zeolite was thoroughly stirred and then a slurry of 20g of modified Kaolin in water was added to it. The mixture was again stirred. Finally lOg of peptized alumina was mixed with it. The whole mass was vigorously stirred. The PH of the mixture was 5.5. This was raised to 6.5 by addition of sodium hydroxide solution. The slurry was aged for 2 hours at room temperature and then dried at 110 C for 16 hours. The dried mass was first washed with warm water by decantation. Water was then replaced by ammonium nitrate solution. Washing was continued till the sodium content in the water fell down 0.5 ppm. The catalyst was finally washed with water before drying at 110 C for 16 hours. The dried catalyst was calcined at 350 C for 2 hours. This was then exchanged at 85 Cfor 2 hours using Lanthanum nitrate solution. The concentration of the solution (2-2.5g/100ml water) was so chosen that not more than 3 wt% of Lanthanum would be exchanged. The exchanged mass was filtered, washed and dried at o 110 C. Analysis showed that it did not contain more than 3 wt% Lanthanum. o The rare earth exchanged catalyst was calcined at 500 C for 2 hours. It was then sieved to get 100-200 mesh size particles. This catalyst was designated as FCZ-4. Example-5 This example describes a process for the preparation of FCC catalyst using 80% dealuminated zeolite-Y after acid extraction of non frame work aluminium (NFAL) removed during dealumination. 30 gms zeolite slurried in 85 ml 1.0 NHCl was refluxed for 30 minutes, filtered and washed free of chloride ions with demineralized water and dried at HOoC for 16 hours. In a typical procedure, sodium silicate solution was diluted to have 5% silica. To this solution, 6 N sulfuric acid was added till the PH of the gel fell down to 6.5. The gel was aged for 24 hours at 40-50 C and then calculated amount of aluminium sulphate was added to it to have a silica-alumina ratio of 80:20. The mixture was aged for 4 hours and the PH raised to 8.5 by the addition of 10% sodium hydroxide solution. The precipitated gel was aged at 40-50 C for 18 hours before other constituents of the catalysts were added to it. Kaolin clay was treated with N/10 hydrochloric acid at room temperature. The treated clay was washed free of chloride ion and then dried at 110 C. Disperal alumina hydrate was peptized by adding 1.0 ml acetic acid to 100 g alumina hydrate. 40 g silica alumina gel prepared above was taken and to it was added the slurry of 30 g of 80% dealuminated zeolite-Y. The mixture of silica alumina gel and zeolite was thoroughly stirred and then a slurry of 20g of modified Kaolin in water was added to it. The mixture was again stirred. Finally lOg of peptized alumina was mixed with it. The whole mass was vigorously stirred. The PH of the mixture was 5.5. This was raised to 8.5 Example-7 This example illustrate the catalytic activities and product selectivities of FCC catalysts prepared by the procedure of the present invention described in example 1 to 5. The deactivated catalyst was subjected to evalution of the activities and product selectivities. 1.33 g of gas oil from a syringe is injected to 4 g of catalyst in a fixed bed quartz reactor at 482 over a period of 75 sees. The gas samples collected during the reaction is analysed by GC and the liquid prduct is analysed in a simulated distillation unit. Coke yield is calculated by measuring the carbon by carbon analyser. From the above data activity of the catalyst is calculated as percent fraction converted to 216 C boiling range product and selectivities to the other products. The reaction conditions used in the study aro as under : Temperature : 475-495 C Time : 75 Sees. Catalyst/oil/g/g : 3.0 Table-4 Catalytic Activity and Product Selectivities of FCC Catalysts (Table Remobved) by addition of sodium hydroxide solution. The slurry was aged for 2 hours at room temperature and then dried at 110 C for 16 hours. The dried mass was first washed with warm water by decantation. Water was then replaced by ammonium nitrato. solution. Washing was continued till the sodium content in the water fell down 0.5 ppm. The catalyst was finally washed with water before drying at 110 C for 16 hours. The dried catalyst was calcined at 350 C for 2 hours. This was then exchanged at 85 Cfor 2 hours using Lanthanum nitrate solution. The concentration of the solution (2-2.5g/100ml water) was so chosen that not more than 3 wt% of Lanthanum would be exchanged. The exchanged mass was filtered, washed and dried at 110 C. Analysis showed that it did not contain more than 3 wt% Lanthanum. The rare earth exchanged catalyst was calcined at 500 C for 2 hours. It was then sieved to get 100-200 mesh size particles. This catalyst was designated as FCZ-5. Example-6 The catalyst prepared by the process described in Examples 1-5 were hydrothermally deactivated in presence of 100% steam at the conditions given below : Temperature : 786-790 C Duration : 3-5 hours The detailed results presented in the table shows that substantially higher yield of middle distillate (total cycle oil (TCO) in the range of 37.02 to 48.12%, lower coke in the range of 1.34 to 1.95% and bottoms ytield in the range of 2.97 to 21.36% at the conversion level of 41.40 to 66.2%. We claim : 1. A process for the preparation of fluid catalytic cracking (FCC) catalyst, which comprises: a) preparing NH4Y Zeolite with aqueous solution of ammonium salt by known methods to achieve silica alumina ratio of 80:20 having concentration range of 1 to 3N at a temperature in the range of 70-100°C to obtain NH4Y Zeolite, b) heating the above said NH4Y Zeolite at a temperature of 380-820°C for a period in the range of 0.1 to 12 hrs. in presence of steam to obtain dealuminated Zeolite Y, c) treating the dealuminated Zeolite Y with mineral acid with concentration range of 0.1 to6N, d) dispersing the 30% dealuminated Zeolite Y into 40% active silica alumina matrix having silica alumina ratio of 80:20 to obtain dispersed dealuminated Zeolite Y, e) stirring the above said dispersed dealuminated Zeolite Y mixture and adding 20% of Kaolin, f) adding 10% of peptized alumina hydrate at a pH range between 6-7.5, g) filtering, washing, drying & calcining at temperature ranging 400 to 600°C to obtain catalyst, h) treating the catalyst obtained with a salt of lanthanum solution having 2-3 wt% lanthanum & drying the rare earth exchanged catalyst for 2-4 hrs at a temperature of 80 to 150°C, i) calcining the catalyst at temperature 400-600°C for 2 to 3 hrs. & sieving to obtain 100-200 mesh size particle catalyst. 2. A process as claimed in claim 1 wherein the said salt is selected from ammonium chloride, sulphate or nitrate preferably ammonium nitrate. 3. A process for the preparation of fluid catalytic cracking (FCC) catalyst substantially as herein described with reference to the examples.

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2625-del-1996-abstract.pdf

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2625-del-1996-complete specification (granded).pdf

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