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• • 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
• • 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
  • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
  • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
  • B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
  • B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
• • 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
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
• • 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
  • B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
• • 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
  • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
  • B01J29/068—Noble metals
• • 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
  • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
  • B01J29/072—Iron group metals or copper
• • 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
  • B01J29/405—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 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
• • 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
  • B01J29/42—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 containing iron group metals, noble metals or copper
  • B01J29/44—Noble metals
• • 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
  • B01J29/42—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 containing iron group metals, noble metals or copper
  • B01J29/46—Iron group metals or copper
• • 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
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
  • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
  • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
• • 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
  • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto 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
  • B01J2229/40—Special temperature treatment, i.e. other than just for template removal

Definitions

• This invention relates to a process of obtaining zeolite catalysts containing metal by microwave and ultrasonic assisted hydrothermal synthesis, at various operating frequencies, catalysts that are used in the processes of pyrolysis of biomass and other carbon-containing materials.
• the invention is particularly useful for the quick obtaining of zeolite catalysts containing high purity metal, uniform particle size distribution, controlled nucleation, large specific area, and controlled distribution of active metal centers.
• Natural or synthetic zeolites are known as materials with catalytic properties for various industrial processes. Zeolites are porous metal silicate materials with a well- defined crystalline structure and unique properties. In these porous structures there are a number of small cavities that can be interconnected with microchannels or micropores. In ideal conditions the cavities and pores of zeolitic materials have uniform dimensions. The size of these pores allow the absorption of molecules with specific size that will eliminate other molecules with larger size, and therefore zeolite materials are referred to in the literature as ’’molecular sieves”, and by exploiting this phenomenon they are used in selective absorption processes. These materials contain a multitude of aluminosilicate positive ions.
• aluminosilicates form a rigid three-dimensional tetrahedral network of SiC and AI04 in which the ratio of oxygen atoms to those of silicium and aluminum varies depending on the nature and type of zeolite. [US 9, 186,659 B2]
• micropore size limits mass transfer, and zeolite morphology affects the absorption capacity and thus the catalytic activity of the material.
• Some zeolites with a one-dimensional micropore (1 D) system have a stem-shaped acyclic morphology, which reduces mass transfer by blocking channels and implicitly results in rapid deactivation of the catalyst due to a much too long diffusion path.
• the morphology of the zeolites can be altered by controlling the crystallization process.
• Zeolite catalysts with higher mass transfer properties can be obtained by reducing crystal sizes to submicron or nanometric values.
• This crystal size reduction mechanism aims to reduce the diffusion pathway of reactant molecules in the active spaces of zeolite crystals. Relatively smaller zeolite crystals show greater catalytic activity, as the reagent diffusion process is much faster through catalyst pores and absorption/desorption phenomena become controllable.
• the nucleation rate directs the crystallization of zeolites and is not significantly influenced by temperature, the internal crystal growth process is thermosensitive, and therefore in conventional hydrothermal synthesis processes it is necessary to reduce the reaction temperature.
• OSDA organic structure-directing agents
• microwave assisted hydrothermal synthesis has many applications in synthetic chemistry, and the major advantage is the drastic reduction of reaction time and the achievement of a controlled particle size distribution with different morphologies.
• This invention is directed to an improved process with respect to known processes of obtaining zeolite based metal catalysts by conventional synthesis, by substantially reducing the synthesis time and implicitly reducing the crystallization time, reducing the reaction temperature and selectively obtaining various types of zeolite structures with high catalytic performance, such as: high selectivity over the end products of biomass pyrolysis, high in-service efficiency and high self-regeneration capacity.
• the technical problem solved by the present invention is to obtain crystalline zeolitic structures with controlled distribution, shape and size, containing metal, in a substantially reduced reaction time, at a substantially reduced reaction temperature.
• a process for obtaining metal-containing zeolite catalysts by microwave and ultrasonic-assisted hydrothermal synthesis according to the invention comprises the following steps:
• the process of the invention can be applied to a wide variety of zeolites.
• a zeolite from the zeolites of type HSZM-5, HSZM-10 and HSZM-20.
• the metal precursor used according to the invention is chosen from the transition metal salts of type Co, Ni, Fe, Ag, Au, Pt, Ti.
• the reducing agent used according to the invention is a primary alcohol-type alcohol, chosen from methyl, ethyl, propyl, isopropyl, butyl, isobutyl alcohol.
• the mass ratio of the reactants in the reaction mixture, zeolite:rmetal precursonreducing agent, is in a ratio x:y:z, where x represents zeolite and is 1 , y represents the metal precursor and is from 5 to 15, z is the reducing agent and is from 6 to 17.
• the aqueous reaction medium may be distilled water or deionized water, to which may be added 0.1-1% cationic or anionic surfactant, the percentages being percentage by mass.
• the process of the invention can be dimensioned and applied industrially using the two types of industrial microwave frequencies of 2.45 GHz and 915 MHz, and an ultrasound regime with an amplitude of 80% and a frequency of 30 to 90 KHz.
• the microwave and ultrasonic-assisted hydrothermal synthesis process of the zeolite structures according to the invention eliminates the disadvantages of the known processes by the fact that it is a selective, energy-efficient, ecological, and extremely fast process.
• the process of this invention has the following advantages: it is selective, energy-efficient and environmentally friendly; the reaction time is very short, maximum 60 minutes, compared to the classical process lasting approximately 48 hours; it can be dimensioned and applied industrially using the two types of microwave frequencies 2.45 GHz and 915 MHz and a frequency range of 30 - 90 KHz for ultrasound; it leads to a uniform dispersion and disaggregation of zeolite structures due to cavitation effects; zeolite structures are obtained with controlled shape, size and distribution; zeolite structures with amorphous structure, large specific area and specific selectivity for pyrolysis products are obtained.
• Figure 1- shows the IR spectrum of the zeolite Co catalyst obtained at different temperatures (continuous line - at a temperature of 40 Q C and interrupted line - at a temperature of 70 a C).
• Figure 2A - shows the SEM image for the zeolite Co catalyst obtained at a temperature of 40 Q C
• Figure 2B- shows the SEM image for the zeolite Co catalyst obtained at a temperature of 70 S C.
• Figure 3A shows the TEM EDX images for the zeolite Co catalyst obtained at 40 Q C.
• Figure 3B shows the TEM EDX images for the zeolite Co catalyst obtained at 70 S C.
• Figure 4A shows the XRD spectrum for the zeolite Fe catalyst obtained at 40 Q C.
• Figure 4B shows the XRD spectrum for the zeolite Fe catalyst obtained at 70 Q C.
• Figure 5 shows the IR spectrum of the zeolite Fe catalyst obtained at different temperatures (continuous line - at a temperature of 40 Q C and interrupted line - at a temperature of 70 Q C).
• Figure 6 shows the IR spectrum of the zeolite Ni catalyst obtained at different temperatures (continuous line - at a temperature of 40 Q C and interrupted line - at a temperature of 70 Q C).
• Figure 7A shows the SEM image for the zeolite Ni catalyst obtained at a temperature of 40 S C.
• Figure 7B shows the SEM image for the zeolite Ni catalyst obtained at a temperature of 70 a C.
• Figure 8A shows the TEM EDX image for the zeolite Ni catalyst obtained at a temperature of 40 Q C.
• Figure 8B shows the TEM EDX image for the Ni zeolite catalyst obtained at a temperature of 70 a C. The following are some embodiments of the invention.
• Example illustrates obtaining the HSZM-5 zeolite catalyst containing Co (Co- HZSM-5)
• Zeolite type HZSM-5 (Acros Organics®) and precursor metal salt Co, CO+ 2 (N0 3 )2 * 6(H 2 0) (Honeywell®) were used to prepare the Co-HZSM 5 catalyst.
• the materials used are of analytical purity and have the physical and chemical characteristics indicated in Table 1.
• the prepared aqueous dispersion of zeolite HZSM-5 is introduced into the microwave field and heated to a temperature of 40°C at an incident microwave power of 50 W.
• the aqueous solution of metal precursor Co+ 2 (N03)2 * 6(H20) is added over the aqueous dispersion of zeolite HZSM-5 heated with microwave and the reaction mixture is maintained at a temperature of 40°C by microwave heating for 15 minutes. A quantity of 20 mL methanol was then added directly to the previously obtained reaction mixture.
• the mixture thus obtained is kept at a constant temperature of 40 e C, at an incident microwave power of 50 W for 15 minutes.
• the entire mixture thus obtained is isolated, cooled to room temperature, transferred to an Erlenmeyer flask and ultrasonated for 30 minutes, at an amplitude of 80% and a frequency of 50 KHz.
• the ultrasonated reaction mixture is centrifuged for 10 minutes at 6000 rpm and the resulting solid is separated from the liquid.
• the recovered solid was washed with distilled water and centrifuged under the same conditions. The washing and centrifugation operation were carried out twice.
• the resulting solid was then calcined at 500 Q C for 4 hours at a heating rate of 5 degrees/min.
• the catalyst thus synthesized was characterized by FT I R spectrophotometry, SEM and TEM microscopic analysis, as shown in Figures 1 , 2A, 2B, 3A,3B.
• Example illustrates obtaining the Fe-containing HSZM-5 zeolite catalyst (Fe HZSM - 5)
• HZSM 5 type zeolite (Acros Organics®) and Fe salt metal precursor, FeCl2 (Honeywell®) were used to prepare the Fe-HZSM 5 catalyst.
• the materials used are of analytical purity and have the physical and chemical characteristics indicated in Table 2. Table 2. Physical and chemical characteristics of reagents for the synthesis of Fe -
• HZSM 5 catalyst A technical balance was used for weighing reagents. Solubilization and homogenization of the reactants was carried out using a Vortex agitator and a magnetic stirrer with constant temperature maintenance function. Microwave field synthesis was performed in a multi-mode cavity where they have multiple reflections on metal walls, equipped with a solid state microwave generator type GMP30KSM56T400FST3IR with a power supply of 2 kW, at a working frequency of 2.45 GFIz, cooled with water. Temperature measurement was performed with an optical fiber model OTG-Q-10-62ST-1 .5PFA-XN-XN-H, Opsense, Canada. Syntheses were performed in a glass reactor with an effective reaction volume of 250 ml_, under continuous magnetic stirring and on-line monitoring of reflected power, incident power, reaction time and temperature.
• the Fe +2 -FIZSM-5 catalyst is obtained in several steps as follows.
• the prepared aqueous zeolite dispersion is introduced into the microwave field and heated to 40 Q C at an incident microwave power of 50 W.
• the aqueous solution of metal precursor FeCl2 is added over the aqueous dispersion of zeolite HZSM-5 heated with microwave and the reaction mixture maintained at a temperature of 40 Q C by microwave heating for 15 minutes.
• the entire mixture thus obtained is isolated, cooled to room temperature, transferred to an Erlenmeyer flask and ultrasonated for 30 min at an amplitude of 80% and a frequency of 50 KHz.
• the ultrasonated reaction mixture is centrifuged for 10 minutes at 6000 rpm and the resulting solid is separated from the liquid.
• the recovered solid was washed with distilled water and centrifuged under the same conditions. The washing and centrifugation operation were carried out twice.
• the resulting solid was then calcined at 500 Q C for 4 hours at a heating rate of 5 degrees/min.
• Example illustrates obtaining the Ni containing zeolite HZSM-5 catalyst (Ni HZSM -
• Zeolite type HZSM-5 (Acros Organics®) and Ni salt metal precursor, Ni+ 2 (NH4)2 * 4(H20) (Honeywell®) were used to prepare the Ni-HZSM 5 catalyst.
• the materials used are of analytical purity and have the physical and chemical characteristics indicated in Table 3.
• a technical balance was used for weighing reagents. Solubilization and homogenization of the reactants was carried out using a Vortex agitator and a magnetic stirrer with constant temperature maintenance function. Microwave field synthesis was performed in a multimode cavity equipped with a solid-state microwave generator type GMP30KSM56T400FST3IR with a power supply of 2 kW, at a working frequency of 915 MHz, cooled with water.
• Temperature measurement was performed with an IR pyrometer model CTM - 3SF75H1 - C3 with USB interface ACCTUSBK kit.
• Syntheses were performed in a glass reactor with an effective reaction volume of 500 ml_, under continuous magnetic stirring and on-line monitoring of reflected power, incident power, reaction time and temperature.
• Ni +2 -HZSM-5 catalyst is obtained in several steps as follows.
• zeolite HZSM-5 20 g was dispersed in 66.8 imL deionized water using 0.1% by weight benzyldimethylhexadecyl ammonium chloride as cationic surfactant under magnetic stirring.
• the prepared aqueous dispersion of zeolite HZSM-5 is introduced into the microwave field and heated to a temperature of 40 S C, at an incident microwave power of 50 W.
• the aqueous solution of metal precursor Ni+ 2 (NH4)2 * 4(H20) is added over the aqueous dispersion of zeolite HZSM-5 heated with microwave and the reaction mixture is maintained at a temperature of 40 Q C by microwave heating for 15 minutes. Then an amount of 20 ml. of methanol was added directly to the previously obtained reaction mixture.
• the mixture thus obtained is maintained at a constant temperature of 40 Q C at an incident microwave power of 50 W for 15 min.
• the entire mixture thus obtained is isolated, cooled to room temperature, transferred to an Erlenmeyer flask and ultrasonated for 30 minutes at an amplitude of 80% and a frequency of 50 KHz.
• the ultrasonated reaction mixture is centrifuged for 10 minutes at 6000 rpm and the resulting solid is separated from the liquid.
• the recovered solid was washed with distilled water and centrifuged under the same conditions. The washing and centrifugation operation were performed twice. The resulting solid was then calcined at 500 Q C for 4 hours at a heating rate of 5 degrees/min.
• the catalyst thus synthesized was characterized by FT IR spectrophotometry, SEM, TEM microscopic analysis, as shown in Figures 6, 7A, 7B, 8A, 8B.

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