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Value Added Spent Fluid Catalytic Cracking Catalyst Composition And A Process For Preparation Thereof

Abstract: A composition of a value added RFCC catalyst and a process of preparation of a composition for a dual function additive catalyst from a spent catalyst are disclosed. The value added spent FCC catalyst offers improved performance, options such as either employing as an additive for passivation of both vanadium and nickel and enhancing catalytic activity, for initial start-up or make-up for attrition losses. The value addition process does not harm any of physical properties of starting material with respect to ABD, attrition index, surface area and particle size distribution. Value added catalyst can be used in a range from 1-99 wt% in fluid catalytic cracking process in which, feeds may have higher metals and carbon.

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Patent Information

Application #
Filing Date
08 July 2010
Publication Number
43/2014
Publication Type
INA
Invention Field
CHEMICAL
Status
Email
Parent Application
Patent Number
Legal Status
Grant Date
2017-05-08
Renewal Date

Applicants

INDIAN OIL CORPORATION LTD.
INDIAN OIL BHAVAN, 2, GARIAHAT ROAD (SOUTH), DHAKURIA, KOLKATA - 700068, WEST BENGAL

Inventors

1. MOHAN PRABHU K
INDIAN OIL CORPORATION LTD, RESEARCH & DEVELOPMENT (R&D) CENTRE, SECTOR-13, FARIDABAD-121007, HARYANA
2. AV KARTHIKEYANI
INDIAN OIL CORPORATION LTD, RESEARCH & DEVELOPMENT (R&D) CENTRE, SECTOR-13, FARIDABAD-121007, HARYANA
3. MANISH AGARWAL
INDIAN OIL CORPORATION LTD, RESEARCH & DEVELOPMENT (R&D) CENTRE, SECTOR-13, FARIDABAD-121007, HARYANA
4. BISWANATH SARKAR
INDIAN OIL CORPORATION LTD, RESEARCH & DEVELOPMENT (R&D) CENTRE, SECTOR-13, FARIDABAD-121007, HARYANA
5. BALAIAH SWAMY
INDIAN OIL CORPORATION LTD, RESEARCH & DEVELOPMENT (R&D) CENTRE, SECTOR-13, FARIDABAD-121007, HARYANA
6. V CHIDAMBARAM
INDIAN OIL CORPORATION LTD, RESEARCH & DEVELOPMENT (R&D) CENTRE, SECTOR-13, FARIDABAD-121007, HARYANA
7. PS CHOUDHURY
INDIAN OIL CORPORATION LTD, RESEARCH & DEVELOPMENT (R&D) CENTRE, SECTOR-13, FARIDABAD-121007, HARYANA
8. S RAJAGOPAL
INDIAN OIL CORPORATION LTD, RESEARCH & DEVELOPMENT (R&D) CENTRE, SECTOR-13, FARIDABAD-121007, HARYANA

Specification

FIELD OF INVENTION
[001] The present invention relates to a value added spent Fluid Catalytic Cracking
(FCC) catalyst composition from a low activity spent FCC catalyst. This invention also relates to a process for preparation thereof. The invention particularly relates to a value added FCC catalyst composition from spent FCC catalyst offering dual functions of simultaneous passivation of metals and also for enhancement of catalytic activity of host Resid Fluid Catalytic Cracking (RFCC) catalyst for processing heavy metal laden feeds in petroleum processing industry. This invention also relates to various value addition processes of spent FCC catalyst.
BACKGROUND OF THE INVENTION
[002] The present invention relates to Fluid Catalytic Cracking (FCC) catalysts and the
process for preparation wherein the value added FCC catalyst composition offering dual functions of simultaneous passivation of metals and also for enhancement of catalytic activity of host Resid Fluid Catalytic Cracking (RFCC) catalyst for processing heavy metal laden feeds in petroleum processing industry. This invention also relates to various value addition processes of spent FCC catalyst.
[003] Fluid Catalytic Cracking (FCC) catalysts used today in cracking process are not
so cost effective hence increasing cost of crude is forcing refineries to process the hydrocarbon feeds having high carbon residue, nitrogen, aromatics and heavy metal contaminants such as nickel and vanadium to be efficiently used in the refinery industry. Among all the contaminants present in feeds, metal contaminants pose the greatest challenge, as some of them permanently cripple the catalytic activity while some metals produce undesired products such as coke and dry gas. Nickel is well known for dehydrogenation of feed and products under normal FCC operation conditions thereby producing higher coke and dry gas. These effects are predominant with catalysts having higher surface area. Vanadium, unlike nickel, is known for zeolite destroying property and for even worse effects by hopping from aged catalyst particle to fresh catalyst particle while carrying out the destructive action. Vanadium pentoxide, formed during severe regeneration operation, gets converted to vanadic acid which reacts with structural alumina of zeolite and also with structure supporting rate earth species. Presence of vanadium in the feed

can permanently reduce activity of the FCC catalyst. Processing such feeds create increasing demand for catalysts having higher metal tolerance. Such a process which processes heavy feeds sourced from streams such as inter oil, heavy oil, deashphatted oil, short residue, heavy gas oil, coker gasoil having nickel in the range 8-50 ppm and vanadium in the range 15-120 ppm while employing high matrix metal tolerant catalysts is known as Resid Fluid Catalytic Cracking (RFCC). Spent catalysts in these processes, accumulate total metals in the range 1-3 wt%. As discussed earlier, nickel and vanadium are the most prominent among all the metals requiring remedy for their undesired properties. Besides, as the catalyst produces higher coke while processing resid feeds, for withstanding higher temperature of catalyst regeneraiion process, hardware needs to have improved metallurgy. Catalysts employed for RFCC operations need to be robust towards high temperature regeneraiion, steam stripping and metal environment under the dynamic conditions of RFCC operation. Due to higher rate of catalyst deactivation in presence of metals and operational severity, catalyst make-up rate is higher in case of RFCC, which is in the range 4-15 wt% of inventory against 0.4-5 wt% in case of FCC. It may be noted, due to lower deactivaiion rate and having lower metals in spent FCC catalysts, there is a significant activity left in such spent catalysts and used for initial start-up or for make-up in RFCC/FCC units.
[004] Catalyst manufacturers, often produce less robust catalysts which are cheaper and
produced from normal NH4Y zeolite and conventional binders. Such catalysts on withdrawal
from the plant cannot be re-employed for start-up or for make-up in case of RFCC units. On the
contrary, RFCC catalysts are produced from thermally stable high silica-alumina USY zeolites
and employing componenss desired for high temperature operation, enhancing metal stability etc.
Inference can be drawn; catalysts employed for VGO/soft feed processing may not be suitable
for RFCC operation. RFCC operation, besides employing high active thermally stable catalysts
may additionally use metal passivator additives. Though, it is desirable to reuse spent or E-
catalyst from FCC for RFCC start-up or for make-up in view of improving the economy of
process, often due to requirement of higher metal and thermal stability, spent catalysts could not
be exploited for RFCC. The present invention describes a process and composition for the
preparation of RFCC catalyst from spent FCC catalyst for further use in RFCC.
[005] US Patent No. 5,520,797 and US Patent No. 4,359,379 describe processes for the
fluid catalytic cracking of heavy oils rich in Ni and V by withdrawing a portion of ferrite-

containing catalyst particles circulating In a fluid catalytic cracking apparatus, by using a magnetic separator.
[006] US Patent No. 5,188,995 refers to a process in which spent metal-contaminated
zeolite-containing catalytic cracking catalyst is reactivated by a process which comprises
contacting the spent catalyst with at least one dissolved carboxylic acid and at least one antimony
compound. This invention more particularly describes a method of reactivating spent, metal-
contaminated zeolite-containing catalytic cracking catalysts. In another aspect, this invention
relates to a catalytic cracking process employing a reactivated spent catalytic cracking catalyst.
[007] US Patent No. 5,151,391 refers to a process in which, spent metal contaminated
zeolite-containing catalytic cracking catalyst composition is reactivated by a process which comprises contacting with an aqueous solution of HCI and/or HN03 and/or H2S04. Thus reactivated catalyst composition can be employed in a catalytic cracking. Further this invention relates to a method of reactivating spent, metal-contaminated zeolite-containing catalytic cracking catalysts. In another aspect, this invention relates to a catalytic cracking process employing a reactivated spent catalytic cracking catalyst.
[008] US Patent No. 5,888,919 refers to a process in which a spent zeolite-containing
hydrocarbon cracking catalyst is treated by regenerating it to remove carbonaceous deposits. A portion of the regenerated catalyst is withdrawn from the circulating catalyst inventory of a hydrocarbon processing unit and slurried with a liquid containing an activating agent. This invention relates to process for improving the activity of fluid catalytic cracking (FCC) or moving bed cracking (TCC) catalyst, including any additives containing zeolitic material as one of the active components and which may be employed with each type catalyst, which process can be integrated with the operations of the hydrocarbon processing unit in which the catalyst is employed.
[009] US Patent No. 4,919,787 refers to a process for an improved method for
passivating metals in a hydrocarbon feedstock during catalytic cracking. Further this invention involves contacting the feedstock with a passivating agent comprising a precipitated porous rare earth oxide, alumina, and aluminum phosphate precipitate. The passivating agent may be coated on a cracking catalyst, be part of the matrix of a cracking catalyst, or be added to the cracking operation as discrete particles.

[010] Patent number EP73874B1 discloses Immobilisation of vanadia deposited on
catalytic materials during the conversion of oil that contains coke precursoss and heavy metals. US application 20100025297Al discloses additives for metal contaminant removal, catalytic cracking additives comprising a metal trapping materia;; and a high activity catalyst. This invention is directed to processes for the catalytic cracking of feedstock comprising contacting said feedstock under catalytic cracking conditions with a composition comprising a bulk catalyst and a catalytic cracking additive, wherein the catalytic cracking additive comprises a metal trapping material; and a high activity catalyst.
[011] Therefore, there is a need to provide an improved process and a catalyst
composition for converting low activity, low metal tolerant spent FCC catalyst to an efficient
catalyst composition to be used in RFCC process for enhancing metal tolerance and also for
enhancing catalytic activity of host catalyst for a more efficient and cost effective method.
[012] The present invention is aimed at avoiding or overcoming the difficulties or
limitations encountered to provide an improved process and a catalyst composition for catalytic cracking of heavy oils in petroleum processing industry.
[013] It will be advantageous to have a composition and an efficient process to prepare
the composition for employing low activity, low metal tolerant spent FCC catalyst for further use
in RFCC in enhancing metal tolerance and also in enhancing catalytic activity of host catalyst.
[014] It will be advantageous to have a product from spent catalyst, which will enhance
the catalytic activity and selectivity of spent catalysts in adverseRFCC operation conditions.
[015] It will also be advantageous to have an efficient process and a product from spent
catalyst, which will enhance the catalytic activity and selectivity of spent catalysts in adverse RFCC operation conditions.
[016] Furthermore, a product and process for improving thermal and metal stability of
spent catalyst through impregnaiion with metal passivation composition, while this value added
spent catalyst can be employed as an additive in RFCC process will be beneficial.
[017] Still further, a process for the preparation of a thermal and metal stable RFCC
catalyst from spent catalyst for processing metal laden heavy feeds will be advantageou..
[018] It will be also advantageous to have a process, by which application of metal
passivation composition on spent catalyst, enhances crystallintty and surface area of a host catalyst.

[019] Process and composition for preparation of a thermal and metal tolerant catalyst
from spent FCC catalyst which can be employed in RFCC process as an additive or as a whole
metal tolerant RFCC catalyst will be beneficial.
[020] The present invention is aimed to provide an efficient process and a composition
for employing low activity, low metal tolerant spent FCC catalyst for further use in RFCC in
enhancing metal tolerance and also in enhancing catalytic activity of host catalyst.
[021] It is another advantage of the invention to provide an efficient process and a
product from spent catalyst, which will enhance the catalytic activity and selectivity of spent
catalysts in adverse RFCC operation conditions.
[022] It is yet another advantage of the invention to provide a process for improving
thermal and metal stability of spent catalyst through impregnation with metal passivation
composition, while this value added spent catalyst can be employed as an additive in RFCC
process.
[023] It is still another advantage of the invention to develop a process for the
preparation of a thermal and metal stable RFCC catalyst from spent catalyst for processing metal
laden heavy feeds.
[024] It is yet another advantage of the invention to provide a process, by which
application of metal passivation composition on spent catalyst, enhances crystallinity and surface
area of a host catalyst.
[025] It is yet further advantage of the invention to develop a process and composition
for preparation of a thermal and metal tolerant catalyst from spent FCC catalyst which can be
employed in RFCC process as an additive or as a whole metal tolerant RFCC catalyst.
DETAILED DESCRIPTION OF THE INVENTION
[026] According to the invention there is provided a value added spent Fluid Catalytic
Cracking (FCC) catalyst composition comprising spent FCC catalyst introduced thereto a substance (activity enhancer) selected from either a rare earth component or an aluminium component or a mixture/combination of the two. The meaning of value addition includes addition of property to the spent FCC catalyst providing dual function for simultaneous passivation of metals and also for enhancing catalytic activity of host Resid Fluid Catalytic

Cracking (RFCC) catalyst for processing heavy metal laden feeds in petroleum processing industry. The value addition further m~ans enhancement of thermal and metal tolerance/stability. The value addition also means enhanced catalytic activity and selectivity of spent catalyst in adverse RFCC operation conditions. The value addition further means enhanced crystallintty and surface area of a host catalyst.
[027] According to this invention there is also provided a process for preparing the said
value added fluid catalytic cracking catalyst which comprises introducing a rare earth and/or an aluminium containing substance to spent FCC catalyst. The rare earth and/or aluminium containing substance is/are used here as an activity enhancer. The rare earth substance can be selected from one or more rare earth metal compounds preferably Lanthanum compounds. Broadly the rare earth compounds can be selected from the sources of oxides, hydroxides, chlorides, nitrates, sulphates, oxalates, carbonates, acetates, formates and hydrates but free from soda. The preferred compound is oxide. The. most preferred compound is Lanthanum rich compound, which leaves minimum anionic residue on process step of high temperature calcination. The aluminium component according to this invention is one or more compounds of aluminium and is selected from aluminium oxide, hydroxide, chloride, nitrate, sulphate, acetate, oxalate, hydroxychloride, hydroxyl nitrate, hydroxyl sulphate and hydrate but free from soda. The preferred compound of aluminum should be capable of leaving least anionic residue on process step of high temperature calcination. The starting spent FCC catalyst has aluminium in the range of 20-55 wt%, silica 20-60 wt%, sodium oxide less than 0.5 wt%, vanadium 200-2000 ppm, nickel 100-1500 ppm and rare earth oxide 0.5-3 wt%. The starting spent FCC catalyst has a surface area of501700 m2 /gm, particle size of201200 microns and apparent bulk density of 0.70-0.90 gm/ml. The value added catalyst of the invention has an apparent bulk density of 0.70-0.98 gm/ml and an attrition index of 0.1-10. The proportion of the activity enhancer introduced to the spent catalyst is such that the obtained value added catalyst has aluminium in the range of 20-60 wt%, silica 20-50 wt%, sodium oxide less than 0.5 wt%, titanium oxide less than 0.5 wt%, vanadium 200-2000 ppm, nickel 100-1500 ppm and rare earth oxide 1-13.5 wt%. The value added catalyst of the invention can be employed as an additive to host RFCC catalyst or as a whole metal tolerant RFCC catalyst. The rare earth and/or aluminium compound as activity enhancer can be loaded in 0.5-10 wt% of spent catalyst on oxide basis. The spent catalyst after

loading with activity enhancer can be used in RFCC process as a dual function additive for both
metal passivation and activity enhancemen,, quantity ranging from 1-99 wt%.
The introduction of the activity enhancer is carried out by wet impregnaiion, ion-exchange or
feeding along with hydrocarbon feed in actual plant operation.
[028] In one embodiment the process for preparing dual function catalyst additive from
spent FCC catalyst comprises the following sequence of steps:
a) Preparing a rare earth and/or aluminium containing solution,
b) Wet impregnaiing spent FCC catalyst with a solution of step (a)
c) Oven drying wet impregnated spent catalyst of step (b) and
d) Calcination of oven dried product of step (c)
[029] In another embodiment the invention provides a process for catalytic cracking of
hydrocarbons to provide higher conversion, naphtha yield and lower bottoms by using the value
added spent catalyst. In yet another embodiment there is provided a process for improving
thermal and metal stability of spent FCC catalyst comprising treating the spent FCC catalyst with
the activity enhancer selected from either rare earth or an aluminium component or a
mixture/combination of the two. In still another embodimen,, the invention deals with the
process of catalytic cracking of hydrocarbons wherein the value added spent catalyst is added to
a host cracking catalyst in a proportion ranging from 1-99 wt% during the catalytic cracking of
hydrocarbons containing vanadium and nickel as undesirable constituenss and for preventing the
adverse effects of vanadium and nickel on the activity of the host cracking catalyst. In yet
another embodiment of the invention there is provided a process for enhancing the catalytic
activity and selectivity of spent FCC catalyst in adverse RFCC conditions comprising treating
spent FCC catalyst with the activity enhancer as described above. In still another embodiment
there is provided a process which enhances the crystallintty and surface area of a host FCC
catalyst by applying the activity enhancer as stated above. Componenss of the catalyst with their
specific embodimenss are further described on component by component basis.
[030] Spent Catalyst - Fresh FCC/RFCC catalysts are produced from shape selective
zeolite material either in ammonia or in rare earth form content ranging from 20-45 wt%. These zeolites are bonded by either silica or alumina or by silica-alumina composite, while clay is used as a diluent/heat sink/low cost filler. Fresh catalysts generally possess very high microactivity (vacuum gas oil conversion) and have surface area in the range 180-300 m2/gm and Y-zeolite

crystallinity above 20% while unit cell size (UCS) above 24.40°A. As these catalysts pass through high temperature and steam zones in FCC/RFCC unit, thereby undergo severe degradation during initial few hours dwell in the unit. Degradation is in terms of surface area, crystallinity and UCS. This is reflected in catalyst performance, where it steeply falls from over 70% to below 65%. After initial few hours steep fall in these parameters, further fall is gradual. During initial stage in the catalyst plant, the zeolite component present in the catalyst undergoes severe dealuminaiion, while silica from matrix keeps healing those vacancies. A stage will be reached where, there is an equilibrium. Such a catalyst is named as equilibrium catalyst (E-catalyst) and will have more or less stable activity. Further, dwell of E-catalyst in the plant, will cause gradual degradation on activity and a stage will be reached where further continuation of catalyst will offset economic benefits over fresh catalyst performanc.. At this time, considerable amount of catalyst is withdrawn from the plant and substituted with fresh catalyst. Such a catalyst is known as spent catalyst and will have surface area in the range 50-170 m2/gm, while Y zeolite crystallintty is in the range 7-15%. Spent catalyst may have metals such as vanadium in the range 200-2000 ppm and nickel from 100-1500 ppm in caseoV VGO (FCC) operation. These metal levels are much higher in case of RFCC units in the range 5000-15000 ppm vanadium and 2000-7000 ppm nickel. The crystallintty and surface area of spent catalyst samples is lower compared to FCC catalysts due to higher operational severity and higher deactivation due to metals.
[031] Activity Enhancer - Oxides of alumina and rare earth have been found to be very
effective in enhancing the activity of spent catalyst products. These can be introduced to spent catalyst by wet impregnaiion, ion-exchang,, feeding along with hydrocarbon feed in actual plant operation. Salts of lanthanum, aluminium such as chlorides, sulphates, nitrates, acetates, oxalates can be employed for wet impregnaiion or ion-exchange. Besides, their respective hydroxide can also be employed. These elements need to be introduced in an optimum range as per requirement in the range 0.5 to 10 wt%, on oxide basis. Following the introduction of activity enhancer, spent catalyst can be used in RFCC process in the range 1 to 99 wt% as a dual function additive.

EXAMPLES
[032] The present invention is further explained in the form of following examples.
However, these examples should not be construed as limiting the scope of the invention.
Example 1
[033] This example illustrates effect of steaming on surface area and X-ray crystallinity
on spent FCC catalyst, drawn from FCC unit employed for cracking of light gasoil, when steamed at 750aC, for 1 hour in presence of 100% steam. It is found surface area of spent FCC catalyst reduced from 156 m2/gm to 134 m2/gm upon steaming. Similarly, X-ray crystallinity also dropped from 8.4% to 6.5%.
Example 2
[034] This example shows effect of steaming on metal loaded spent catalyst.
For this, spent FCC catalyst was doped with 10500 ppm of vanadium and 4000 ppm of nickel employing Mitchell method (Julius Scherzer-I) following which, steamed at 750aC, for 3 hours in presence of 100% steam. It is found surface area of metal impregnated steamed spent catalyst reduced to 57 m2/gm. Similarly, X-ray crystallinity also dropped from 8.4% to 4%.
Example 3
[035] This example illustrates a procedure for enhancing steam and metal stability of
spent FCC catalyst. Spent FCC catalyst, referred in example 1 was calcined at 500aC for 1 hour and cooled in a desiccator. 300 gm of calcined spent catalyst was divided into 3 equal parts and subjected to wet impregnation with required concentration of rare earth nitrate solution (minimum of 85 wt% La203, maximum 2 wt% Pr6011, maximum 5 wt% Nd203, maximum 1 wt% Ce203 and non-rare earth impurities such as Fe203, CaO, MgO, Ti02 maximum up to 1.5 wt% represented on volatile free basis) to give final dry catalyst having 2 wt%, 4 wt%, 6 wt% rare earth oxide on volatile free basis. Thus prepared catalysts were oven dried at 120aC for 12 hours and calcined to 500°C for1 hour.

Example 4
[036] This example offers a procedure for enhancing steam and metal stability of spent
catalyst, employing lanthanum acetate of purity 99% as a rare earth source, replacing rare earth nitrate under example 3. Spent catalyst was wet impregnated to give 6 wt% of La203 on volatile free basis from a required quantity and concentrated solution of lanthanum acetate.
Example 5
[037] This example offers a procedure for enhancing steam and metal stability of spent
catalyst, employing aluminum nitrate of purity 99% as an aluminum source in place of lanthanum under example 3. Spent catalyst was wet impregnated to give 6 wt% of A1203 on volatile free basis from a required quantity and concentrated solution of aluminum nitrate.
Exampee 6
[038] This example refers to the performance of value added spent catalysts prepared
under examples 3, 4 and 5. To a fresh RFCC catalyst having crystallintty 25%, surface area 300 m2/gm, 10 wt% of value added spent catalysts prepared under example 3, 4 and 5 were blended in independent experiments, while one reference catalyst was prepared by blending 10 wt% of spent catalyst, employed as starting materia.. All of seven blends were doped with 10500 ppm of vanadium and 4000 ppm of nickel employing respective vanadium and nickel metals naphthenates. For this well established Mitchell method was employed. All the seven blends were oven dried at 120°C for 3 hours and calcined at 500°C for 1 hour followed by steaming at 750°C for 3 hours under 100% steam. Fresh and steamed composites were characterized for surface area, X-ray crystallinity and composition. The physico-chemical properties of fresh and steamed blends are shown in Table-1. Performance evaluation of reference and value added blend catalyst was carried in an ACE MAT unit employing standard procedure and feed. The feed properties are shown in Table-2. Performance data comparison is shown in Table-3.

[039] Table 1. Physico-chemical properiies of spent catalyst and blend of value added catalyst in fresh catalyst


[040] Table 2. Properties of RFCC Feed used for Testing Performance of value added spent catalyst samples.


[041] Table 3: Performance of Steam Deactivated Catalyst Samples of Example 3,4 and 5

* : Base catalyst is fresh RFCC catalyst with 300m2/g surface area, crystallinity 25%.
[042] Reference:
Fluid Catalytic Cracking: Science and technology, Volume 76, J.S Magee, M.M Mitchell, jr
(Elesevier, 1993), Page-242.

WE CLAIM:
1. A value added spent fluid catalytic cracking (FCC) catalyst composition comprising spent FCC catalyst introduced thereto a substance (activity enhancer) selected from either a rare earth component or an aluminium component or a mixture Icombination of the two.
2. A composition as claimed in claim 1, wherein the substance is a rare earth compound.
3. A composition as claimed in claim 1, wherein the substance is an aluminium compound.
4. A composition as claimed in claim 1, wherein the substance is a mixture Icombination of both rare earth compound and an aluminium compound.
5. A composition as claimed in claims 1,2 and 4, wherein the rare earth compound is selected from one or more of rare earth compound..
6. A composition as claimed in claims 1, 2, 4 and 5, wherein the rare earth compound is selected as a Lanthanum compound.
7. A composition as claimed in claims 1, 2, 4 to 6, wherein the rare earth compound is selected from the sources of rare earth oxides, -hydroxide,, -chlorides, -nitrates, -su1phates, -oxalates, -carbonates, -acetates, -formates and -hydrates but free from soda.
8. A composition as claimed in claims 1,3 and 4, wherein the aluminium compound is selected from the sources of aluminium oxide, -hydroxide, -chloride, -nitrate, -sulphate, -acetate, -oxalate, -hydroxychloride, -hydroxyl nitrate, -hydroxyl sulphate and -hydrate but free from soda.
9. A composition as claimed in claim 7, wherein the rare earth compound is selected as oxide.

10. A composition as claimed in claim 8, wherein the aluminium compound is selected as oxide.
11. A composition as claimed in claim 1 and 4, wherein the rare earth and aluminium compounds are both used as oxides.
12. A composition as claimed in claims 1-11, wherein the substance (activity enhancer) introduced is in the range of 0.5-10 wt% on oxide basis.
13. A composition as claimed in claims 1-12, wherein the spent FCC catalyst has aluminium in the range of 20-55 wt%, silica 20-60 wt%, sodium oxide less than 0.5 wt%, vanadium 200-2000 ppm, nickel I00-1500 ppm and rare earth oxide 0.5 to 3 wt%.
14. A composition as claimed in claims 1-13, wherein the spent FCC catalyst has a surface area of 50-170m2/gm, particle size of 20-120 microns and apparent bulk density of 0.70-0.90 gm/ml.
15. A composition as claimed in claims 1-14 has an apparent bulk density of 0.70-0.98 gm/ml and an attrition index of 0.1-10.
16. A value added spent FCC catalyst composition as claimed in claims I-15, wherein the term "value" means property of dual function for simultaneous passivation of metals and also for enhancing catalytic activity of host resid fluid catalyst cracking (RFCC) catalyst for processing heavy metal laden feeds in petroleum processing industry.
17. A composition as claimed in claims 1-16 where the term "value" means property of enhanced thermal and metal tolerance/stability.
18. A composition as claimed in claims 1-17 where the term "value" means property of enhanced catalytic activity and selectivity of spent catalysts in adverse RFCC operation conditions.

19. A composition as claimed in claims 1-18 where the term "value" means enhanced crystallinity and surface area of a host catalyst.
20. A composition as claimed in any of claims 1-19, wherein the proportion of the substance (activity enhancer) introduced to the spent catalyst is such that the value added catalyst composition has aluminium in the range of 20-60 wt%, silica 20-50 wt%, sodium oxide less than 0.5 wt%, titanium oxide less than 0.5 wt%, vanadium 200-2000 ppm, nickel 100-1500 ppm and rare earth oxide 1-13.5 wt%.
21. A catalyst composition as claimed in claims 1-20 which is employable as an additive to host RFCC catalyst.
22. A catalyst composition as claimed in claims 1-20 which is employable as a whole metal tolerant RFCC catalyst.
23. A catalyst composition as claimed in claims 1-22 which is capable to be added to a host cracking catalyst in proportions ranging from 1-99 wt% during the catalytic cracking of hydrocarbons containing vanadium and nickel as undesirable constituents, and for preventing the adverse effects of vanadium and nickel on the activity of the host cracking catalyst.
24. A process for preparing a value added spent fluid catalytic cracking (FCC) catalyst composition comprising introducing a rare earth and/or an aluminium containing substance (activity enhancer) to spent FCC catalyst.
25. A process as claimed in claim 24, wherein a rare earth containing substance is introduced.
26. A process as claimed in claim 24, wherein an aluminium containing substance is introduced.

27. A process as claimed in claim 24, wherein a mixture or combination of both rare earth and aluminium containing substance is introduced.
28. A process as claimed in claims 24, 25 and 27, wherein the rare earth containing substance is selected from one or more of the sources of rare earth oxides, hydroxides, -chlorides, -nitrates, -sulphates, -oxalates, -carbonates, -acetates, -formates and hydrate but free from soda.
29. A process as claimed in claims 24, 25, 27 and 28, wherein the rare earth containing substance is a rare earth oxide.
30. A process as claimed in claims 24, 25, 27, 28 and 29, wherein the rare earth containing substance is Lanthanum oxide.
31. A process as claimed in claims 24, 26 and 27, wherein the amuminium containing substance is selected from one or more of aluminium oxide, -hydroxide, -sulphate, -chloride, -nitrate, -hydroxy chloride, -hydroxyl nitrate, -hydroxyl sulphate, -acetate, -oxalate and -hydrate but free from soda.
32. A process as claimed in claim 31, wherein the aluminium containing substance is aluminium oxide.
33. A process as claimed in claims 28 and 31, wherein rare earth and aluminium compounds selected are as their oxides.
34. A process as claimed in claims 24-33, wherein the spent FCC catalyst has aluminium in the range of 20-55 wt%, silica 20-60 wt%, sodium oxide less than 0.5 wt%, vanadium 200-2000 ppm, nickel 100-1500 ppm, rare earth oxide 0.5-3 wt%.

35. A process as claimed in claims 24-34, wherein the spent FCC catalyst has a surface area of 50-170 m2/gm, particle size of201200 microns and apparent bulk density of 0.70-0.90gm/ml.
36. A process as claimed in claims 24-35, wherein the proportion of rare earth and/or aluminium containing substance to the spent FCC catalyst is such that the obtained value added catalyst has aluminium in the range of 20-60 wt%, silica 20-50 wt%, sodium oxide less than 0.5 wt%, titanium oxide less than 0.5 wt%, vanadium 200-2000 ppm and rare earth oxide in the range of 1-13.5 wt%.
37. A process as claimed in claims 24-36, wherein the introduction of the activity enhancer is carried out by wet impregnaiion, ion-exchange or feeding along with hydrocarbon feed in actual plant operation.
38. A process as claimed in claims 24-37, wherein the proportion of activity enhancer substance with respect to spent FCC catalyst is in the range of 0.5-10 wt% on oxide basis.
39. A process as claimed in any of claims 24-38 wherein the term "value" has meanings such as herein described.
40. A process for preparing dual function catalyst additive composition from spent FCC catalyst comprising the following sequence of steps:

a) preparation of a rare earth and/or aluminium containing solutions,
b) wet impregnation of spent FCC catalyst with a solution of step (a),
c) oven drying of wet impregnated spent catalyst of step (b),
d) calcination of oven dried product of step (c).

41. A process for catalytic cracking of hydrocarbons to provide higher conversion, naphtha yield and lower bottoms characterized in that a catalyst composition of claims 1-23 is used.
42. A process as claimed in claim 40, wherein the value added spent catalyst is added to a host cracking catalyst in a proportion ranging from 1-99 wt% during the catalytic cracking of hydrocarbons containing vanadium and nickel as undesirable constituents, and for preventing the adverse effect of vanadium and nickel on the activity of the host cracking catalyst.
43. A process for improving thermal and metal stability of spent FCC catalyst comprising treating as herein described the spent FCC catalyst with a substance (activity enhancer) selected from either a rare earth component or an aluminium component or a mixture/combination of the two.
44. A process for enhancing the catalytic activity and selectivity of spent FCC catalyst in adverse RFCC conditions comprising treating as herein described spent FCC catalyst with a substance (activity enhancer) selected from either a rare earth component or an aluminium component or a mixture/combination of the two.
45. A process for enhancing crystallintty and surface area of a host FCC catalyst comprising applying activity enhancer substance such as herein described on spent FCC catalyst.

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Orders

Section Controller Decision Date
section 15 Bhaskar Ghosh 2017-05-08
section 15 Bhaskar Ghosh 2017-05-08

Application Documents

# Name Date
1 746-KOL-2010-RELEVANT DOCUMENTS [28-08-2023(online)].pdf 2023-08-28
1 746-kol-2010-specification.pdf 2011-10-07
2 746-KOL-2010-PA.pdf 2011-10-07
2 746-KOL-2010-RELEVANT DOCUMENTS [29-08-2022(online)].pdf 2022-08-29
3 746-KOL-2010-RELEVANT DOCUMENTS [07-10-2021(online)].pdf 2021-10-07
3 746-KOL-2010-FORM 5.pdf 2011-10-07
4 746-KOL-2010-RELEVANT DOCUMENTS [16-03-2020(online)].pdf 2020-03-16
4 746-KOL-2010-FORM 3.pdf 2011-10-07
5 746-KOL-2010-RELEVANT DOCUMENTS [18-03-2019(online)].pdf 2019-03-18
5 746-kol-2010-form 2.pdf 2011-10-07
6 746-KOL-2010-RELEVANT DOCUMENTS [10-03-2018(online)].pdf 2018-03-10
6 746-KOL-2010-FORM 2-1.2.pdf 2011-10-07
7 746-KOL-2010-FORM 2-1.1.pdf 2011-10-07
7 746-KOL-2010-CORRESPONDENCE.pdf 2017-05-29
8 746-kol-2010-form 1.pdf 2011-10-07
8 746-KOL-2010-DECISION.pdf 2017-05-29
9 746-KOL-2010-EXAMINATION REPORT.pdf 2017-05-29
9 746-KOL-2010-FORM 1-1.1.pdf 2011-10-07
10 746-kol-2010-description (provisional).pdf 2011-10-07
10 746-KOL-2010-FORM 18-1.1.pdf 2017-05-29
11 746-KOL-2010-DESCRIPTION (COMPLETE).pdf 2011-10-07
11 746-KOL-2010-GPA.pdf 2017-05-29
12 746-KOL-2010-AMANDED CLAIMS.pdf 2011-10-07
12 746-KOL-2010-GRANTED-ABSTRACT.pdf 2017-05-29
13 746-kol-2010-abstract.pdf 2011-10-07
13 746-KOL-2010-GRANTED-CLAIMS.pdf 2017-05-29
14 746-KOL-2010-ABSTRACT 1.1.pdf 2011-10-07
14 746-KOL-2010-GRANTED-DESCRIPTION (COMPLETE).pdf 2017-05-29
15 746-KOL-2010-FORM-18.pdf 2012-07-03
15 746-KOL-2010-GRANTED-FORM 1.pdf 2017-05-29
16 746-KOL-2010-(01-08-2012)-CORRESPONDENCE.pdf 2012-08-01
16 746-KOL-2010-GRANTED-FORM 2.pdf 2017-05-29
17 746-KOL-2010-GRANTED-FORM 3.pdf 2017-05-29
17 746-KOL-2010-(01-08-2012)-ASSIGNMENT.pdf 2012-08-01
18 746-KOL-2010-GRANTED-FORM 5.pdf 2017-05-29
18 Fresh Form 1.pdf 2013-12-18
19 746-KOL-2010-GRANTED-LETTER PATENT.pdf 2017-05-29
19 Form 26.pdf 2013-12-18
20 746-KOL-2010-GRANTED-SPECIFICATION-COMPLETE.pdf 2017-05-29
20 Form 13.pdf 2013-12-18
21 746-KOL-2010-HEARING NOTICE.pdf 2017-05-29
21 746-KOL-2010_EXAMREPORT.pdf 2016-06-30
22 Other Patent Document [31-03-2017(online)].pdf 2017-03-31
22 Petition Under Rule 137 [22-08-2016(online)].pdf_82.pdf 2016-08-22
23 Other Patent Document [29-03-2017(online)].pdf 2017-03-29
23 Petition Under Rule 137 [22-08-2016(online)].pdf 2016-08-22
24 Other Document [22-08-2016(online)].pdf 2016-08-22
24 Claims [22-08-2016(online)].pdf 2016-08-22
25 Description(Complete) [22-08-2016(online)].pdf 2016-08-22
25 Examination Report Reply Recieved [22-08-2016(online)].pdf 2016-08-22
26 Description(Complete) [22-08-2016(online)].pdf 2016-08-22
26 Examination Report Reply Recieved [22-08-2016(online)].pdf 2016-08-22
27 Claims [22-08-2016(online)].pdf 2016-08-22
27 Other Document [22-08-2016(online)].pdf 2016-08-22
28 Other Patent Document [29-03-2017(online)].pdf 2017-03-29
28 Petition Under Rule 137 [22-08-2016(online)].pdf 2016-08-22
29 Other Patent Document [31-03-2017(online)].pdf 2017-03-31
29 Petition Under Rule 137 [22-08-2016(online)].pdf_82.pdf 2016-08-22
30 746-KOL-2010-HEARING NOTICE.pdf 2017-05-29
30 746-KOL-2010_EXAMREPORT.pdf 2016-06-30
31 746-KOL-2010-GRANTED-SPECIFICATION-COMPLETE.pdf 2017-05-29
31 Form 13.pdf 2013-12-18
32 746-KOL-2010-GRANTED-LETTER PATENT.pdf 2017-05-29
32 Form 26.pdf 2013-12-18
33 746-KOL-2010-GRANTED-FORM 5.pdf 2017-05-29
33 Fresh Form 1.pdf 2013-12-18
34 746-KOL-2010-(01-08-2012)-ASSIGNMENT.pdf 2012-08-01
34 746-KOL-2010-GRANTED-FORM 3.pdf 2017-05-29
35 746-KOL-2010-GRANTED-FORM 2.pdf 2017-05-29
35 746-KOL-2010-(01-08-2012)-CORRESPONDENCE.pdf 2012-08-01
36 746-KOL-2010-FORM-18.pdf 2012-07-03
36 746-KOL-2010-GRANTED-FORM 1.pdf 2017-05-29
37 746-KOL-2010-ABSTRACT 1.1.pdf 2011-10-07
37 746-KOL-2010-GRANTED-DESCRIPTION (COMPLETE).pdf 2017-05-29
38 746-kol-2010-abstract.pdf 2011-10-07
38 746-KOL-2010-GRANTED-CLAIMS.pdf 2017-05-29
39 746-KOL-2010-AMANDED CLAIMS.pdf 2011-10-07
39 746-KOL-2010-GRANTED-ABSTRACT.pdf 2017-05-29
40 746-KOL-2010-DESCRIPTION (COMPLETE).pdf 2011-10-07
40 746-KOL-2010-GPA.pdf 2017-05-29
41 746-kol-2010-description (provisional).pdf 2011-10-07
41 746-KOL-2010-FORM 18-1.1.pdf 2017-05-29
42 746-KOL-2010-EXAMINATION REPORT.pdf 2017-05-29
42 746-KOL-2010-FORM 1-1.1.pdf 2011-10-07
43 746-KOL-2010-DECISION.pdf 2017-05-29
43 746-kol-2010-form 1.pdf 2011-10-07
44 746-KOL-2010-CORRESPONDENCE.pdf 2017-05-29
44 746-KOL-2010-FORM 2-1.1.pdf 2011-10-07
45 746-KOL-2010-RELEVANT DOCUMENTS [10-03-2018(online)].pdf 2018-03-10
45 746-KOL-2010-FORM 2-1.2.pdf 2011-10-07
46 746-KOL-2010-RELEVANT DOCUMENTS [18-03-2019(online)].pdf 2019-03-18
46 746-kol-2010-form 2.pdf 2011-10-07
47 746-KOL-2010-RELEVANT DOCUMENTS [16-03-2020(online)].pdf 2020-03-16
47 746-KOL-2010-FORM 3.pdf 2011-10-07
48 746-KOL-2010-RELEVANT DOCUMENTS [07-10-2021(online)].pdf 2021-10-07
48 746-KOL-2010-FORM 5.pdf 2011-10-07
49 746-KOL-2010-RELEVANT DOCUMENTS [29-08-2022(online)].pdf 2022-08-29
49 746-KOL-2010-PA.pdf 2011-10-07
50 746-KOL-2010-RELEVANT DOCUMENTS [28-08-2023(online)].pdf 2023-08-28
50 746-kol-2010-specification.pdf 2011-10-07

ERegister / Renewals

3rd: 15 May 2017

From 08/07/2012 - To 08/07/2013

4th: 15 May 2017

From 08/07/2013 - To 08/07/2014

5th: 15 May 2017

From 08/07/2014 - To 08/07/2015

6th: 15 May 2017

From 08/07/2015 - To 08/07/2016

7th: 15 May 2017

From 08/07/2016 - To 08/07/2017

8th: 15 May 2017

From 08/07/2017 - To 08/07/2018

9th: 16 Feb 2018

From 08/07/2018 - To 08/07/2019

10th: 22 Feb 2019

From 08/07/2019 - To 08/07/2020

11th: 03 Feb 2020

From 08/07/2020 - To 08/07/2021

12th: 01 Jul 2021

From 08/07/2021 - To 08/07/2022

13th: 05 Jul 2022

From 08/07/2022 - To 08/07/2023

14th: 07 Jul 2023

From 08/07/2023 - To 08/07/2024

15th: 28 Jun 2024

From 08/07/2024 - To 08/07/2025

16th: 08 Jul 2025

From 08/07/2025 - To 08/07/2026