WO2016087956A1 - Hydrothermally stable fcc catalyst additive composition - Google Patents

Hydrothermally stable fcc catalyst additive composition Download PDF

Info

Publication number
WO2016087956A1
WO2016087956A1 PCT/IB2015/056062 IB2015056062W WO2016087956A1 WO 2016087956 A1 WO2016087956 A1 WO 2016087956A1 IB 2015056062 W IB2015056062 W IB 2015056062W WO 2016087956 A1 WO2016087956 A1 WO 2016087956A1
Authority
WO
WIPO (PCT)
Prior art keywords
zeolite
catalyst additive
fcc catalyst
steaming
range
Prior art date
Application number
PCT/IB2015/056062
Other languages
French (fr)
Inventor
Praveen Kumar CHINTHALA
Gopal Ravichandran
Tejas Dineshbhai DOSHI
Vasudev Nagesh SHETTI
Sukumar Mandal
Asit Kumar Das
Original Assignee
Reliance Industries Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Reliance Industries Limited filed Critical Reliance Industries Limited
Publication of WO2016087956A1 publication Critical patent/WO2016087956A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/90—Regeneration or reactivation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/28—Phosphorising
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/36—Steaming
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/088—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/31—Density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres

Definitions

  • the present disclosure relates to catalyst additive compositions used in refinery processes particularly in fluid catalytic cracking (FCC) process and the process of preparation for the same.
  • FCC fluid catalytic cracking
  • the fluid catalytic cracking (FCC) processes are mostly carried out by using a catalyst that comprises a mixture of large pore size crystalline zeolite (pore size greater than
  • the FCC processes executed at industrial scale involve the recycling of spent catalyst and before recycling, the spent catalyst is subjected to regeneration.
  • the regeneration of the spent catalyst is either carried out thermally or hydro thermally.
  • Hydrothermal stability of zeolites is one of the major concerns in FCC processes. Each regeneration step results into partial deactivation of catalyst/additive due to de-alumination of zeolites by loss of Al-OH-Si groups, responsible for the Bronsted acidity of the zeolites. Therefore, preventing or minimizing de-alumination is a topic of continuous interest in the field of FCC applications.
  • FCC catalyst and additives in lab or pilot scale are tested for deactivation by subjecting the catalyst/additive to hydrothermal deactivation at 650-820 °C for 3-20 hours under 60-100% steam to simulate commercial FCC plant steam deactivation conditions.
  • the FCC catalyst comprising USY based zeolite deactivates fast and attains equilibrium rapidly i.e., 3-20 hours of the steam deactivation.
  • the typical steaming protocol for FCC catalyst involves 3-20 hours at 650-820 °C.
  • deactivation of zeolite in ZSM-5 additives is continuous with time and it is tricky to select appropriate steaming conditions for lab or pilot testing to predict commercial FCC plant performance of the catalyst additive.
  • Another object of the present disclosure is to provide a hydrothermally stable FCC catalyst additive which demonstrates excellent stability and catalytic activity.
  • the present disclosure relates to a catalyst additive for fluid catalytic cracking of the hydrocarbon oil comprising a zeolite, a binder, and a clay, characterized in that the said catalyst additive comprises: a. phosphorous content in the form of P 2 0 5 ;
  • colloidal silica as a binder
  • the present disclosure also relates to a process for the preparation of the catalyst additive.
  • FIGS 1A of the accompanying drawings illustrate nitrogen adsorption- isotherms of pure ZSM-5 zeolites at -196 °C (zeolites present in the FCC catalyst additive composition of examples 1 and 2)
  • FIG. IB of the accompanying drawings illustrate the nitrogen adsorption isotherms of catalyst additives of the present disclosure (Ex-1 and Ex- 2) and conventional FCC catalyst additive (Comp. Ex), wherein all the additives are steamed at simulated conditions of steam treatment, in accordance with the present disclosure;
  • FIG. 1C of the accompanying drawings illustrates pore size distribution (BJH desorption pore volume) of FCC catalyst additives (Ex-1 and Ex- 2) of the present disclosure and conventional FCC catalyst additive (Comp. Ex) after steaming at simulated conditions of steam treatment, in accordance with the present disclosure;
  • FIGS. 2A, 2B and 2C of the accompanying drawings illustrate scanning electron microscope images of FCC catalyst additives of the present disclosure (Ex-1 and Ex-2) and conventional FCC catalyst additive (Comp. Ex), respectively after steaming at the simulated conditions of steam treatment, in accordance with the present disclosure;
  • FIGS. 3A and 3B of the accompanying drawings illustrate X-ray diffraction patterns of crystalline ZSM-5 zeolites, FCC catalyst additives of the present disclosure (Ex-1 and Ex-2), and conventional FCC catalyst additive (Comp. Ex.), respectively, wherein all the FCC catalyst additives are steamed at simulated conditions of steam treatment, in accordance with the present disclosure;
  • FIGS. 4A and 4B of the accompanying drawings illustrate temperature programmed desorption of ammonia patterns of ZSM-5 zeolites and FCC catalyst additives of the present disclosure (Ex-1 and Ex- 2) and conventional FCC catalyst additive (Comp.Ex), respectively wherein all the FCC catalyst additives are steamed at simulated conditions of steam treatment, in accordance with the present disclosure;
  • FIG. 5A of the accompanying drawings illustrates 27 Al MAS NMR spectra of ZSM-5 zeolites of different crystal size used in the present invention
  • FIG. 5B of the accompanying drawings illustrates 27 Al MAS NMR spectra of conventional FCC catalyst additive (Comp. Ex.), wherein graph “b” denotes 27 Al MAS NMR spectra before steaming and graph "a” denotes 27 Al MAS NMR spectra after steaming at the simulated conditions of steam treatment;
  • FIG. 5C of the accompanying drawings illustrates 27 Al MAS NMR spectra of the FCC catalyst additive of the present disclosure (Ex-1) wherein graph "b” denotes 27 Al MAS NMR spectra before steaming and graph "a” denotes 27 Al MAS NMR spectra after steaming at the simulated conditions of steam treatment, in accordance with the present disclosure; and
  • FIG. 5D of the accompanying drawings illustrates 27 Al MAS NMR spectra of the FCC catalyst additive of the present disclosure (Ex-2) wherein graph "a” denotes 27 Al MAS NMR spectra before steaming and graph "b” denotes 27 Al MAS NMR spectra after steaming at the simulated conditions of stream treatment, in accordance with the present disclosure.
  • an FCC catalyst additive composition comprising ZSM-5 zeolite, phosphorous, a binder and a clay, characterized in that the FCC catalyst additive exhibits ZSM-5 zeolite content is 30 to 60%; phosphorous content in the form of P 2 0 5 of at least 5.5 wt%; binder containing colloidal silica, presence of at least one 27 Al MAS NMR peak having maxima at the values ranging from 50 to 60 ppm, 30 to 50 ppm, and -15 to +15 ppm corresponding to zeolite framework tetrahedral aluminum, zeolite framework distorted tetrahedral aluminum and non-framework octahedral aluminum, respectively; and absence of an X-ray diffraction peak at 2 ⁇ value of 21.6° corresponding to aluminum phosphate crystal phase (A1P0 4 ).
  • the alumina content of the FCC catalyst additive of the present disclosure ranges from 14 wt% to 22 wt%. In accordance with one of the embodiments of the present disclosure, the alumina content ranges from 15 to 19 wt%.
  • the phosphorous content in the form of P 2 0 5 typically ranges from 5.5 to 12 wt%. In accordance with one of the embodiments of the present disclosure, the phosphorous content in the form of P 2 0 5 ranges from 6 to 10 wt%.
  • the alumina and the phosphorous contents of the FCC catalyst additive composition are measured by using an inductively coupled plasma atomic emission spectroscopy (ICP-AES).
  • ICP-AES inductively coupled plasma atomic emission spectroscopy
  • the binder does not contain any alumina.
  • the FCC catalyst additive composition of the present disclosure shows distinctive 27 Al MAS NMR peaks at 53-59 ppm, 30-40 ppm and -5 to -15 ppm which are attributed to tetrahedral Al, distorted tetrahedral Al and octahedral Al, respectively.
  • the resonance near 55 ppm is attributed to zeolite framework tetrahedral Al which overlaps with another centered broad resonance in between 20-50 ppm is attributed to distorted tetrahedral Al resulting from bonding with zeolite framework aluminum and phosphorous.
  • Another signal at -6 ppm (refer to Figure 5C of the accompanying drawings) and -14 ppm (refer to Figure 5D of the accompanying drawings) are due to octahedral aluminum resulting from kaolin clay.
  • the FCC catalyst additive of the present disclosure is substantially free from aluminum phosphate (A1P0 4 ) crystal phase due to interaction of matrix aluminum and phosphorous oxides.
  • the X-ray diffraction pattern of the FCC catalyst additive shows an absence of a peak at 2 ⁇ value of 21.6° attributed to aluminum phosphate crystal phase (A1P0 4 ).
  • the relative crystallinity (%) of the FCC catalyst additive composition of the present disclosure typically ranges from 28 to 42 %, preferably from 30 to 37 %, as measured in accordance with XRD.
  • the inventors have analyzed different characteristic properties such as surface morphology, surface area, pore volume, pore size distribution, pore diameters and the like.
  • the surface morphology analyzed by scanning electron microscopy shows the presence of smooth spherical shaped crystals with uniform distribution of the catalyst additive components (refer to Figure 2A and Figure 2B of the accompanying drawings for the scanning electron microscope images of the FCC catalyst additive of the present disclosure).
  • the FCC catalyst additive of the present disclosure has total surface area in the range of 90 to 120 m 2 /g and preferably 95-115 m 2 /g; zeolite surface area in the range of 65 to 76 m 2 /g before steaming whereas after steaming zeolite surface area is in the range of 45 to 70 m 2 /g; matrix surface area before steaming is in the range of 35-50 m /g and after steaming matrix surface area is 60- 100 m 2 /g; total pore volume before steaming is in the range of 0.06 to 0.22 cc/g, and after steaming total pore volume is in the range of 0.07 to 0.16 cc/g; micro pore volume before and after steaming is in the range of 0.025 to 0.045 cc/g; and average pore diameter (BJH) before steaming is in the range of 70 to 120 A and after steaming average pore diameter (BJH) is 50 to 100 A.
  • the total acidity of the FCC catalyst additive composition of the present disclosure typically before steaming ranges from 200 to 500 ⁇ /g and after steaming it decreases to 30 to 70 ⁇ /g, as measured in accordance with temperature programmed desorption (TPD) of ammonia (Reference: Autochem 2920 operators' manual and ASTM 4824 (2008)).
  • TPD temperature programmed desorption
  • the characteristic features of the FCC catalyst additive composition of the present disclosure as herein above described represent the characteristic attributes before steaming the catalyst additive under simulated conditions of steam treatment.
  • the FCC catalyst additive composition of the present disclosure sustains its stability and catalytic activity even after subjecting the additive under severe hydrothermal deactivation conditions that are particularly employed in a commercial FCC regenerator during the treatment of the spent FCC catalyst and additives.
  • the FCC catalyst additive is subjected to pre-determined simulated conditions of steam treatment at the laboratory scale.
  • the pre-determined simulated conditions of steam treatment typically includes a temperature varying from 750 to 850 °C, preferably from 780 to 810 °C for a time period varying from 3 to 200 hours, preferably from 20 to 150 hours under 60-100 % steam.
  • the FCC catalyst additive composition thus obtained after steaming is further analyzed for its characteristic features similar to the characterization of the FCC catalyst additive composition before steaming as herein above described.
  • the 27 Al MAS NMR spectrum of the FCC catalyst additive of the present disclosure after steaming is also illustrated in Figure 5C and Figure 5D of the accompanying drawings.
  • the 27 Al MAS NMR spectra of the FCC catalyst additive after steaming show a single sharp and intense signal having maxima at the value 40 to 45 ppm which is attributed to tetrahedral aluminum in a distorted position at zeolite framework wherein Al is in bonding with phosphorous (Al-P-O).
  • a minor broad signal is also observed near -10 ppm which is due to octahedral aluminum sites of the kaolin clay.
  • the peak corresponding to the octahedral alumina of the clay was very intense before steaming and almost absent after steaming due to kaolin clay phase transformation.
  • the distinctive feature of the FCC catalyst additive of the present disclosure is the absence of the octahedral aluminum species after steaming.
  • the conventional FCC catalyst additive shows the presence of distorted tetrahedral framework aluminum resonance at 40 ppm and non-framework octahedral aluminum peak at 12 ppm arising either from alumina matrix or non-framework aluminum in coordination with phosphorous (A1P0 4 ) species.
  • the FCC catalyst additive composition of the present disclosure after steaming is also subjected to X-ray diffraction analysis.
  • the X-ray diffraction (XRD) pattern of the FCC catalyst additives of the present disclosure and conventional FCC catalyst additive after steaming are illustrated in Figure 3B of the accompanying drawings.
  • the XRD pattern of the FCC catalyst additive composition of the present disclosure clearly illustrates an absence of a XRD reflection at 2 ⁇ value of 21.6° attributed to aluminum phosphate crystal phase (A1P0 4 ).
  • the absence of A1P0 4 phase is the distinctive feature of the FCC catalyst additive of the present disclosure as compared to the conventional FCC catalyst additive composition.
  • the relative crystallinity (%) of the FCC catalyst additive of the present disclosure also remains intact even after steaming and is found to be varying from 28 to 38 %, preferably from 30 to 36% (Reference: Integrated Peak Area Method, ASTM D 5758-01).
  • the acidity of the FCC catalyst additive after steaming under the simulated conditions of steam treatment decreases as compared to the FCC catalyst additive before steaming.
  • the total acidity of the FCC catalyst additive of the present disclosure after steaming typically ranges from 25 to 100 ⁇ /g, preferably 40 to 70 ⁇ /g.
  • the decrease in the acidity of the FCC catalyst additive after steaming is due to the de-alumination of zeolite framework aluminum.
  • the FCC catalyst additive of the present disclosure after steaming shows lesser decline in the acidity as compared to the conventional FCC catalyst additives wherein a sharp decline in the acidity of the catalyst additive after steaming is observed. This is attributed to lesser de-alumination of the zeolite framework in the FCC catalyst additive of the present disclosure.
  • the total surface area of the FCC catalyst additive after steaming increases as compared to the total surface area of the FCC catalyst additive before steaming. Similar trends are also observed for the matrix surface area of the FCC catalyst additive composition.
  • the increase in matrix surface area is due to the relocation of aluminum/phosphorous sites outside the framework and vacation of phosphate ions from the zeolite pores which happens during the hydrothermal deactivation conditions.
  • increase in zeolite surface area and matrix surface area depends on the phosphate content and the binders used in the formulation.
  • the higher matrix surface area/total surface area of the present FCC catalyst additive after steaming specifies better stability and superior performance.
  • the total surface area of the FCC catalyst additive of the present disclosure after steaming ranges from 130-200 and most preferably 140-170 m 2 /g
  • zeolite surface area ranges from 60- 80 m 2 /g and preferably 68 to 70 m 2 /g
  • the matrix surface area ranges from 70-120 m 2 /g and preferably 83 to 98 m 2 /g.
  • the zeolite surface area and thereby total surface area are found to be decreased due to different stabilization methodology as the binder and phosphate sources are different (Table 2).
  • the present disclosure also provides a process for the preparation of a catalyst additive for fluid catalytic cracking of the hydrocarbon oil.
  • zeolite slurry is prepared and stabilized of by addition of phosphate slurry followed by aging.
  • binder slurry is prepared and treated with an acid to which the clay slurry is added to obtain clay-binder slurry. Then the clay-binder slurry is added to zeolite slurry to obtain zeolite-clay-binder slurry having a maximum viscosity of 2000 cP. which is spray dried to obtain microspheres. The microspheres are then calcined to obtain the catalyst additive.
  • steps of stabilization of zeolite slurry with phosphate and treatment of binder slurry with acid are collectively optimized in such a manner that the pH of the zeolite-clay-binder slurry at the end of step of spray drying is maintained in the range of 5.5 to 7.0.
  • At least one organic polar compound selected from the group consisting of alcohols, diols, triols and polyols is added to the zeolite-clay-binder slurry to reduce the viscosity of slurry and bulk density of finished products.
  • the organic polar compound is at least single alcohol having carbon atoms in the range of 1 to 4.
  • microsphere particles of FCC catalyst additive compositions as shown in Table- 1 were subjected to various physiochemical techniques for the evaluation of various physical properties like surface area (SA), average particle size (APS), apparent bulk density (ABD) and attrition index (AI) as per ASTM D5757.
  • SA surface area
  • APS average particle size
  • ABS apparent bulk density
  • AI attrition index
  • microsphere particles of conventional FCC catalyst additive composition were also subjected to various physicochemical analysis for the evaluation of physical properties like surface area (SA), average particles size (APS), apparent bulk density (ABD) and attrition index (AI) as per .
  • SA surface area
  • APS average particles size
  • ABS apparent bulk density
  • AI attrition index
  • Table 1 Composition details of FCC catalyst additives of example- 1 and example-2 (Ex-1 and Ex-2) and conventional FCC catalyst additive (Comp. Ex).
  • Table 2 Physico-chemical properties of the FCC catalyst additive compositions of example -1 (Ex-1) and example-2 (Ex-2) and conventional FCC catalyst additive composition (Comp. Ex).
  • the conventional FCC catalyst additive also demonstrates reduced attrition properties and more fines generation as compared to the catalyst additives of examples- 1 and 2 (Ex-1 and Ex-2).
  • Attrition index is one the key properties of the FCC catalyst additives.
  • Attrition index (AI) less than 10 is highly desirable for most of the FCC units.
  • High AI (>10) samples generates more fines causes environmental issues due stack emission. Further, it also leads to reliability and operational issues in the operation of FCC unit having Power Recovery Turbine (PRT) unit, since these fines deposit on the turbine blades result in PRT vibrations.
  • PRT Power Recovery Turbine
  • the better stability performance of the FCC catalyst additives of examples- 1 and 2 (Ex-1 and Ex-2), after steaming, as compared to the conventional FCC catalyst additive is attributed to better stabilization of zeolite framework.
  • Example 2 (Ex-1 and Ex-2) illustrates smooth surface and uniform distribution of various components of the composition, whereas SEM of Comp. Ex composition illustrates poor sphericity with uneven particles. Further, some fine particles ( ⁇ 15 ⁇ ) are found to be glued on large particles.
  • Relative crystallinity (%) of the FCC catalyst additive compositions are measured by X-Ray Diffraction (XRD),.
  • XRD X-Ray Diffraction
  • Figure 3(B) clearly illustrates the absence of aluminum phosphate phase (A1P0 4 ) in the FCC catalyst additives Ex-1 and Ex-2 after steaming under simulated conditions of steam treatment.
  • the XRD observations are similar for FCC catalyst additives Ex-1 and Ex-2 before steaming.
  • Acidity of the FCC catalyst additive compositions of examples- 1 and 2 (Ex-1 and Ex-2) and conventional FCC catalyst additive composition (Comp. Ex) are measured by temperature programmed desorption of ammonia method (TPD).
  • Figure 4(A) and 4(B) illustrate TPD of ammonia pattern of ZSM-5 zeolites used in the FCC catalyst additive compositions of examples- 1 and 2 and the FCC catalyst additives (Ex-1, Ex-2, Comp.Ex) after steaming, respectively. It is evident from the figure that after steaming at the simulated conditions of steam treatment, the FCC catalyst additives of examples- 1 and 2 (Ex-1 and Ex-2) show superior acidity as compared to the conventional FCC catalyst additive (Comp. Ex) and these acid sites are responsible for better catalytic activity and high propylene yield in the FCC process.
  • Figure 5A of the accompanying drawing shows the presence of an intense signal at 60 ppm due to tetrahedral aluminum of zeolite framework in the ZSM-5 zeolite used in the FCC catalyst additive composition of example- 1.
  • Another signal at 6 ppm is of typical non- framework (NF) octahedral aluminum.
  • the zeolite used in FCC catalyst additive composition of example-2 shows an intense signal at 57 ppm due to tetrahedral aluminum and is substantially free of non-framework aluminum species as the signal due to octahedral aluminum is weak at 0.5 ppm.
  • the 27 Al MAS NMR spectra of conventional FCC catalyst additive Comp.
  • FIG. 5C of the accompanying drawings illustrates 27 Al MAS NMR spectra of the FCC catalyst additive composition of example- 1 before and after steaming.
  • the FCC catalyst additive composition Ex-1 before steaming shows three signals at 59 ppm, 40 ppm and -6 ppm.
  • the signal at 59 ppm is due to tetrahedral aluminum of the zeolite framework and other signal at 40 ppm is due to the distorted tetrahedral aluminum.
  • the signal at -6 ppm is attributed to octahedral aluminum of the kaolin clay, and to a lesser extent, from extra- framework aluminum sites of the zeolite.
  • a sharp intense signal at 40 ppm was observed which was attributed to tetrahedral aluminum in a distorted position at zeolite framework where Al is stabilized (bonding) with phosphorous.
  • FIG. 5D of the accompanying drawings illustrates 27 Al MAS NMR spectra of the FCC catalyst additive composition of example-2 before and after steaming.
  • the FCC catalyst additive Ex-2 before steaming shows two major signals at 53 ppm and - 14 ppm.
  • the signal at 53 ppm is due to tetrahedral aluminum of the zeolite framework and other signal at -14 ppm is assigned due to octahedral aluminum of the kaolin clay.
  • There was a broad signal in the range of 10-40 ppm is attributed to bonding/interaction of framework aluminum with phosphate (Al-O-P-).
  • the spectrum of Ex-2 is dominated by a very high intense and sharp peak at 39 ppm due to aluminum in a distorted tetrahedral environment at zeolite framework position (Al-O-P-).
  • Example-3 The distinctive features of the FCC catalyst additive compositions of examples- 1 and 2 (Ex- land Ex-2) is the absence of octahedral aluminum species coordinated with extra framework aluminum phosphate or alumina present in the matrix in comparison to the conventional FCC catalyst additive (Com. Ex).
  • Example-3 The distinctive features of the FCC catalyst additive compositions of examples- 1 and 2 (Ex- land Ex-2) is the absence of octahedral aluminum species coordinated with extra framework aluminum phosphate or alumina present in the matrix in comparison to the conventional FCC catalyst additive (Com. Ex).
  • Example-3 The distinctive features of the FCC catalyst additive compositions of examples- 1 and 2 (Ex- land Ex-2) is the absence of octahedral aluminum species coordinated with extra framework aluminum phosphate or alumina present in the matrix in comparison to the conventional FCC catalyst additive (Com. Ex).
  • This example describes a fluid catalytic cracking process carried out by using a catalyst composition comprising a combination of a conventional FCC catalyst (RE USY based) and the FCC catalyst additives Ex-1 and Ex-2 of examples 1 and 2.
  • the FCC catalyst additives Ex-1 and Ex-2 used for the purpose of the FCC process are the steamed FCC catalyst additives Ex-1 and Ex-2.
  • the conventional FCC catalyst (RE USY) was also steamed under the simulated conditions of steam treatment at laboratory scale that includes steaming of the FCC catalyst at 800 °C for 20 hours at 100 % steam.
  • the steamed FCC catalyst and the steamed FCC catalyst additive Ex-1 were mixed in weight ratio of 75:25, and were loaded in a fixed fluid bed ACE micro reactor.
  • the microreactor was electrically heated to maintain the catalyst bed temperature at 545 °C.
  • the hydrotreated Vacuum Gas Oil (VGO) was injected in the fluidized bed for 30 seconds to generate the cracking data at various catalysts to oil ratios.
  • the properties of VGO are shown in Table 3.
  • the product yields at 77% conversion of VGO are provided in Table 4.
  • the FCC catalyst additives Ex-1 and Ex-2 showed high performance and higher propylene yield in comparison to conventional FCC catalyst additive (comp.Ex).
  • the use of alumina and silica binders based conventional FCC catalyst additive (Comp.Ex) gives lower gasoline cracking, and thereby lower propylene yield.
  • the superior performance the FCC catalyst additive compositions Ex-1 and Ex-2 is attributed to better stabilized zeolite framework aluminum sites of the additive composition.
  • hydrothermally stable FCC catalyst additive composition has several technical advancements that include but are not limited to the realization of:
  • FCC catalyst additive composition is consisting of binder free from alumina ,
  • FCC catalyst additive composition is free from aluminum phosphate crystal phase in comparison to the conventional catalyst additive; the absence of aluminum phosphate crystal phase possibly reduces the pore blockage of zeolite or external surface thereby providing better catalytic activity and stability, and

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present disclosure relates to an FCC catalyst additive comprising a zeolite, a binder and a clay, wherein the phosphorous content is in the form of P2O5 and colloidal silica as a binder. The FCC catalyst additive is characterized by absence of aluminum phosphate crystal phase and presence of at least one of the species of zeolite framework tetrahedral aluminum, zeolite framework distorted tetrahedral aluminum and non-framework octahedral aluminum. The present disclosure also relates to a process of the preparation of said FCC catalyst additive.

Description

HYDROTHERMALLY STABLE FCC CATALYST ADDITIVE COMPOSITION
The present disclosure relates to catalyst additive compositions used in refinery processes particularly in fluid catalytic cracking (FCC) process and the process of preparation for the same.
BACKGROUND:
In refinery, the fluid catalytic cracking (FCC) processes are mostly carried out by using a catalyst that comprises a mixture of large pore size crystalline zeolite (pore size greater than
7 A (angstrom units)) containing FCC catalyst and medium pore size zeolite (pore size lower than 7 A (angstrom units)) containing additive. The use of ZSM-5 type zeolite containing additives in FCC process is well known for the maximization of lower olefins (C2, C3 & C4).
The FCC processes, executed at industrial scale involve the recycling of spent catalyst and before recycling, the spent catalyst is subjected to regeneration. The regeneration of the spent catalyst is either carried out thermally or hydro thermally. Hydrothermal stability of zeolites is one of the major concerns in FCC processes. Each regeneration step results into partial deactivation of catalyst/additive due to de-alumination of zeolites by loss of Al-OH-Si groups, responsible for the Bronsted acidity of the zeolites. Therefore, preventing or minimizing de-alumination is a topic of continuous interest in the field of FCC applications.
Generally, FCC catalyst and additives in lab or pilot scale are tested for deactivation by subjecting the catalyst/additive to hydrothermal deactivation at 650-820 °C for 3-20 hours under 60-100% steam to simulate commercial FCC plant steam deactivation conditions. It is known that the FCC catalyst comprising USY based zeolite deactivates fast and attains equilibrium rapidly i.e., 3-20 hours of the steam deactivation. Hence, the typical steaming protocol for FCC catalyst involves 3-20 hours at 650-820 °C. On the contrary, deactivation of zeolite in ZSM-5 additives is continuous with time and it is tricky to select appropriate steaming conditions for lab or pilot testing to predict commercial FCC plant performance of the catalyst additive.
Therefore, there is felt a need to provide an FCC catalyst additive composition that demonstrates better stability and sustained catalyst activity.
OBJECTS:
Some of the objects of the present disclosure are described herein below:
It is an object of the present disclosure to provide a hydrothermally stable FCC catalyst additive that retains its physical and chemical properties for a considerably longer period of time.
Another object of the present disclosure is to provide a hydrothermally stable FCC catalyst additive which demonstrates excellent stability and catalytic activity.
Other objects and advantages of the present invention will be more apparent from the following description when read in conjunction with the accompanying figures, which are not intended to limit the scope of the present invention.
SUMMARY:
The present disclosure relates to a catalyst additive for fluid catalytic cracking of the hydrocarbon oil comprising a zeolite, a binder, and a clay, characterized in that the said catalyst additive comprises: a. phosphorous content in the form of P205;
b. colloidal silica as a binder;
c. presence of at least one 27 Al MAS NMR peak having maxima at each of the values in the range of 50-60 ppm, 30-50 ppm and -15 to +15 ppm corresponding to the zeolite framework tetrahedral aluminum, zeolite framework distorted tetrahedral aluminum and non-framework octahedral aluminum, respectively, before the steaming protocol; d. presence of said distorted tetrahedral and absence of said non-framework octahedral Al peak in the 27 Al MAS NMR after steaming, substantiates the non- addition of external alumina; and
e. absence of an X-ray diffraction peak at the 2Θ value of 21.60° corresponding to aluminum phosphate crystal phase (A1P04).
The present disclosure also relates to a process for the preparation of the catalyst additive.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS:
Figures 1A of the accompanying drawings illustrate nitrogen adsorption- isotherms of pure ZSM-5 zeolites at -196 °C (zeolites present in the FCC catalyst additive composition of examples 1 and 2)
Figure IB of the accompanying drawings illustrate the nitrogen adsorption isotherms of catalyst additives of the present disclosure (Ex-1 and Ex- 2) and conventional FCC catalyst additive (Comp. Ex), wherein all the additives are steamed at simulated conditions of steam treatment, in accordance with the present disclosure;
Figure 1C of the accompanying drawings illustrates pore size distribution (BJH desorption pore volume) of FCC catalyst additives (Ex-1 and Ex- 2) of the present disclosure and conventional FCC catalyst additive (Comp. Ex) after steaming at simulated conditions of steam treatment, in accordance with the present disclosure;
Figures 2A, 2B and 2C of the accompanying drawings illustrate scanning electron microscope images of FCC catalyst additives of the present disclosure (Ex-1 and Ex-2) and conventional FCC catalyst additive (Comp. Ex), respectively after steaming at the simulated conditions of steam treatment, in accordance with the present disclosure;
Figures 3A and 3B of the accompanying drawings illustrate X-ray diffraction patterns of crystalline ZSM-5 zeolites, FCC catalyst additives of the present disclosure (Ex-1 and Ex-2), and conventional FCC catalyst additive (Comp. Ex.), respectively, wherein all the FCC catalyst additives are steamed at simulated conditions of steam treatment, in accordance with the present disclosure;
Figures 4A and 4B of the accompanying drawings illustrate temperature programmed desorption of ammonia patterns of ZSM-5 zeolites and FCC catalyst additives of the present disclosure (Ex-1 and Ex- 2) and conventional FCC catalyst additive (Comp.Ex), respectively wherein all the FCC catalyst additives are steamed at simulated conditions of steam treatment, in accordance with the present disclosure;
Figure 5A of the accompanying drawings illustrates 27 Al MAS NMR spectra of ZSM-5 zeolites of different crystal size used in the present invention;
Figure 5B of the accompanying drawings illustrates 27 Al MAS NMR spectra of conventional FCC catalyst additive (Comp. Ex.), wherein graph "b" denotes 27 Al MAS NMR spectra before steaming and graph "a" denotes 27 Al MAS NMR spectra after steaming at the simulated conditions of steam treatment;
Figure 5C of the accompanying drawings illustrates 27 Al MAS NMR spectra of the FCC catalyst additive of the present disclosure (Ex-1) wherein graph "b" denotes 27 Al MAS NMR spectra before steaming and graph "a" denotes 27 Al MAS NMR spectra after steaming at the simulated conditions of steam treatment, in accordance with the present disclosure; and
Figure 5D of the accompanying drawings illustrates 27 Al MAS NMR spectra of the FCC catalyst additive of the present disclosure (Ex-2) wherein graph "a" denotes 27 Al MAS NMR spectra before steaming and graph "b" denotes 27 Al MAS NMR spectra after steaming at the simulated conditions of stream treatment, in accordance with the present disclosure.
DETAILED DESCRIPTION:
In accordance with the present disclosure, there is provided an FCC catalyst additive composition comprising ZSM-5 zeolite, phosphorous, a binder and a clay, characterized in that the FCC catalyst additive exhibits ZSM-5 zeolite content is 30 to 60%; phosphorous content in the form of P205 of at least 5.5 wt%; binder containing colloidal silica, presence of at least one 27 Al MAS NMR peak having maxima at the values ranging from 50 to 60 ppm, 30 to 50 ppm, and -15 to +15 ppm corresponding to zeolite framework tetrahedral aluminum, zeolite framework distorted tetrahedral aluminum and non-framework octahedral aluminum, respectively; and absence of an X-ray diffraction peak at 2Θ value of 21.6° corresponding to aluminum phosphate crystal phase (A1P04).
The alumina content of the FCC catalyst additive of the present disclosure ranges from 14 wt% to 22 wt%. In accordance with one of the embodiments of the present disclosure, the alumina content ranges from 15 to 19 wt%.
The phosphorous content in the form of P205 typically ranges from 5.5 to 12 wt%. In accordance with one of the embodiments of the present disclosure, the phosphorous content in the form of P205 ranges from 6 to 10 wt%.
The alumina and the phosphorous contents of the FCC catalyst additive composition are measured by using an inductively coupled plasma atomic emission spectroscopy (ICP-AES). In accordance with the present disclosure the binder does not contain any alumina.
In accordance with one of the embodiments of the present disclosure, the FCC catalyst additive composition of the present disclosure shows distinctive 27 Al MAS NMR peaks at 53-59 ppm, 30-40 ppm and -5 to -15 ppm which are attributed to tetrahedral Al, distorted tetrahedral Al and octahedral Al, respectively. The 27 Al MAS, NMR spectra of the FCC catalyst additive of the present disclosure illustrated in Figure 5C and Figure 5D of the accompanying drawings. The resonance near 55 ppm is attributed to zeolite framework tetrahedral Al which overlaps with another centered broad resonance in between 20-50 ppm is attributed to distorted tetrahedral Al resulting from bonding with zeolite framework aluminum and phosphorous. Another signal at -6 ppm (refer to Figure 5C of the accompanying drawings) and -14 ppm (refer to Figure 5D of the accompanying drawings) are due to octahedral aluminum resulting from kaolin clay.
The FCC catalyst additive of the present disclosure is substantially free from aluminum phosphate (A1P04) crystal phase due to interaction of matrix aluminum and phosphorous oxides. The X-ray diffraction pattern of the FCC catalyst additive shows an absence of a peak at 2Θ value of 21.6° attributed to aluminum phosphate crystal phase (A1P04). (Refer to Figure 3B of the accompanying drawings). Further, the relative crystallinity (%) of the FCC catalyst additive composition of the present disclosure typically ranges from 28 to 42 %, preferably from 30 to 37 %, as measured in accordance with XRD.
To further differentiate the distinguishable properties of the FCC catalyst additive composition of the present disclosure, the inventors have analyzed different characteristic properties such as surface morphology, surface area, pore volume, pore size distribution, pore diameters and the like. The surface morphology analyzed by scanning electron microscopy shows the presence of smooth spherical shaped crystals with uniform distribution of the catalyst additive components (refer to Figure 2A and Figure 2B of the accompanying drawings for the scanning electron microscope images of the FCC catalyst additive of the present disclosure).
The FCC catalyst additive of the present disclosure has total surface area in the range of 90 to 120 m2/g and preferably 95-115 m2/g; zeolite surface area in the range of 65 to 76 m2/g before steaming whereas after steaming zeolite surface area is in the range of 45 to 70 m2/g; matrix surface area before steaming is in the range of 35-50 m /g and after steaming matrix surface area is 60- 100 m2/g; total pore volume before steaming is in the range of 0.06 to 0.22 cc/g, and after steaming total pore volume is in the range of 0.07 to 0.16 cc/g; micro pore volume before and after steaming is in the range of 0.025 to 0.045 cc/g; and average pore diameter (BJH) before steaming is in the range of 70 to 120 A and after steaming average pore diameter (BJH) is 50 to 100 A. The surface area and pore volume of the FCC catalyst additive composition of the present disclosure are measured by BET techniques and zeolite surface area and matrix surface areas are measured by t-plot method (Reference: ASAP Operators' manual and ASTM D 4365 - 95).
The total acidity of the FCC catalyst additive composition of the present disclosure typically before steaming ranges from 200 to 500 μηιοΐ/g and after steaming it decreases to 30 to 70 μπιοΐ/g, as measured in accordance with temperature programmed desorption (TPD) of ammonia (Reference: Autochem 2920 operators' manual and ASTM 4824 (2008)). The characteristic features of the FCC catalyst additive composition of the present disclosure as herein above described represent the characteristic attributes before steaming the catalyst additive under simulated conditions of steam treatment.
The FCC catalyst additive composition of the present disclosure sustains its stability and catalytic activity even after subjecting the additive under severe hydrothermal deactivation conditions that are particularly employed in a commercial FCC regenerator during the treatment of the spent FCC catalyst and additives. In order to evaluate the catalytic activity and stability of the FCC catalyst additive composition of the present disclosure, the FCC catalyst additive is subjected to pre-determined simulated conditions of steam treatment at the laboratory scale. The pre-determined simulated conditions of steam treatment typically includes a temperature varying from 750 to 850 °C, preferably from 780 to 810 °C for a time period varying from 3 to 200 hours, preferably from 20 to 150 hours under 60-100 % steam. The FCC catalyst additive composition thus obtained after steaming is further analyzed for its characteristic features similar to the characterization of the FCC catalyst additive composition before steaming as herein above described.
The 27 Al MAS NMR spectrum of the FCC catalyst additive of the present disclosure after steaming is also illustrated in Figure 5C and Figure 5D of the accompanying drawings. The 27 Al MAS NMR spectra of the FCC catalyst additive after steaming show a single sharp and intense signal having maxima at the value 40 to 45 ppm which is attributed to tetrahedral aluminum in a distorted position at zeolite framework wherein Al is in bonding with phosphorous (Al-P-O). A minor broad signal is also observed near -10 ppm which is due to octahedral aluminum sites of the kaolin clay. The peak corresponding to the octahedral alumina of the clay was very intense before steaming and almost absent after steaming due to kaolin clay phase transformation. The distinctive feature of the FCC catalyst additive of the present disclosure is the absence of the octahedral aluminum species after steaming. In contrast, the conventional FCC catalyst additive shows the presence of distorted tetrahedral framework aluminum resonance at 40 ppm and non-framework octahedral aluminum peak at 12 ppm arising either from alumina matrix or non-framework aluminum in coordination with phosphorous (A1P04) species. The FCC catalyst additive composition of the present disclosure after steaming is also subjected to X-ray diffraction analysis. The X-ray diffraction (XRD) pattern of the FCC catalyst additives of the present disclosure and conventional FCC catalyst additive after steaming are illustrated in Figure 3B of the accompanying drawings. The XRD pattern of the FCC catalyst additive composition of the present disclosure clearly illustrates an absence of a XRD reflection at 2Θ value of 21.6° attributed to aluminum phosphate crystal phase (A1P04). The absence of A1P04 phase is the distinctive feature of the FCC catalyst additive of the present disclosure as compared to the conventional FCC catalyst additive composition. Further, the relative crystallinity (%) of the FCC catalyst additive of the present disclosure also remains intact even after steaming and is found to be varying from 28 to 38 %, preferably from 30 to 36% (Reference: Integrated Peak Area Method, ASTM D 5758-01).
The acidity of the FCC catalyst additive after steaming under the simulated conditions of steam treatment decreases as compared to the FCC catalyst additive before steaming. The total acidity of the FCC catalyst additive of the present disclosure after steaming typically ranges from 25 to 100 μηιοΐ/g, preferably 40 to 70 μπιοΐ/g. The decrease in the acidity of the FCC catalyst additive after steaming is due to the de-alumination of zeolite framework aluminum. However, the FCC catalyst additive of the present disclosure after steaming shows lesser decline in the acidity as compared to the conventional FCC catalyst additives wherein a sharp decline in the acidity of the catalyst additive after steaming is observed. This is attributed to lesser de-alumination of the zeolite framework in the FCC catalyst additive of the present disclosure.
The total surface area of the FCC catalyst additive after steaming increases as compared to the total surface area of the FCC catalyst additive before steaming. Similar trends are also observed for the matrix surface area of the FCC catalyst additive composition. The increase in matrix surface area is due to the relocation of aluminum/phosphorous sites outside the framework and vacation of phosphate ions from the zeolite pores which happens during the hydrothermal deactivation conditions. Hence, increase in zeolite surface area and matrix surface area depends on the phosphate content and the binders used in the formulation. Thus, the higher matrix surface area/total surface area of the present FCC catalyst additive after steaming specifies better stability and superior performance.
The total surface area of the FCC catalyst additive of the present disclosure after steaming ranges from 130-200 and most preferably 140-170 m2/g, zeolite surface area ranges from 60- 80 m2/g and preferably 68 to 70 m2/g and the matrix surface area ranges from 70-120 m2/g and preferably 83 to 98 m2/g. In case of conventional FCC catalyst additive composition, after steaming at the simulated conditions of steam treatment as herein above described, the zeolite surface area and thereby total surface area are found to be decreased due to different stabilization methodology as the binder and phosphate sources are different (Table 2).
From the evaluation of the physical properties of the FCC catalyst additive composition of the present disclosure as herein above described it is clearly evident that the FCC catalyst additive composition of the present disclosure sustains most of the physical properties even after subjecting the additive under severe conditions of hydrothermal deactivation.
The present disclosure also provides a process for the preparation of a catalyst additive for fluid catalytic cracking of the hydrocarbon oil.
Initially, zeolite slurry is prepared and stabilized of by addition of phosphate slurry followed by aging.
Simultaneously, binder slurry is prepared and treated with an acid to which the clay slurry is added to obtain clay-binder slurry. Then the clay-binder slurry is added to zeolite slurry to obtain zeolite-clay-binder slurry having a maximum viscosity of 2000 cP. which is spray dried to obtain microspheres. The microspheres are then calcined to obtain the catalyst additive.
In the steps of stabilization of zeolite slurry with phosphate and treatment of binder slurry with acid are collectively optimized in such a manner that the pH of the zeolite-clay-binder slurry at the end of step of spray drying is maintained in the range of 5.5 to 7.0.
In one of the embodiments of the present disclosure at least one organic polar compound selected from the group consisting of alcohols, diols, triols and polyols is added to the zeolite-clay-binder slurry to reduce the viscosity of slurry and bulk density of finished products. In particular embodiment of the present disclosure the organic polar compound is at least single alcohol having carbon atoms in the range of 1 to 4.
The embodiments herein and the various features and advantageous details thereof are explained with reference to the non-limiting embodiments in the following description. Descriptions of well-known components and processing techniques are omitted so as to not unnecessarily obscure the embodiments herein. The examples used herein are intended merely to facilitate an understanding of ways in which the embodiments herein may be practiced and to further enable those of skill in the art to practice the embodiments herein. Accordingly, the examples should not be construed as limiting the scope of the embodiments herein.
Examples 1 to 2 (Ex-1 to Ex-2):
The microsphere particles of FCC catalyst additive compositions as shown in Table- 1 were subjected to various physiochemical techniques for the evaluation of various physical properties like surface area (SA), average particle size (APS), apparent bulk density (ABD) and attrition index (AI) as per ASTM D5757. The composition details and physicochemical properties of catalyst additives compositions (Ex-1, Ex-2) are shown in Table 1 and Table 2 respectively.
In order to evaluate the performance of the FCC catalyst additive compositions Ex-1 and Ex- 2, the microsphere particles of the FCC catalyst additive compositions Ex-1 and Ex-2 were subjected to severe simulated conditions of steam treatment at the laboratory scale. The simulated conditions of steam treatment at laboratory scale include steaming of the additive composition at a temperature of 800 °C for 100 hours using 100 % steam at atmospheric pressure. Comparative Example: Conventional FCC catalyst additive (Comp. Ex):
The microsphere particles of conventional FCC catalyst additive composition were also subjected to various physicochemical analysis for the evaluation of physical properties like surface area (SA), average particles size (APS), apparent bulk density (ABD) and attrition index (AI) as per . Similar to the FCC catalyst additive compositions Ex-1 and Ex-2, the conventional FCC catalyst additive composition (Comp.Ex) was also subjected to severe simulated conditions of steam treatment at laboratory scale. The composition and physicochemical properties of conventional FCC catalyst additive (Comp.Ex.) before and after steaming are also shown in Table 1 and Table 2 respectively.
Table 1: Composition details of FCC catalyst additives of example- 1 and example-2 (Ex-1 and Ex-2) and conventional FCC catalyst additive (Comp. Ex).
Figure imgf000012_0001
measured from scanning electron microscopy (SEM)
Table 2: Physico-chemical properties of the FCC catalyst additive compositions of example -1 (Ex-1) and example-2 (Ex-2) and conventional FCC catalyst additive composition (Comp. Ex).
Figure imgf000012_0002
Figure imgf000013_0001
Figure imgf000014_0001
It is clear from the data tabulated in Table-2 that the FCC catalyst additives of examples 1 and 2 (Ex-1 and Ex-2) retain their most of the physical properties such as surface area, pore volume, pore diameter, relative crystallinity (%) even after subjecting the additives under the severe hydrothermal deactivation conditions. However, the conventional FCC catalyst additive (Comp. Ex) shows inferior physical properties after steaming under the severe hydrothermal deactivation conditions.
The conventional FCC catalyst additive also demonstrates reduced attrition properties and more fines generation as compared to the catalyst additives of examples- 1 and 2 (Ex-1 and Ex-2). Attrition index is one the key properties of the FCC catalyst additives. Attrition index (AI) less than 10 is highly desirable for most of the FCC units. High AI (>10) samples generates more fines causes environmental issues due stack emission. Further, it also leads to reliability and operational issues in the operation of FCC unit having Power Recovery Turbine (PRT) unit, since these fines deposit on the turbine blades result in PRT vibrations. The better stability performance of the FCC catalyst additives of examples- 1 and 2 (Ex-1 and Ex-2), after steaming, as compared to the conventional FCC catalyst additive is attributed to better stabilization of zeolite framework.
The nitrogen adsorption isotherms of the FCC catalyst additive compositions of examples- 1 and 2 (Ex-1 and Ex-2) and conventional FCC catalyst additive composition (Comp. Ex) after steaming are provided in Figure- 1(B) of the accompanying drawings. Figure- 1(B) clearly illustrates that there is a variation in the shape of the isotherms of Ex-1, Ex-2 and Comp. Ex which indicates that deactivation has occurred much in Comp. Ex as compared to Ex-1 and Ex-2, thereby indicating lower porosity in Comp. Ex.
Pore size distribution of the FCC catalyst additive compositions of examples- 1 and 2 (Ex-1 and Ex-2) and conventional FCC catalyst additive composition (Comp. Ex) after steaming are illustrated in Figure- 1 (C) of the accompanying drawings. The FCC catalyst additives Ex-
1 and Ex-2 even after steaming possess higher pore volume as compared to the conventional FCC catalyst additive composition (Comp. Ex). The high pore volume is better diffusion of hydrocarbons (gasoline range) and there by better cracking and higher propylene yields in Ex-1 and Ex-2 of the present disclosure as against conventional catalyst additive (Comp. Ex.).
The surface study of the present invention FCC catalyst additives of examples- 1 and 2 (Ex-1 & Ex-2) and conventional FCC catalyst additive (Comp. Ex) after steaming are conducted by scanning electron microscopy (SEM). The SEM images of catalyst additives Ex-1, Ex-2 and Comp. Ex after steaming are provided in Figure-2 (A), Figure 2(B) and Figure 2(C) of the accompanying drawings, respectively. SEM of the FCC catalyst additives of examples- 1 and
2 (Ex-1 and Ex-2) illustrates smooth surface and uniform distribution of various components of the composition, whereas SEM of Comp. Ex composition illustrates poor sphericity with uneven particles. Further, some fine particles (<15 μ) are found to be glued on large particles.
Relative crystallinity (%) of the FCC catalyst additive compositions are measured by X-Ray Diffraction (XRD),. The XRD pattern of crystalline ZSM-5 zeolite and the FCC catalyst additive compositions (Ex-1, Ex-2 and Comp. Ex.) are provided in Figure 3(A) and Figure 3(B) of the accompanying drawings, respectively. Figure 3(B) clearly illustrates the absence of aluminum phosphate phase (A1P04) in the FCC catalyst additives Ex-1 and Ex-2 after steaming under simulated conditions of steam treatment. The XRD observations are similar for FCC catalyst additives Ex-1 and Ex-2 before steaming.
Acidity of the FCC catalyst additive compositions of examples- 1 and 2 (Ex-1 and Ex-2) and conventional FCC catalyst additive composition (Comp. Ex) are measured by temperature programmed desorption of ammonia method (TPD). Figure 4(A) and 4(B) illustrate TPD of ammonia pattern of ZSM-5 zeolites used in the FCC catalyst additive compositions of examples- 1 and 2 and the FCC catalyst additives (Ex-1, Ex-2, Comp.Ex) after steaming, respectively. It is evident from the figure that after steaming at the simulated conditions of steam treatment, the FCC catalyst additives of examples- 1 and 2 (Ex-1 and Ex-2) show superior acidity as compared to the conventional FCC catalyst additive (Comp. Ex) and these acid sites are responsible for better catalytic activity and high propylene yield in the FCC process.
27 Al MAS NMR spectra of crystalline ZSM-5 zeolites, conventional FCC catalyst additive (comp. Ex) before and after steaming, and the FCC catalyst additive compositions Ex-1 and Ex-2 before and after steaming are illustrated in Figures 5A, 5B, 5C and 5 D of the accompanying drawings , respectively.
Figure 5A of the accompanying drawing shows the presence of an intense signal at 60 ppm due to tetrahedral aluminum of zeolite framework in the ZSM-5 zeolite used in the FCC catalyst additive composition of example- 1. Another signal at 6 ppm is of typical non- framework (NF) octahedral aluminum. The zeolite used in FCC catalyst additive composition of example-2 shows an intense signal at 57 ppm due to tetrahedral aluminum and is substantially free of non-framework aluminum species as the signal due to octahedral aluminum is weak at 0.5 ppm. The 27 Al MAS NMR spectra of conventional FCC catalyst additive (Comp. Ex) as illustrated in Figure 5B of the accompanying drawings before and after steaming clearly illustrate the presence of two peaks; an intense and sharp peak at 40 ppm which is attributed to distorted aluminum species of the zeolite framework. The drift in chemical shift of tetrahedral aluminum signal from 55 to 40 ppm is due to bonding/interaction of framework aluminum with phosphorous (Al-O-P-). The other peak at 12 ppm is attributed to octahedral aluminum species arising mainly from aluminum matrix and to a lesser extent, from extra-framework aluminum species in the zeolite. This signal may also be attributed to octahedral aluminum coordinated with water in extra-framework A1P04. The similar findings of A1P04 crystal phase has also been identified in XRD studies of the conventional FCC catalyst additive composition (Comp. Ex) (refer to Figure 3B of the accompanying drawings). The signals due to distorted tetrahedral and octahedral aluminum species are almost similar before and after steaming at the simulated conditions of steam treatment in the conventional FCC catalyst additive composition (Comp. Ex) and the intensity of the distorted tetrahedral signal are lower after steaming.
Figure 5C of the accompanying drawings illustrates 27 Al MAS NMR spectra of the FCC catalyst additive composition of example- 1 before and after steaming. The FCC catalyst additive composition Ex-1 before steaming shows three signals at 59 ppm, 40 ppm and -6 ppm. The signal at 59 ppm is due to tetrahedral aluminum of the zeolite framework and other signal at 40 ppm is due to the distorted tetrahedral aluminum. The signal at -6 ppm is attributed to octahedral aluminum of the kaolin clay, and to a lesser extent, from extra- framework aluminum sites of the zeolite. After steaming, a sharp intense signal at 40 ppm was observed which was attributed to tetrahedral aluminum in a distorted position at zeolite framework where Al is stabilized (bonding) with phosphorous.
Figure 5D of the accompanying drawings illustrates 27 Al MAS NMR spectra of the FCC catalyst additive composition of example-2 before and after steaming. The FCC catalyst additive Ex-2 before steaming shows two major signals at 53 ppm and - 14 ppm. The signal at 53 ppm is due to tetrahedral aluminum of the zeolite framework and other signal at -14 ppm is assigned due to octahedral aluminum of the kaolin clay. There was a broad signal in the range of 10-40 ppm is attributed to bonding/interaction of framework aluminum with phosphate (Al-O-P-). After steaming, the spectrum of Ex-2 is dominated by a very high intense and sharp peak at 39 ppm due to aluminum in a distorted tetrahedral environment at zeolite framework position (Al-O-P-).
The distinctive features of the FCC catalyst additive compositions of examples- 1 and 2 (Ex- land Ex-2) is the absence of octahedral aluminum species coordinated with extra framework aluminum phosphate or alumina present in the matrix in comparison to the conventional FCC catalyst additive (Com. Ex). Example-3:
This example describes a fluid catalytic cracking process carried out by using a catalyst composition comprising a combination of a conventional FCC catalyst (RE USY based) and the FCC catalyst additives Ex-1 and Ex-2 of examples 1 and 2. The FCC catalyst additives Ex-1 and Ex-2 used for the purpose of the FCC process are the steamed FCC catalyst additives Ex-1 and Ex-2.
The conventional FCC catalyst (RE USY) was also steamed under the simulated conditions of steam treatment at laboratory scale that includes steaming of the FCC catalyst at 800 °C for 20 hours at 100 % steam. The steamed FCC catalyst and the steamed FCC catalyst additive Ex-1 were mixed in weight ratio of 75:25, and were loaded in a fixed fluid bed ACE micro reactor. The microreactor was electrically heated to maintain the catalyst bed temperature at 545 °C. The hydrotreated Vacuum Gas Oil (VGO) was injected in the fluidized bed for 30 seconds to generate the cracking data at various catalysts to oil ratios. The properties of VGO are shown in Table 3. The product yields at 77% conversion of VGO are provided in Table 4.
Table 3: The properties of the VGO feed:
Figure imgf000018_0001
Properties
Distillation (SIM Dist D2887) in °C
5 wt% 327
10 wt% 350
30 wt% 401
50 wt% 433
70 wt% 470
90 wt% 518
Table 4: Product yields of a FCC process at 77% conversion:
Figure imgf000019_0001
As it is evident from Table 4, the FCC catalyst additives Ex-1 and Ex-2 showed high performance and higher propylene yield in comparison to conventional FCC catalyst additive (comp.Ex). The use of alumina and silica binders based conventional FCC catalyst additive (Comp.Ex) gives lower gasoline cracking, and thereby lower propylene yield. Further, the superior performance the FCC catalyst additive compositions Ex-1 and Ex-2 is attributed to better stabilized zeolite framework aluminum sites of the additive composition.
TECHNICAL ADVANCEMENTS:
The present disclosure that relates to hydrothermally stable FCC catalyst additive composition has several technical advancements that include but are not limited to the realization of:
• FCC catalyst additive composition is consisting of binder free from alumina ,
• FCC catalyst additive composition is free from aluminum phosphate crystal phase in comparison to the conventional catalyst additive; the absence of aluminum phosphate crystal phase possibly reduces the pore blockage of zeolite or external surface thereby providing better catalytic activity and stability, and
• Hydrothermally stable FCC catalyst additive with improved stability and catalytic activity.
The numerical values mentioned for the various physical parameters, dimensions or quantities are only approximations and it is envisaged that the values higher/lower than the numerical values assigned to the parameters, dimensions or quantities fall within the scope of the invention, unless there is a statement in the specification specific to the contrary.
The foregoing description of the specific embodiments will so fully reveal the general nature of the embodiments herein that others can, by applying current knowledge, readily modify and/or adapt for various applications such specific embodiments without departing from the generic concept, and, therefore, such adaptations and modifications should and are intended to be comprehended within the meaning and range of equivalents of the disclosed embodiments. It is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation. Therefore, while the embodiments herein have been described in terms of preferred embodiments, those skilled in the art will recognize that the embodiments herein can be practiced with modification within the spirit and scope of the embodiments as described herein.

Claims

CLAIMS:
1. A catalyst additive for fluid catalytic cracking of the hydrocarbon oil comprising a zeolite, a binder, and a clay, characterized in that the said catalyst additive comprises : a. phosphorous content in the form of P205;
b. colloidal silica as a binder;
c. presence of at least one 27 Al MAS NMR peak having maxima at each of the values in the range of 50-60 ppm, 30-50 ppm and -15 to +15 ppm corresponding to the zeolite framework tetrahedral aluminum, zeolite framework distorted tetrahedral aluminum and non-framework octahedral aluminum, respectively, before the steaming protocol;
d. presence of said distorted tetrahedral and absence of said non-framework octahedral Al peak in the 27 Al MAS NMR after steaming; and
e. absence of an X-ray diffraction peak at the 2Θ value of 21.60° corresponding to aluminum phosphate crystal phase (A1P04).
2. The catalyst additive as claimed in claim 1, wherein the zeolite is ZSM-5 zeolite and said zeolite content ranges from 30 to 60 wt%.
3. The catalyst additive as claimed in claim 1, wherein the phosphorous content in the form of P205 ranges from 5.5 to 12 wt%.
4. The catalyst additive as claimed in claim 1, wherein the binder is substantially free of alumina or its derivatives.
5. The catalyst additive as claimed in claim 1, wherein the clay is selected from the group consisting of kaolin, holloysite, bentonite and mixtures thereof.
6. The catalyst additive as claimed in claim 1, wherein the clay is kaolin.
7. The catalyst additive as claimed in claim 1, wherein said catalyst additive composition has a. total acidity in the range of the 200-500 μηιοΐ/g before steaming protocol and in the range of 30-70 μπιοΐ/g after steaming protocol;
b. zeolite surface area in the range of 65 to 76 m /g before steaming protocol and in the range of 45 to 70 m2/g after steaming protocol;
c. matrix surface area in the range of 35 to 50 m /g before steaming protocol and in the range of 60 to 100 m /g after steaming protocol;
d. total pore volume in the range of 0.06 to 0.22 cc/g before steaming protocol and in the range of 0.08 to 0.16 cc/g after steaming protocol;
e. micro pore volume in the range of 0.025 to 0.045 cc/g before and after steaming protocol; and
f. average pore diameter in the range of 70 to 120 A before steaming protocol and in the range of 50 to 100 A after steaming protocol;
wherein said surface areas, pore volumes and pore diameter are measured by nitrogen adsorption in accordance with t-plot method.
8. The process for preparation of a catalyst additive for fluid catalytic cracking of the hydrocarbon oil comprising
a. preparing zeolite slurry and stabilizing said zeolite slurry by addition of phosphate slurry followed by aging;
b. preparing binder slurry and treating said binder slurry with acid;
c. preparing and adding clay slurry to said binder slurry to obtain clay-binder slurry;
d. adding clay-binder slurry to said stabilized zeolite slurry to obtain zeolite-clay- binder slurry;
e. spray drying said zeolite-clay-binder slurry to obtain microspheres; and f. calcining said microspheres to obtain catalyst additive ;
wherein the stabilization of zeolite with phosphate in step (a) and treatment with acid in step (b) are collectively optimized in such a manner that the pH of the zeolite-clay-binder slurry at the end of step (e) is maintained in the range of 5.5 to 7.0.
9. The process of claim 8, wherein the maximum viscosity of the stabilized zeolite-clay- binder slurry is 2000 cP.
10. The process as claimed in claim 8, wherein the process step (d) optionally further includes the step of adding at least one organic polar compound to said zeolite-clay- binder slurry, wherein said organic polar compound is selected from the group consisting of alcohols, diols, triols and polyols.
11. The process as claimed in claim 10, wherein said organic polar compound is at least one alcohol having carbon atoms in the range of 1 to 4.
PCT/IB2015/056062 2014-12-06 2015-08-10 Hydrothermally stable fcc catalyst additive composition WO2016087956A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN3920MU2014 2014-12-06
IN3920/MUM/2014 2014-12-06

Publications (1)

Publication Number Publication Date
WO2016087956A1 true WO2016087956A1 (en) 2016-06-09

Family

ID=56091087

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2015/056062 WO2016087956A1 (en) 2014-12-06 2015-08-10 Hydrothermally stable fcc catalyst additive composition

Country Status (3)

Country Link
AR (1) AR102889A1 (en)
TW (1) TW201621034A (en)
WO (1) WO2016087956A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018173269A1 (en) * 2017-03-24 2018-09-27 日揮株式会社 Zeolite-containing catalyst, ad method for producing low-grade olefin
EP3999615A4 (en) * 2019-10-04 2023-08-02 Reliance Industries Limited An fcc catalyst composition and a process for its preparation

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1097285A (en) * 1966-06-15 1968-01-03 Mobil Oil Corp Catalyst composition
AU2005243748A1 (en) * 2004-04-29 2005-11-24 Engelhard Corporation ZSM-5 additive
US20120258852A1 (en) * 2011-04-08 2012-10-11 Rive Technology, Inc. Mesoporous framework-modified zeolites
US20140206526A1 (en) * 2013-01-23 2014-07-24 Basf Corporation Zsm-5 additive activity enhancement by improved zeolite and phosphorus interaction

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1097285A (en) * 1966-06-15 1968-01-03 Mobil Oil Corp Catalyst composition
AU2005243748A1 (en) * 2004-04-29 2005-11-24 Engelhard Corporation ZSM-5 additive
US20120258852A1 (en) * 2011-04-08 2012-10-11 Rive Technology, Inc. Mesoporous framework-modified zeolites
US20140206526A1 (en) * 2013-01-23 2014-07-24 Basf Corporation Zsm-5 additive activity enhancement by improved zeolite and phosphorus interaction

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018173269A1 (en) * 2017-03-24 2018-09-27 日揮株式会社 Zeolite-containing catalyst, ad method for producing low-grade olefin
JPWO2018173269A1 (en) * 2017-03-24 2020-02-13 日揮グローバル株式会社 Zeolite-containing catalyst and method for producing lower olefin
EP3999615A4 (en) * 2019-10-04 2023-08-02 Reliance Industries Limited An fcc catalyst composition and a process for its preparation

Also Published As

Publication number Publication date
AR102889A1 (en) 2017-03-29
TW201621034A (en) 2016-06-16

Similar Documents

Publication Publication Date Title
US4968405A (en) Fluid catalytic cracking using catalysts containing monodispersed mesoporous matrices
JP5336480B2 (en) Structurally enhanced cracking catalyst
RU2755891C2 (en) Catalytic cracking catalyst and its preparation
JP5860516B2 (en) Additives having a complex system of zeolite and process for preparation
US8715487B2 (en) Low small mesoporous peak cracking catalyst and method of using
KR102431720B1 (en) FCC catalyst with alumina derived from crystalline boehmite
TW201029929A (en) Novel ultra stable zeolite Y and method for manufacturing the same
US11207661B2 (en) Process to peptize alumina for fluidizable catalysts
WO2016087956A1 (en) Hydrothermally stable fcc catalyst additive composition
KR100893954B1 (en) Zeolite based catalyst of ultra-high kinetic conversion activity
US10005072B2 (en) High matrix surface area catalytic cracking catalyst stabilized with magnesium and silica
JP7046763B2 (en) Fluid cracking catalyst for hydrocarbon oil
KR20150036718A (en) Magnesium stabilized ultra low soda cracking catalysts
JP7178829B2 (en) Fluid catalytic cracking catalyst for hydrocarbon oil
Aghamohammadi et al. Application of resin and NH 4 NO 3 as an ion exchange agent for microspherical preparation of nanostructured kaolin-SAPO-34 catalyst for methanol to light olefins reaction in a fluidized bed reactor
JP7123864B2 (en) Fluid catalytic cracking catalyst for hydrocarbon oil
US11731114B2 (en) Fluid catalytic cracking catalyst for hydrocarbon oil
RU2799090C1 (en) Fcc catalytic composition and method for its production
KR20180075687A (en) Flow catalytic cracking catalyst for increasing butylene yield
Pavlov et al. Synthesis and investigation of ZSM-5 zeolite-based catalysts for benzene alkylation with ethylene
WO2020044859A1 (en) Fluid catalytic cracking catalyst for hydrocarbon oil
石原篤 et al. Catalytic Properties of Amorphous Silica-alumina Prepared Using Dicarboxylic and Tricarboxylic Acids as Matrix in Catalytic Cracking of n-Dodecane
KR20140120330A (en) Process for producing at least one of ethene, propene, and gasoline

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15864748

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15864748

Country of ref document: EP

Kind code of ref document: A1