WO2021107801A1 - Process of obtaining zeolite catalysts containing metal by microwave- and ultrasonic-assisted hydrothermal synthesis - Google Patents
Process of obtaining zeolite catalysts containing metal by microwave- and ultrasonic-assisted hydrothermal synthesis Download PDFInfo
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- WO2021107801A1 WO2021107801A1 PCT/RO2020/050005 RO2020050005W WO2021107801A1 WO 2021107801 A1 WO2021107801 A1 WO 2021107801A1 RO 2020050005 W RO2020050005 W RO 2020050005W WO 2021107801 A1 WO2021107801 A1 WO 2021107801A1
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- zeolite
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000010457 zeolite Substances 0.000 title claims abstract description 61
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 50
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000008569 process Effects 0.000 title claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 25
- 239000002184 metal Substances 0.000 title claims abstract description 25
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 11
- 239000011541 reaction mixture Substances 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 239000012736 aqueous medium Substances 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000007791 liquid phase Substances 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229940035429 isobutyl alcohol Drugs 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 2
- 235000019441 ethanol Nutrition 0.000 claims 1
- 150000003624 transition metals Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 238000000197 pyrolysis Methods 0.000 abstract description 4
- 239000002028 Biomass Substances 0.000 abstract description 3
- 238000002604 ultrasonography Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 9
- 229910001868 water Inorganic materials 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000003426 co-catalyst Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000009529 body temperature measurement Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000265 homogenisation Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000007928 solubilization Effects 0.000 description 3
- 238000005063 solubilization Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007431 microscopic evaluation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012431 aqueous reaction media Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- SXPWTBGAZSPLHA-UHFFFAOYSA-M cetalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SXPWTBGAZSPLHA-UHFFFAOYSA-M 0.000 description 1
- 229960000228 cetalkonium chloride Drugs 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- -1 transition metal salts Chemical class 0.000 description 1
Classifications
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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
- 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
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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
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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
- 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
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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
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/068—Noble metals
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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
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/072—Iron group metals or copper
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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
- 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
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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
- 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
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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
- 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
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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
- 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
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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
- 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
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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
- 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
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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
- 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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Abstract
The present invention relates to a process of obtaining metal-containing zeolite catalysts, by microwave and ultrasonic assisted hydrothermal synthesis, at various operating frequencies, catalysts for use in biomass pyrolysis processes and other carbon-containing materials. The process of the invention comprises the following steps: microwave application to a reaction mixture obtained by dispersing a zeolite in an aqueous medium to which a metal precursor is first added and subsequently a reducing agent, at a temperature in the range from 30ºC to 75ºC for a maximum of 30 minutes followed by cooling the resulting reaction mixture to room temperature and then ultrasonic application to the reaction mixture for a maximum of 30 minutes, after which separation of the reaction product obtained in solid form from the liquid phase, optionally washing and then calcination is performed. 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.
Description
Process of obtaining zeolite catalysts containing metal by microwave- and ultrasonic-assisted hydrothermal synthesis
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. These 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]
Since the catalytic activity of zeolites is affected on the one hand by the size of the channels and micropores responsible for selective absorption, the size of the micropores is an important characteristic of these materials. In addition, 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. While 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. Consequently, conventional hydrothermal synthesis processes require an exceedingly long reaction time to achieve crystallization of the zeolite structure in order to obtain relatively small crystals. A long period of crystallization not only reduces the productivity of the process, but also increases the risk of impurities of crystalline structures with other undesirable materials.[U.S. 3,328,119; U.S. 3,329,480; U.S. 3,329,481 ; U.S. 4,414,423; U.S. 4,417,088]
An approach to this dilemma involves the use of structure- directing agents that favorably influence the crystallization. When small organic molecules act for this purpose, they are called organic structure-directing agents (OSDA).
The use of 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.
Li and collaborators reported rapid production of zeolites, where the reaction time was reduced to 6 hours at 190aC. The use of this method in the presence of AODS has been reported for a number of zeolites in U.S. Patent 4,778,666.
Known processes have a number of disadvantages, such as very long synthesis times - minimum 48 hours, high reaction temperature - above 150QC in the case of microwave hydrothermal synthesis process, obtaining uneven zeolite structures in terms of crystal distribution, size, and shape.
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:
- microwave application to a reaction mixture carried out by dispersion of a zeolite in an aqueous medium to which a metal precursor is first added and subsequently a reducing agent, at a temperature in the range from 30SC to 75SC, for a maximum of 30 minutes followed by cooling of the resulting reaction mixture to room temperature and then by
- ultrasonic application of the reaction mixture for a maximum of 30 minutes, followed by
- separation of the reaction product obtained in solid form from the liquid phase, optionally washing and then its calcination.
The process of the invention can be applied to a wide variety of zeolites.
In a preferred embodiment of the invention it is selected 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.
Also, 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.
This invention is further illustrated with reference to the following figures:
Figure 1- shows the IR spectrum of the zeolite Co catalyst obtained at different temperatures (continuous line - at a temperature of 40QC and interrupted line - at a temperature of 70aC).
Figure 2A - shows the SEM image for the zeolite Co catalyst obtained at a temperature of 40QC,
Figure 2B- shows the SEM image for the zeolite Co catalyst obtained at a temperature of 70SC. Figure 3A shows the TEM EDX images for the zeolite Co catalyst obtained at 40QC. Figure 3B shows the TEM EDX images for the zeolite Co catalyst obtained at 70SC. Figure 4A shows the XRD spectrum for the zeolite Fe catalyst obtained at 40QC. Figure 4B shows the XRD spectrum for the zeolite Fe catalyst obtained at 70QC. Figure 5 shows the IR spectrum of the zeolite Fe catalyst obtained at different temperatures (continuous line - at a temperature of 40QC and interrupted line - at a temperature of 70QC).
Figure 6 shows the IR spectrum of the zeolite Ni catalyst obtained at different temperatures (continuous line - at a temperature of 40QC and interrupted line - at a temperature of 70QC). Figure 7A shows the SEM image for the zeolite Ni catalyst obtained at a temperature of 40SC.
Figure 7B shows the SEM image for the zeolite Ni catalyst obtained at a temperature of 70aC.
Figure 8A shows the TEM EDX image for the zeolite Ni catalyst obtained at a temperature of 40QC.
Figure 8B shows the TEM EDX image for the Ni zeolite catalyst obtained at a temperature of 70aC. The following are some embodiments of the invention.
Example 1
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(N03)2*6(H20) (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.
Table 1 . Physical and chemical characteristics of reagents for catalyst synthesis Co - HZSM 5
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 single-mode cavity equipped with a solid state microwave generator type GMP 30K SM 56T 400 FCA 31 R, with a power supply of 3 x 400 V ± 10%, at a working frequency of 2.45 GHz, 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 Co+2-HZSM-5 catalyst is obtained in several steps as follows.
1.48 g CO+2(NC>3)2*6(H20) were added to 6.68 imL deionized water and mixed by mechanical stirring on the Vortex system to ensure complete solubility.
20 g of HZSM-5 zeolite were dispersed in 66.8 ml_ of deionized water using magnetic stirring.
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 40eC, 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. To obtain a high purity zeolite structure, 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 500QC 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 2
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.
1.48 g of FeCl2 were added to 6.68 mL deionized water and mixed by mechanical stirring on the Vortex system to ensure complete solubility.
20 g of FIZSM-5 zeolite were dispersed in 66.8 mL of deionized water using magnetic stirring.
The prepared aqueous zeolite dispersion is introduced into the microwave field and heated to 40QC 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 40QC 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 kept at a constant temperature of 40SC 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 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. To obtain a high purity zeolite structure, 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 500QC for 4 hours at a heating rate of 5 degrees/min.
The catalyst thus synthesized has been characterized by XRD and FT IR spectrophotometry as shown in Figures 4A, 4B, 5. Example 3
Example illustrates obtaining the Ni containing zeolite HZSM-5 catalyst (Ni HZSM -
5)
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.
Table 3. Physical and chemical properties of reagents for the synthesis of Ni - 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 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.
The Ni+2-HZSM-5 catalyst is obtained in several steps as follows.
1.48 g Ni +2(NH )2*4(H20) was added to 6.68 ml_ deionized water and stirred by mechanical stirring on the Vortex system to ensure complete solubility.
20 g of zeolite HZSM-5 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 40SC, 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 40QC 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 40QC 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. To obtain a high purity zeolite structure, 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 500QC 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.
Claims
1. Process of obtaining metal-containing zeolite catalysts by microwave and ultrasonic hydrothermal synthesis, characterized in that it comprises the following steps:
- microwave application to a reaction mixture carried out by dispersion of a zeolite in an aqueous medium to which a metal precursor is first added and subsequently a reducing agent, at a temperature in the range from 30QC to 75QC, for a maximum of 30 minutes followed by cooling of the resulting reaction mixture to room temperature and then by
- ultrasonic application to the reaction mixture for a maximum of 30 minutes, followed by
- separation of the reaction product obtained in solid form from the liquid phase, optionally washing and then its calcination.
2. The process of claim 1 characterized in that the mass ratio of the reactants in the reaction mixture, zeolite/metal precursor/reducing 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.
3. The process of claim 1 characterized in that the zeolite is selected from the zeolites of type HZSM-5, HZSM-10 or HZSM-20.
4. The process of claim 1 characterized in that the metal precursor is chosen from the transition metals Co, Ni, Fe, Ag, Au, Pt, Ti in the form of salts.
5. The process of claim 1 characterized in that the reducing agent is selected from methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol.
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2019
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