Adsorbent for removal of con-carbon and contaminant metal present in hydrocarbon feed
09616408 ยท 2017-04-11
Assignee
Inventors
- Arumugam Velayutham Karthikeyani (Faridabad, IN)
- Mohan Prabhu Kuvettu (Fairdabad, IN)
- Biswanath Sarkar (Faridabad, IN)
- Gadari Saidulu (Faridabad, IN)
- Shiba Prasad Choudhury (Faridabad, IN)
- Sudhir Kumar Pande (Faridabad, IN)
- Arvind Mahant (Faridabad, IN)
- Brijesh Kumar (Faridabad, IN)
- Santanam Rajagopal (Faridabad, IN)
- Ravinder Kumar MALHOTRA (Faridabad, IN)
- Velusamy Chidambaram (Faridabad, IN)
Cpc classification
C10G25/03
CHEMISTRY; METALLURGY
B01J20/3085
PERFORMING OPERATIONS; TRANSPORTING
B01J20/3064
PERFORMING OPERATIONS; TRANSPORTING
B01J20/28085
PERFORMING OPERATIONS; TRANSPORTING
B01J20/3007
PERFORMING OPERATIONS; TRANSPORTING
B01J20/12
PERFORMING OPERATIONS; TRANSPORTING
B01J20/28092
PERFORMING OPERATIONS; TRANSPORTING
C10G55/06
CHEMISTRY; METALLURGY
International classification
B01J20/30
PERFORMING OPERATIONS; TRANSPORTING
C10G55/06
CHEMISTRY; METALLURGY
B01J20/28
PERFORMING OPERATIONS; TRANSPORTING
C10G25/03
CHEMISTRY; METALLURGY
Abstract
The present invention provides an adsorbent for removal of con-carbon and contaminant metals in feed, said adsorbent composition consisting of clay in the range of 30-70 wt. % and silica in the range of 70-30 wt. %, wherein the adsorbent has a pore volume in the range of 0.25-0.45 cc/gm; a pore size in the range of 20 to 2000 and a bi-modal pore size distribution characteristics, with a maximum of about 32% of the adsorbent having a pore size in the range of 20-200 and a minimum of about 68% of the adsorbent having a pore size in the range of 200-2000 . The present invention also provides a process for preparing the said adsorbent.
Claims
1. An adsorbent for removal of con-carbon and contaminant metals in feed, said adsorbent consisting of: (a) clay in the range of 30-70 wt. %; and (b) silica in the range of 70-30 wt. %, wherein the adsorbent has a pore volume in the range of 0.25-0.45 cc/gm; a pore size in the range of 20 to 2000 ; and a bi-modal pore size distribution characteristics, with a maximum of about 32% of the adsorbent having a pore size in the range of 20-200 and a minimum of about 68% of the adsorbent having a pore size in the range of 200-2000 .
2. The adsorbent as claimed in claim 1, wherein the clay is in the range of 35-65 wt. %, and silica is in the range of 65-35 wt. %.
3. The adsorbent as claimed in claim 1, wherein the clay is in the range of 40-50 wt. %, and silica is in the range of 60-50 wt. %.
4. The adsorbent as claimed in claim 1, wherein a maximum of 30% of the adsorbent have a pore size in the range of 20-200 and a minimum of 70% of the adsorbent having a pore size in the range of 200-2000 .
5. The adsorbent as claimed in claim 1, wherein the silica is formed/sourced from a group comprising of sodium silicate both neutral and alkaline, silicic acid, sodium or ammonium stabilized colloidal silica, or combination thereof.
6. The adsorbent as claimed in claim 1, wherein the clay is selected from a group comprising of kaolinite, bentonite, illite, vermiculite, smectite, dolomite, or combination thereof.
7. A process for preparing an adsorbent consisting of 30-70 wt. % of clay and 70-30 wt. % of silica, wherein the adsorbent has a pore volume in the range of 0.25-0.45 cc/gm; a pore size in the range of 20 to 2000 ; and a bi-modal pore size distribution characteristics, with a maximum of 32% of the adsorbent having a pore size in the range of 20-200 and a minimum of 68% of the adsorbent having a pore size in the range of 200-2000 , said process comprising the steps of: (a) preparing a silica sol by adding source of silica to an acid; (b) preparing clay slurry by adding demineralized water containing dispersant; (c) adding a clay material to the silica sol so as to obtain a clay-silica slurry; (d) adding a pore regulating agent to the clay-silica slurry and forming shaped microsphere/extrudate from the same; and (e) calcining the shaped microsphere/extrudate so as to remove the pore regulating agent therefrom to thereby obtain the adsorbent.
8. The process as claimed in claim 7, wherein the source of silica is selected from a group comprising of sodium silicate both neutral and alkaline, silicic acid, sodium or ammonium stabilized colloidal silica, or combination thereof.
9. The process as claimed in claim 7, wherein the clay material is selected from a group comprising of kaolinite, bentonite, illite, vermiculite, smectite, dolomite, or combination thereof.
10. The process as claimed in claim 7, wherein the pore regulating agent is selected from a group comprising of acrylamide polymer, propylene oxide polymer, ethylene oxide polymer, polyvinyl alcohol, C12-C25 surfactants or combination thereof.
11. The process as claimed in claim 7, wherein the acid is selected from a group comprising of sulfuric acid, nitric acid, hydrochloric acid, formic acid or combination thereof.
12. The process as claimed in claim 7, wherein the silica sol is prepared by adding source of silica to an acid under controlled temperature between 10-30 C. with pH below 3.
13. The process as claimed in claim 7, wherein the dispersant is sold under the trademark TAMOL, which is neutral sodium salt of a condensed arylsufonic acid.
Description
BRIEF DESCRIPTION OF DRAWING
(1)
DETAILED DESCRIPTION OF INVENTION
(2) While the invention is susceptible to various modifications and alternative forms, specific embodiment thereof will be described in detail below. It should be understood, however that it is not intended to limit the invention to the particular forms disclosed, but on the contrary, the invention is to cover all modifications, equivalents, and alternative falling within the scope of the invention as defined by the appended claims.
(3) The present invention discloses an adsorbent which can selectively adsorb metal contaminants and con-carbon from hydrocarbon feeds. The hydrocarbon feeds according to the invention contains very high concentrations of metals such as nickel, vanadium, sodium, iron and so forth. The adsorbent used is a neutral inorganic composition. Following removal, soft feed can be cracked over zeolitic FCC catalyst.
(4) In accordance with the present invention the neutral adsorbent comprises of clay from 30-70%, silica from 70-30% and is prepared by employing a volatile pore regulating template. Further, the adsorbent is suitable for removal of con-carbon and metals present in the feed from 10 wt % and 10-200 ppm.
(5) According to the invention, the adsorbent has a microspheroidal shape with particle size ranging from 20-150 microns or is an extrudate with cross-section 0.5 mm to 3 mm or any other suitable required form.
(6) The adsorbent has pore volume from 0.25-0.45 cc/gm with a maximum of about 32% of the adsorbent having a pore size in the range of 20-200 and a minimum of about 68% of the adsorbent having a pore size in the range of 200-2000 .
(7) Further, the invention provides a process for preparation of the adsorbent. The adsorbent is prepared by, selecting a silica based binder sourced from sodium silicate both neutral and alkaline, silicic acid, sodium or ammonium stabilized colloidal silica, pore regulating agent sourced from acrylamide polymer, propylene oxide polymer, ethylene oxide polymer, polyvinyl alcohol, C12-C25 surfactants, clay sourced from kaolinite, bentonite, illite, vermiculite, smectite or dolomite, selecting a acid from sulfuric acid, nitric acid, hydrochloric acid, formic acid and producing a silica sol by, addition of silica source to a dilute acid under controlled temperature between 10-30 C. under vigorous mixing conditions with pH below 3, adding a clay material and finally adding pore regulating agent to obtain a fine slurry with solid content ranging from 15-45 wt %. The slurry is further processed to prepare the adsorbent in various forms such as microspheres, extrudates and so forth.
(8) Accordingly, the present invention provides an adsorbent for removal of con-carbon and contaminant metals in feed, said adsorbent consisting of: (a) clay in the range of 30-70 wt. %; and (b) silica in the range of 70-30 wt. %,
wherein the adsorbent has a pore volume in the range of 0.25-0.45 cc/gm; a pore size in the range of 20 to 2000 ; and a bi-modal pore size distribution characteristics, with a maximum of about 32% of the adsorbent having a pore size in the range of 20-200 and a minimum of about 68% of the adsorbent having a pore size in the range of 200-2000 .
(9) In one embodiment of the present invention, the clay is in the range of 35-65 wt. %, and silica is in the range of 65-35 wt. %. Most preferably the clay is in the range of 40-50 wt. %, and silica is in the range of 60-50 wt. %.
(10) In another embodiment of the present invention, a maximum of 30% of the adsorbent have a pore size in the range of 20-200 and a minimum of 70% of the adsorbent having a pore size in the range of 200-2000 .
(11) In yet another embodiment of the present invention, the silica is selected from a group comprising of sodium silicate both neutral and alkaline, silicic acid, sodium or ammonium stabilized colloidal silica, or combination thereof.
(12) In still an embodiment of the present invention, the clay is selected from a group comprising of kaolinite, bentonite, illite, vermiculite, smectite, dolomite, or combination thereof.
(13) The present invention also provides a process for preparing an adsorbent consisting of 30-70 wt. % of clay and 70-30 wt. % of silica, wherein the adsorbent has a pore volume in the range of 0.25-0.45 cc/gm; a pore size in the range of 20 to 2000 ; and a bi-modal pore size distribution characteristics, with a maximum of 32% of the adsorbent having a pore size in the range of 20-200 and a minimum of 68% of the adsorbent having a pore size in the range of 200-2000 , said process comprises the steps of: (a) preparing a silica sol by adding source of silica to an acid; (b) preparing clay slurry by adding demineralized water contains dispersant; (c) adding a clay material to the silica sol so as to obtain a clay-silica slurry; (d) adding a pore regulating agent to the clay-silica slurry and forming shaped microsphere/extrudate from the same; and (e) processing the shaped microsphere/extrudate so as to remove the pore regulating agent therefrom to thereby obtain the adsorbent.
(14) In yet another embodiment of the present invention, the pore regulating agent is selected from a group comprising of acrylamide polymer, propylene oxide polymer, ethylene oxide polymer, polyvinyl alcohol, C12-C25 surfactants or combination thereof.
(15) In still an embodiment of the present invention, the acid is selected from a group comprising of sulfuric acid, nitric acid, hydrochloric acid, formic acid or combination thereof.
(16) In yet another embodiment of the present invention, the silica sol is prepared by adding source of silica to an acid under controlled temperature between 10-30 C. with pH below 3.
(17) The present invention further provides that the adsorbent is used for removal of con-carbon and metals present in the feed from 10 wt % and 10-200 ppm.
(18) For residue feed applications pore size distribution of matrix component requires a special attention. Therefore the current invention has targeted with the different matrix structures. Current adsorbent has a macro pores 200-2000 to allow deposition of metals & CCR and to assist in the further cracking of large asphalting molecules. Although this macro pores have a low activity (conversion about 30-40 wt %) due to silica-based matrix possessing a weak acidity, but they act as a guide for large molecules to access active sites in microspores (20-50 ). Sufficient meso porosity (20-200 ) has also been maintained in the adsorbent to ensure cracking of the naphthenic structures and alkyl substituent from aromatic rings, whereas micro porosity is necessary to crack straight alkyl chains.
(19) The optimal amount and type of silica matrix was selected to provide adequate resistance to deactivation by metals, particularly by V and Ni. Clay was added to provide desirable density of the catalyst as well as to passivate the detrimental effect of Ni & V.
(20) Also in the current invention a correlation has been made/maintained between the pore volume and the matrix surface area for optimizing the catalyst performance for different residues. Overall the adsorbent removes the CCR & metals simultaneously and thereby increase the life of cracking catalyst. The content of CCR in the feed may be an indication of the presence of metals in the feed, i.e., higher content of CCR higher content of metals.
(21) There are two main constraints during the operation of the FCC/RFCC units while handling heavier hydro carbon feedstock, i.e., the activity limited conversion and delta-coke (the difference between the amount of coke on spent catalyst entering the regenerator and that on the regenerated catalyst exiting the regenerator and entering the riser) limited conversion.
(22) The former reflects the limitation in conversion and/or yield of the unwanted gaseous products in the riser, as well as a higher coke formation due to low catalyst activity. This problem can be alleviated either by using a more active catalyst or changing the catalyst/feed ratio.
(23) The delta coke limitations reflect the situation in regenerator caused by the excessive amount of coke deposited on catalyst in the riser. The increased values of delta-coke require larger air supply to regenerator which may cause unwanted temperature excursion. This problem can be controlled in the riser-reactor either by decreasing the dehydrogenation activity of catalyst (due to Ni) or by increasing the catalyst/feed ratio.
(24) The large pore adsorbent can remove metal (particularly Ni & V) and CCR present in the heavier hydrocarbon feedstock and make the feedstock free from contaminants, which indirectly increase the life of cracking catalyst. Also the silica-clay based adsorbent is cheaper in cost.
(25) The following non-limiting examples illustrate in details about the invention. However, they are, not intended to be limiting the scope of present invention in any way.
Example 1
Preparation Procedure for Making Adsorbent Clay-Silica (50:50)
(26) 290 g of clay (loss on ignition 14.19 wt. %) was slurried in 300 g of demineralised water (DM) which contained 0.5 wt % dispersant (Tamol) and kept under stirring. 12 gms Formic acid (dilute acid) was added into 100 ml of DM water. Silica sol was prepared by adding 833 g of ammonium polysilicate (30 wt. % SiO.sub.2) to the dilute acid under controlled temperature between 10-30 C. under vigorous mixing conditions with pH below 3, which was kept under stirring for 30 minutes. The prepared Silica sol was added to the clay slurry. Then 2 g of pore regulating agent in 100 ml DM water was added to the Clay-Silica slurry and the final slurry with a solid content of 35 wt % was spray dried and the fraction between 20-120 microns with an average particle size of 85 microns was separated for further study. The calcined product was tested for ABD and attrition index, which were measured respectively as 0.85 g/ml and 3.0.
Example-2
Process for Preparing Spray Dried Adsorbent in the Shape of Microsphere
(27) The slurry with a solid content ranging from 15-45 wt % is spray dried to produce microspheres in particle size range 20 to 150 microns. As the microspheres may contain significant amount of sodium salts, spray dried microspheres are washed off sodium by dispersing in hot demineralised water in temperature range 40-100 C. Washed microspheres are then flash dried and calcined for further application as an adsorbent. The final product has silica in the range 30-70 wt %, alumina in the range 10-50 wt % and residual sodium <0.5 wt %. Thus produced microspheres have average particle size in the range 20-150 microns, ABD (Apparent Bulk Density) in the range 0.65 to 0.95 g/cc and exhibit attrition index below 6. Calcined microspheres when analysed showed pore volume in the range 0.25 to 0.45 cc/gm occupying 20-200 pores 25% of pore volume and 200-2000 pores occupying 75% of pore volume.
Example-3
Procedure for Preparing Adsorbent in the Shape of Extrudates
(28) The pH of free flowing slurry prepared was raised above 3.5 and held for 3-12 hrs to form a gel. This gel was extruded to desired shape and dried in an oven. The dried extrudates were washed off sodium to a concentration below 0.5 wt % and calcined for use as adsorbent.
(29) Effect of Pore Regulating Agents on Pore Volume of Adsorbent:
(30) TABLE-US-00001 TABLE 1 Table-1: Identification of proper pore regulating agent: Clay = 50 wt % Silica = 50 wt % Pore Regulating agent Concentration, wt % Pore volume, cc/gm C.sub.12-C.sub.25 surfactants 6 0.45 C.sub.12-C.sub.25 surfactants 6 0.41 Ethylene oxide polymer 6 0.3 propylene oxide polymer 6 035
(31) TABLE-US-00002 TABLE 2 Table-2: Optimization of Pore regulating agent: Clay Silica Pore regulating Pore volume Wt % Wt % agent (I), Wt % Cc/gm 1 50 50 2 0.34 2 50 50 3 0.37 3 50 50 4 0.4 4 50 50 6 0.45
(32) TABLE-US-00003 TABLE 3 Table-3: Optimization of Adsorbent composition: Pore Clay Silica Pore regulating volume Pore size Wt % Wt % agent (I), Wt % Cc/gm A 1 85 15 6 0.22 20-200 = 35% 200-2000 = 65% 3 70 30 6 0.28 20-200 = 32% 200-2000 = 68% 4 50 50 6 0.45 20-200 = 25% 200-2000 = 75% 5 40 60 6 0.38 20-200 = 30% 200-2000 = 70% 6 25 75 6 0.35 20-200 = 35% 200-2000 = 65%
(33) Distinct bi-modal pore size distribution observed and that can be seen in the
Example-4
(34) This example explains the properties of spray dried micro sphere samples at maximum metal level (Ni-15000 ppm & V-30000 ppm) prepared as per procedure mentioned in example-2 above and is given in Table-4. The adsorbent was first metal doped by conventional Mitchel method (Ref: B R Mitchell Metal contaminants of catalytic cracking Ind Eng Chem Prod Res & Dev 209, 19, 1980) at required nickel and vanadium levels. Then samples were reduced with partial pressure hydrogen to bring the metals in reduced state and steamed at temperature of 788 deg.C. for 3 hours using 100% steam. The surface area achieved in the range of 37-64 m.sup.2/gm and pore volume in the range of 0.25-0.45 gm/cc.
(35) TABLE-US-00004 TABLE 4 Table-4: Properties of adsorbent Adsorbent-A Adsorbent-B Adsorbent-C Adsorbent-D Properties Fresh Metal doped Metal doped Metal doped Metal on Adsorbent, ppm Ni 0 4000 10000 15000 V 0 10500 20000 30000 Surface area, 63.36 54.26 46.49 37.90 m2/gm Pore volume, 0.45 0.37 0.29 0.25 cc/gm
Micro Activity Test (MAT):
(36) The steamed adsorbent (fresh and metal doped) was subjected to CCR (canradson carbon residue) and metal removal study in ACE R+MAT unit under the typical conditions as shown in Table-5. After removing CCR & metal the product was subjected to activity test in Fixed Bed Auto MAT unit under the typical conditions as shown in Table-5. Coke on catalyst is determined by in-situ regeneration with fluidized air by heating at 660 C. The gas sample is analyzed with online micro GC. The H2, C1, C2, C3, C4 and C5 lump is determined quantitatively. The liquid products are analyzed by ASTM 2887 procedure in a simulated distillation analyzer, Perkin Elmer. The percentage of the liquid products boiling in the range of gasoline (C5-150 C.), heavy naphtha (C150-216 C.), Light Cycle Oil (C-216 C.-370 C.) and Clarified Oil (370 C.+) is calculated. Carbon on catalyst was determined by online IR analyzer.
(37) TABLE-US-00005 TABLE 5 Table-5: Reaction conditions used in micro reactor experiment Fixed bed Conditions ACE R+ unit Auto MAT unit Weight of catalyst loaded, gms 6-12 2.5-3.5 Feed Injection time, sec 30-45 10-75 Reactor temperature, C. 450-550 500-650 Feed rate, gm/min 1.5-3.5 1.5-6
(38) TABLE-US-00006 TABLE 6 Table-6: Properties of feedstock used in the current invention Feed-3 (Cracked product Properties Feed-1 Feed-2 from Feed-2) Density, gm/cc 0.946 0.9053 CCR, wt % 5.86 10.37 0.19 Metal, ppm Nickel <1 15 <1 Vanadium <1 51 <1 PONA, wt % Aromatic 40.74 32 Saturates 59.26 68 Sulfur, wt % 0.28 2.48 0.02
Table-7: Performance Evaluation of Clay-Silica (50:50) Vis--Vis Clay-Silica (25:75) & Clay-Silica (85:15) to Check the CCR Removal Capability:
(39) The prepared Clay-Silica samples without metal were evaluated in ACE R+ unit under ROT of 550 C. and cat/oil 5.0 with respect to feed stock-1. The products were analyzed as per the procedure described in the section Micro Activity Test (MAT). The product was also analyzed for CCR & metal content in it. This example illustrates the cracking and CCR & metals (Ni&V) removable capability of various Clay-Silica samples.
(40) TABLE-US-00007 TABLE 7 Description Feed-1 Feed-1 Feed-1 Adsorbent Clay- Clay- Clay- Silica Silica Silica (50:50) (25:75) (85:15) Metal on catalyst, ppm Ni Nil Nil Nil V Nil Nil Nil Temperature, deg. C. 550 550 550 WHSV, hr1 24 24 24 Cat/Oil 5.0 5.0 5.0 Yield, wt % Hydrogen 0.09 0.04 0.05 Dry gas 1.08 1.7 1.22 LPG 9.83 3.21 2.34 Gasoline (C5-150 deg. C.) 14.50 10.22 5.05 Heavy naphtha (150-216 deg. C.) 6.82 5.13 3.85 Light cycle oil (216-370 deg. C.) 23.78 22.23 18.51 Clarified oil (370 deg. C.+) 31.30 46.44 56.98 Coke 12.60 11.03 12 216 deg. C. Conversion 44.92 31.33 24.51 CCR, wt % 0 0.78 1.25
(41) Adsorbent Clay-Silica shows zero CCR in the liquid sample when compare to Clay-Silica 25:75 (0.78 wt %) & Clay-Silica 85:15 (1.25 wt %).
(42) Table-8: Performance Evaluation of Clay-Silica (50:50) Vis--Vis Clay-Alumina-La.sub.2O.sub.3:
(43) The prepared Clay-Silica (50:50) sample & Clay-Alumina-La.sub.2O.sub.3 sample without metal were evaluated in ACE R+ unit under ROT of 550 C. and cat/oil 5.0 with respect to feed stock-1. The products were analyzed as per the procedure described in the section Micro Activity Test (MAT). The product was also analyzed for CCR & metal content in it.
(44) TABLE-US-00008 TABLE 8 Catalyst Name ADSORBENT Clay-Alumina-La.sub.2O.sub.3 Clay-Silica (w/o pore (50:50) regulating agent) Feed I.D. Feed-1 Feed-1 Cracking Temperature, C. 550 550 Injection Time, sec 30 30 Catalyst-to-Oil, wt/wt 5.00 5.00 YIELDS, wt %: Hydrogen 0.09 0.1 Dry gas 1.08 1.71 LPG 9.83 11.05 Gasoline (C5-150 deg. C.) 14.5 14.16 Heavy naphtha 6.82 6.11 (150-216 deg. C.) Light cycle oil 23.78 21.3 (216-370 deg. C.) Clarified oil (370 deg. C.+) 31.3 29.95 Coke 12.6 15.62 216 deg. C. Conversion, wt % 44.92 48.75 CCR, wt % 0 1.33
(45) Adsorbent Clay-Silica shows reduction in coke (12.6 wt. %) yield when compare to Clay-Alumina-La.sub.2O.sub.3 system (15.62 wt. %). Also adsorbent Clay-Silica shows zero CCR in the liquid sample when compare to Clay-Alumina-La.sub.2O.sub.3 system (i.e. 1.33 wt. %).
Example-5
Activity and Selectivity of Adsorbent
(46) Adsorbent A without metal was evaluated in ACE R+ unit under ROT of 550 C. and cat/oil 5.0 with respect to feed stock-1. The products were analyzed as per the procedure mentioned in Example-4. The product was also analyzed for CCR & metal content in it. This example illustrates that adsorbent without metal can remove CCR & metals (Ni&V) fully from the feed sample and is able to increase the propylene selectivity in LPG of 40%.
(47) Adsorbent B with metals nickel 4000 ppm and vanadium 10500 ppm was evaluated in ACE R+MAT unit under ROT 550 C. & cat/oil 5.0 with respect to feed stock 1 & 2. The products were analyzed as per the procedure mentioned in Example-4. Adsorbent with metal can crack various hydrocarbon feed stocks having CCR 5.56 wt % and 10.37 wt % and able to increase the propylene selectivity in LPG of 47.78% and 37.60% (Table-9). The ethylene selectivity in dry gas could be achieved in the range of 26.3-30.59%.
(48) TABLE-US-00009 TABLE 9 Description Feed-1 Feed-1 Feed-2 Adsorbent Adsorbent A Adsorbent B Adsorbent B Metal on catalyst, ppm Ni 4000 4000 V 10500 10500 Temperature, deg. C. 550 550 550 WHSV, hr1 24 24 24 Cat/Oil 5.0 5.0 5.0 Yield, wt % Hydrogen 0.09 0.04 0.25 Dry gas 1.08 2.7 1.02 LPG 9.83 4.27 3.46 Gasoline (C5-150 deg. C.) 14.50 13.72 7.05 Heavy naphtha 6.82 5.47 3.96 (150-216 deg. C.) Light cycle oil 23.78 23.29 20.43 (216-370 deg. C.) Clarified oil (370 deg. C.+) 31.30 39.48 45.83 Coke 12.60 11.03 18 216 deg. C. Conversion 44.92 37.23 33.74 Ethylene in Dry gas 30.71 26.30 30.59 Propylene in LPG 40.00 47.78 37.60 CCR, wt % 0 0.05 0.19
Example-6
Combined Yield with Feed 2 & 3
(49) Adsorbent B impregnated with metals nickel 4000 ppm and vanadium 10500 ppm was evaluated in ACE R+MAT unit under ROT 550 C., Feed-2 & cat/oil 5.0 and the products were analyzed as per the procedure mentioned in Example-4. The cracked liquid product were analyzed for CCR and metal and achieved the value of 0.19 wt % and <1 ppm. The cracked liquid products were collected and evaluated in fixed bed MAT unit in presence of Y-zeolite base catalyst, ZSM-5 additive and residue up gradation additive. The propylene selectivity in LPG could be achieved as 49.13% (Table-10). The ethylene selectivity in dry gas that could be achieved is 61.46%.
(50) TABLE-US-00010 TABLE 10 Description Combined yield of Feed-2 Feed-3 Feed 2 & 3 Metal on catalyst, ppm Ni 4000 Nil V 10500 Nil Catalyst Adsorbent Catalyst (40%) + B ZSM-5 additive (40%) + Residue upgrading additive (20%) Temperature, 550 580 deg. C. WHSV, hr1 24 59.14 Cat/Oil 5.0 6.09 Yield, wt % Hydrogen 0.25 0.24 0.25 Dry gas 1.02 13.44 6.43 LPG 3.46 31.57 15.70 Gasoline 7.05 21.44 13.31 (C5-150 deg. C.) Heavy naphtha 3.96 10.67 6.88 (150-216 deg. C.) Light cycle oil 20.43 11.00 16.30 (216-370 deg. C.) Clarified oil 45.83 2.14 26.76 (370 deg. C.+) Coke 18 9.75 14.39 216 deg. C. 33.74 86.87 56.94 Conversion Ethylene in Dry gas 30.59 61.46 Propylene in LPG 37.60 49.13 Other light 47.37 25.40 olefin in LPG CCR, wt % 0.19 Metal (Ni, V, <1 Na, Fe), ppm