Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
  • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
  • C07C4/06—Catalytic processes
• • 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
  • 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
  • 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
  • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
  • B01J35/45—Nanoparticles
• • 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
• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2529/00—Catalysts comprising molecular sieves
  • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
  • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2529/00—Catalysts comprising molecular sieves
  • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
  • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2529/00—Catalysts comprising molecular sieves
  • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
  • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • C07C2529/80—Mixtures of different zeolites
• • 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
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/20—C2-C4 olefins

Definitions

• Embodiments of the present disclosure generally relate to fluid catalytic cracking processes, and more specifically relate to cracking catalysts used in high severity fluid catalytic cracking (HSFCC) systems, where the cracking catalyst comprises nano-ZSM-5 zeolites.
• HSFCC high severity fluid catalytic cracking
• the HSFCC process is capable of producing yields of propylene up to four times higher than the traditional fluid catalytic cracking unit and higher conversion levels for a range of petroleum steams. That being said, achieving maximum propylene and conversion from a wide range of feed qualities offers considerable challenges to the catalyst design for the HSFCC.
• zeolites to an HSFCC catalyst is utilized for improving the yield of light olefins due to its shape selectivity, special pore structure and large specific surface area.
• the crystal size of the zeolites is close to the molecular diameter of light hydrocarbons, the diffusion of the reactant/product molecules within the micropores is usually the rate-limiting step of the reaction.
• the crystal surface of the zeolites are susceptible to coke formation, which obstructs the accessibility of the micropores and thus deactivates the catalyst.
• Embodiments of the present disclosure are directed to improved HSFCC cracking systems, which convert gas condensate into light olefins using catalysts with nano-ZSM-5 catalysts, while reducing coke formation and pore diffusion on the nano-ZSM-5 zeolites.
• a method of converting gas condensate into a product stream comprising propylene comprises feeding gas condensate at a top region of a downflow high severity fluidized catalytic cracking reactor (HSFCC), where the gas condensate comprises at least 50% by weight paraffins, and, in some embodiments, less than 0.1% by weight olefins.
• HSFCC downflow high severity fluidized catalytic cracking reactor
• the method further comprises feeding catalyst to the top region of the downflow HSFCC reactor in an amount characterized by a catalyst to gas condensate weight ratio of about 5: 1 to about 40: 1, where the catalyst comprises a nano- ZSM-5 zeolite catalyst having an average particle diameter from 0.01 to 0.2 ⁇ , a Si/Al atomic ratio from 20 to 40, and a surface area of at least 20 cm /g.
• the method further comprises cracking the gas condensate in the presence of the catalyst at a reaction temperature of about 500° C to about 700° C to produce the product stream comprising propylene.
• FIG. 1 is a schematic depiction of a downflow HS-FCC reactor according to one or more embodiments of the present disclosure.
• FIG. 2A is an X-ray Diffraction (XRD) pattern of the nano-ZSM-5 based catalyst embodiments at various of sodium hydroxide.
• FIG. 2B is an enlarged segment of the XRD pattern of FIG. 2A.
• FIG. 3 is a graphical illustration of the phase selectivity of catalyst synthesis solutions based on the Al/Si and Na/Si ratios in the synthesis solution.
• FIG. 4A is an environmental scanning electron microscopy (ESEM) micrograph of micron-size ZSM-5 zeolite embodiments.
• FIG. 4B is an ESEM micrograph of nano-ZSM-5 zeolite embodiments.
• FIG. 5 A is a graphical plot of Weight Fraction vs. Temperature which depicts the results of thermogravimetric analysis (TGA) conducted on ZSM-5 zeolite embodiments synthesized with different Na and Al concentrations.
• TGA thermogravimetric analysis
• FIG. 5B is a graphical plot of Differential Gravimetric Analysis vs. Temperature which depicts further results of the TGA analysis of FIG. 5A conducted on ZSM-5 zeolite embodiments synthesized with different Na and Al concentrations.
• TPD Thermal Desorption Spectroscopy
• FIG. 7A is an ESEM image of a Y zeolite embodiment.
• FIG. 7B is Energy Dispersive Spectrum (EDS) of the Y zeolite embodiment which corresponds to the ESEM of FIG. 7A.
• EDS Energy Dispersive Spectrum
• FIG. 8A is an ESEM image of a lanthanum-impregnated Y zeolite embodiment.
• FIG. 8B is an EDS of the lanthanum-impregnated Y zeolite embodiment which corresponds to the ESEM of FIG. 8A.
• FIG. 9 is an XRD pattern of a parent Y zeolite embodiment versus its lanthanum impregnated Y zeolite form.
• Embodiments of the present disclosure are directed of systems and methods of converting gas condensate into a product stream comprising propylene in a downflow high severity fluidized catalytic cracking (HSFCC) reactor in the presence of catalyst slurry comprising a nano-ZSM-5 zeolite catalyst.
• HSFCC downflow high severity fluidized catalytic cracking
• the system and methods utilize a downflow HSFCC reactor 100, where the gas condensate 110 may be fed at a top region 105 of the FCC reactor 100.
• the catalyst 120 may be fed at the top region 105 of the HSFCC reactor 100 in an amount characterized by a catalyst 120 to gas condensate 110 weight ratio of about 5: 1 to about 40: 1.
• the catalyst 120 and gas condensate 110 may be fed via different inlet ports at the top region 105 of the downflow HSFCC reactor 100.
• the gas condensate 110 is cracked in the presence of the catalyst 120 at a reaction temperature of about 500° C to about 700° C to produce the product stream 140 comprising propylene.
• a catalyst bed may be fixed at the bottom of the HSFCC reactor 100. While not shown, steam may be injected into the downflow HSFCC to achieve the requisite high operating temperatures. Referring to FIG. 1, the gas condensate 110 is cracked as it travels a downward path as indicated by arrow 130. As shown, the catalyst 120 and the product stream 140 may be separated through a separator region 107 at the bottom of the HSFCC reactor 100, and are then passed out of the downflow HSFCC reactor 100 separately. The gas condensate 110 and the product stream 140 comprising propylene may be separated in the separator region 107. In some embodiments, the liquid products may be collected in a liquid receiver and the gaseous products may be collected in a gas burette by water displacement.
• the present embodiments may provide a greater propylene yield in the product stream 140 as compared to conventional HSFCC reactors.
• the product stream 140 comprises at least a 20 wt% yield of propylene.
• the product stream 140 may comprise at least a 10 wt% yield of ethylene.
• the product stream 140 may comprise at least a 30 wt% yield of ethylene and propylene.
• the product stream may comprise less than a 3 wt% yield of coke, or less than 1 wt% yield of coke.
• the present downflow HSFCC reactor 100 is characterized by high temperature, shorter residence times, and a high catalyst to oil ratio.
• the reaction temperature is from 500 °C to 700 °C, or from 550 °C to 630 °C.
• the gas condensate may have a residence time of 0.7 seconds to 10 seconds, or from 1 second to 5 seconds, or from 1 second to 2 seconds.
• the catalyst to gas condensate ratio may be from 5: 1 to 40: 1, or from 5: 1 to 25: 1, or from 5: 1 to about 15: 1, or from 5: 1 to about 10: 1.
• the gas condensate 110 is a heavily paraffinic composition including at least 50% by weight paraffins and less than 0.1 % by weight olefins. Additionally, the gas condensate 110 may comprise naphthenes and aromatics. From a property standpoint, the gas condensate 110 may have an initial boiling point of at least 0 °C and a final boiling point of at least 450 °C when measured according to a true boiling point analysis. The gas condensate may have a research octane number (RON) of 70 to 75 according to ASTM 2699 or ASTM 2700.
• RON research octane number
• the gas condensate may comprise Khuff Gas Condensate (KGC) which comprises 65 wt% paraffins, 0 wt% olefins, 21 wt% naphthenes, and 15 wt% aromatics.
• KGC Khuff Gas Condensate
• Feeds like KGC have attractive feedstock properties in terms of low sulfur, nitrogen, metals and Conradson Carbon Residue (CCR). That being said, the highly paraffinic nature of gas condensate, for example, KGC, makes it quite challenging for cracking into light olefins, such as propylene.
• the present downflow HSFCC system overcomes these challenges and produces excellent propylene yield using KGC, while being complementary to the current refinery FCC reactors
• the catalyst 120 which may be in slurry form, comprises nano-ZSM-5 zeolites having an average particle diameter from 0.01 to 0.2 ⁇ , a Si/Al molar ratio from 20 to 40, and a surface area of at least 20 cm /g.
• the Si/Al molar ratio is from 25 to 35
• the nano ZSM-5 has a surface area of at least 30 cm /g.
• the nano ZSM-5 has a surface area of from 30 cm /g to 60 cm /g, or from 40
• the nano-ZSM-5 zeolites solve the diffusional limitations encountered during the cracking reactions, thereby enhancing the rate of the cracking reactions to produce more olefins. Moreover, the nano-ZSM-5 zeolites reduces coke formation on the surface of the catalyst, thereby prolonging the life of the nano-ZSM-5 zeolite catalyst.
• the nano-ZSM-5 zeolite catalyst may be impregnated with additional components.
• the nano ZSM-5 catalyst is impregnated with phosphorus.
• the nano ZSM-5 catalyst comprises 1 to 20 wt% of phosphorus, or from 2 to 10 wt% of phosphorus.
• the nano ZSM-5 catalyst is impregnated with rare earth oxides.
• the catalyst may comprise from 10 to 50 wt% of nano ZSM-5 catalyst, or from 15 to 40 wt% of nano ZSM-5 catalyst, or from 15 to 25 wt% of nano ZSM-5 catalyst.
• the catalyst may also comprise USY (Ultrastable Y zeolite).
• USY Ultrastable Y zeolite
• the USY catalyst may also be impregnated with additional components.
• the USY catalyst may be impregnated with lanthanum.
• the catalyst may comprise 10 to 50 wt% of USY catalyst, or from 15 to 40 wt% of USY catalyst, or from 15 to 25 wt% of USY catalyst.
• USY zeolite impregnation with lanthanum impacts the selectivity towards light olefins.
• the impregnation with rare earth can also work as an enhancer to the stability and activity of the catalyst.
• Lanthanum impregnation in the USY zeolite also called Y zeolites is used to improve both the activity and hydrothermal stability, since it acts as a dealumination inhibitor in the zeolite structure.
• the catalyst comprises 2 to 20 wt% of alumina, or from 5 to 15 wt% of alumina.
• the catalyst may also comprise silica.
• the catalyst comprises 0.1 to 10 wt% of silica, or from 1 to 5 wt% of silica.
• the alumina may act as a binder for the catalyst.
• the clay comprises one or more components selected from kaolin, montmorilonite, halloysite, and bentonite.
• the clay comprises kaolin.
• the catalyst may comprise 30 to 70 wt% of clay, or 40 to 60 wt% of clay.
• the catalyst may comprise the nano ZSM-5 catalyst, USY catalyst, alumina, clay, and silica.
• the catalyst comprises from 10 to 50 wt% of nano ZSM-5 catalyst, 10 to 50 wt% of USY catalyst, 2 to 20 wt% of alumina, 30 to 70 wt % of clay, and 0.1 to 10 wt % of silica.
• the catalyst may comprise from 15 to 25 wt% of nano ZSM-5 catalyst, 15 to 25 wt% of USY catalyst, 5 to 15 wt% of alumina, 40 to 60 wt % of clay, and 1 to 5 wt % of silica.
• KGC Khuff Gas Condensate
• the details for the synthesis of a micron size ZSM-5 zeolites with Si-to-Al molar ratio of 100 are shown in Table 3 as follows.
• the details for the synthesis of nano ZSM-5 zeolites having Si-to-Al ratios of 20 and 33 are shown in Table 4 and Table 5, respectively.
• the precursor synthesis solutions were prepared by mixing all components and reagents together and stirring them for one day at room temperature. The mixture was then transferred into Teflon lined stainless steel autoclaves and heated to 140 °C for 4 days. After that, the solutions were centrifuged and the solid products were collected. The solid products were then dispersed in deionized water, centrifuged to obtain the final products which were then dried in the oven at 80 °C.
• the products were calcined using the following program. Using a heating rate of 3 °C/min the products were maintained at 200 °C for two hours and at 550 °C for 8 hours.
• the micron sized ZSM-5 were produced with a particle diameter of 1.1 ⁇ , while the nano-ZSM-5 zeolites were produced with a particle size of 0.07 ⁇ for a Si-to-Al molar ratio of 20 in one example, and a particle size of 0.084 ⁇ for a Si-to-Al molar ratio of 33 in a second example.
• Table 3 Completed synthesis solution compositions, synthesis details, yield, and phase selectivity for nano-ZSM-5 zeolites having Si-to-Al molar ratio of 100.
• Table 4 Completed synthesis solution compositions, synthesis details, yield, and phase selectivity for nano ZSM-5 zeolites having Si-to-Al molar ratio of 20.
• Table 5 Completed synthesis solution compositions, synthesis details, yield, and phase selectivity for nano ZSM-5 zeolites having Si-to-Al molar ratio of 33.
• Table 6 Catalyst composition for in-house made HSFCC catalyst.
• ZSM-5 zeolites were impregnated with phosphorous and Y zeolites were impregnated with lanthanum.
• the impregnated zeolites were mixed with alumina binder, silica and clay and were stirred for 1 hour.
• the obtained slurry was placed in temperature programmed oven for drying and calcination as per the following program: (rate(°C/min):Temperature(°C):time(hrs))
• the calcined catalyst was grounded to a fine powder by means of a mortar and a pestle. Then, the grounded catalyst was sieved for a fraction between 40-120 ⁇ and used for characterization and evaluation.
• the MAT results from the micro and nano-ZSM-5 based catalysts are shown in Table 7. As can be seen, high propylene yields of greater than 18 wt% were obtained for the three catalysts.
• the nano-ZSM-5 having Si-to-Al molar ratio of 33 achieved the highest propylene yield of 21.12 wt% compared to 20.07 wt% propylene yield obtained with the nano-ZSM-5 having Si-to-Al molar ratio of 20.
• the micron sized ZSM-5 achieved the lowest propylene yield of 18.78 wt% which signifies the role of the higher surface area provided by the nano ZSM-5 zeolites for the selective production of light olefins.
• the XRD was also used to develop a phase envelope where [A10 2 /4]/[Si0 2 /4] was plotted along the ordinate while NaOH/[Si0 2 /4] was plotted along the abscissa as presented in FIG. 3.
• the diagram determined that the MFI-type zeolite is only formed in a small region in the phase space. Solutions with relatively low concentrations of the sodium hydroxide (i.e., Si / Na ⁇ 5) and aluminum (i.e., Si / Al ⁇ 25) were found to lead to pure MFI-type products. Lower concentrations of the sodium hydroxide and alumina were observed to give some mixed phase products that included unknowns and relatively important concentrations of amorphous phases as shown in FIG. 3.
• Table 8 BET measurement of ZSM-5 zeolite.
• thermogravimetric (TGA) analysis of any newly synthesized zeolites is an important characterization as the catalysts have to withstand a temperature range of 500-750 °C typical for the HSFCC process.
• TGA thermogravimetric
• the water and tetrapropylammonium (TPA+) content of the synthesized zeolites were calculated from the weight loss upon heating. The weight loss between 25-200 °C was attributed to water content desorbing from the zeolite. It was observed that the water desorbed between 25-200 °C was proportional to sodium content in the zeolite. In contrast, the more TPA+ in the sample, the less water desorbed from the sample in the heating process.
• TPA+ is relatively large as compared to sodium ions.
• the TPA+ has hydrophobic properties that prevent the water molecules from adsorbing inside the zeolite samples.
• the TPA+ fills the majority of the microspores leaving no space for water to attach to the zeolites (See Table 9).
• the TPA+ converts to tripropylammonia and releases a propylene molecule. This gives rise to the weight loss, which is presented in FIGS. 5 A and 5B. From TGA traces, the number of TPA atoms per unit cell can be calculated assuming no defect in the unit cell structure.
• An ideal MFI-type zeolite that is defect-free has the following molecular formula (ITPAnl[Al n Si96-nOi8 2 ])- Therefore, the number of TPA+ can be calculated using weight loss fraction and the molecular formula of MFI-type type zeolite as shown in Table 9.
• Table 9 TGA analysis of ZSM-5 zeolites synthesized with different Na and Al concentrations.
• temperature programmed desorption curves of high silicate sample and low silicate sample were collected.
• the mass to charge curves of 16, 17, and 18 corresponds to NH 2 +, NH 3 +, H 2 0+ ions, respectively.
• the high silica sample exhibited two peaks with different energies.
• the low energy peak occurred at 109 °C and was attributed to weakly bonded ammonia. This low energy (low temperature) peak suggests the presence of silanol groups to which the ammonia was physisorbed.
• the peak at 350 °C was a high energy peak which represented strongly bonded ammonia into the strong Br0nsted acid sites.
• Table 10 BET measurements of Y zeolite.

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