US20210139336A1 - Systems and methods for synthesis of zsm-22 zeolite - Google Patents
Systems and methods for synthesis of zsm-22 zeolite Download PDFInfo
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- US20210139336A1 US20210139336A1 US17/069,544 US202017069544A US2021139336A1 US 20210139336 A1 US20210139336 A1 US 20210139336A1 US 202017069544 A US202017069544 A US 202017069544A US 2021139336 A1 US2021139336 A1 US 2021139336A1
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- 239000010457 zeolite Substances 0.000 title claims abstract description 81
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 75
- 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 75
- 238000000034 method Methods 0.000 title abstract description 33
- 230000015572 biosynthetic process Effects 0.000 title 1
- 238000003786 synthesis reaction Methods 0.000 title 1
- 239000013078 crystal Substances 0.000 claims abstract description 65
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000002156 mixing Methods 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 150000004645 aluminates Chemical class 0.000 claims abstract description 25
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 25
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 238000004891 communication Methods 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- -1 polyoxyethylene Polymers 0.000 description 47
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 41
- 239000004094 surface-active agent Substances 0.000 description 17
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 16
- 230000008569 process Effects 0.000 description 15
- 239000002105 nanoparticle Substances 0.000 description 13
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-UHFFFAOYSA-N 0.000 description 12
- 229930195733 hydrocarbon Natural products 0.000 description 12
- 150000002430 hydrocarbons Chemical class 0.000 description 12
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000005054 agglomeration Methods 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 description 7
- FDCJDKXCCYFOCV-UHFFFAOYSA-N 1-hexadecoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCC FDCJDKXCCYFOCV-UHFFFAOYSA-N 0.000 description 6
- CSHOPPGMNYULAD-UHFFFAOYSA-N 1-tridecoxytridecane Chemical compound CCCCCCCCCCCCCOCCCCCCCCCCCCC CSHOPPGMNYULAD-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- HBXWUCXDUUJDRB-UHFFFAOYSA-N 1-octadecoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCCCC HBXWUCXDUUJDRB-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- 229920001213 Polysorbate 20 Polymers 0.000 description 4
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 4
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 4
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 4
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 description 4
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 2
- UCRIXEWTILHNCG-UHFFFAOYSA-N 1-ethyl-2h-pyridine Chemical compound CCN1CC=CC=C1 UCRIXEWTILHNCG-UHFFFAOYSA-N 0.000 description 2
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920001214 Polysorbate 60 Polymers 0.000 description 2
- 239000004147 Sorbitan trioleate Substances 0.000 description 2
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- HYQBVSXBLGKEDT-UHFFFAOYSA-N hexane-1,4-diamine Chemical compound CCC(N)CCCN HYQBVSXBLGKEDT-UHFFFAOYSA-N 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 2
- 235000010483 polyoxyethylene sorbitan monopalmitate Nutrition 0.000 description 2
- 239000000249 polyoxyethylene sorbitan monopalmitate Substances 0.000 description 2
- 239000001816 polyoxyethylene sorbitan tristearate Substances 0.000 description 2
- 235000010988 polyoxyethylene sorbitan tristearate Nutrition 0.000 description 2
- 229920000053 polysorbate 80 Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229940035044 sorbitan monolaurate Drugs 0.000 description 2
- 235000019337 sorbitan trioleate Nutrition 0.000 description 2
- 229960000391 sorbitan trioleate Drugs 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
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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
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
- B01J6/001—Calcining
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/126—Microwaves
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7042—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/12—Particle morphology extending in one dimension, e.g. needle-like with a cylindrical shape
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Definitions
- Embodiments of systems and methods disclosed here allow for several size ranges of nano-scale ZSM-22 zeolite crystals to be consistently produced without agglomeration and without impurities.
- ZSM-22 zeolite crystals of three unique size ranges are produced with lengths varying from about 50 nm to about 600 nm, and with widths ranging from about 55 nm to about 75 nm.
- one or more non-ionic surfactant and microwave heating is applied in four isothermal steps.
- Nonionic surfactants suitable in embodiments here include those nonionic surfactants based on polyoxyethylene.
- Systems and methods can be scaled to an industrial scale to manufacture nano zeolites for oil upgrading and hydrocarbon conversion reactions. By reducing crystals size, catalytic activity of the ZSM-22 crystals is surprisingly and unexpectedly enhanced.
- the method includes the steps of neutralizing pH of the produced consistently-sized ZSM-22 zeolite catalyst crystals, water washing the produced consistently-sized ZSM-22 zeolite catalyst crystals, drying the produced consistently-sized ZSM-22 zeolite catalyst crystals, and calcining the produced consistently-sized ZSM-22 zeolite catalyst crystals.
- FIG. 5 shows X-ray diffraction (XRD) patterns confirming ZSM-22 structured zeolite was produced.
- Surfactant-microwave mixing unit 400 operates after the separate solutions of aluminate and silica are introduced to the unit via inlets 405 and 410 .
- four separate stages of isothermal heating are carried out with electrical heater 440 producing microwave irradiation 450 to synthesize the nano-sized ZSM-22.
- electrical heater 440 operates to heat the solution mixture in surfactant-microwave mixing unit 400 to between about 35° C. and about 65° C., or to between about 45° C. and about 55° C., for between about 3 minutes and about 7 minutes, preferably about 5 minutes.
- Mixing via stirring rod 420 is applied when microwave application begins via electrical heater 440 at a speed between about 200 rpm and about 300 rpm, preferably about 250 rpm.
- nonionic surfactants has several advantages versus long chain alcohols as there are no electronic charge groups or limited charge in the nonionic molecules.
- the utilization of surfactant helps control the sizes of nano-scale crystals of ZSM-22 without negatively affecting the zeolite framework and crystallinity.
- Systems and processes adapt the use of one or more nonionic surfactant to ZSM-22 zeolite crystal production under controlled microwave irradiation in order to meet the crystallinity of the ZSM-22 framework and synthesize different size scales of nano-sized of ZSM-22.
- zeolite aging is applied and electrical heater 440 is set such that the temperature of surfactant-microwave mixing unit 400 is between about 35° C. and about 65° C., or is between about 45° C. and about 55° C., and stirring is applied via stirring rod 420 at a speed of between about 350 rpm and about 450 rpm, preferably 400 rpm, for about 60 to about 80 hours, preferably about 72 hours.
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- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Electromagnetism (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
- This application is a divisional application of and claims priority to and the benefit of U.S. Non-Provisional Patent Application No. 16/682,515, filed Nov. 13, 2019, the entire disclosure of which is incorporated herein by reference in its entirety.
- The present disclosure relates to systems and methods for producing consistently-sized ZSM-22 zeolite catalyst crystals. Specifically, the disclosure presents systems and methods that apply microwave heating to a zeolite solution comprising non-ionic surfactant for producing consistently-sized nano-scale ZSM-22 zeolite catalyst crystals.
- Hydrocarbon conversion reactions for petrochemical processes largely utilize zeolite-type materials for catalysts. Zeolites have been the subject of continuous developments and modifications for many years. The zeolites of Beta-type (BEA), Y-type, and ZSM-5-type structure are important as catalytic materials for chemical industry applications. ZSM-22 zeolite is identified as a one-dimensional-pore zeolite, and was discovered by Mobil Oil Corporation in the early 1980's. ZSM-22 is known as an orthorhombic, high-silica zeolite of a TON framework topology.
- Zeolites are used in automotive emissions control, industrial off-gas purification, volatile organic carbon (VOC) reduction, and nitrogen oxides (NOx) reduction technologies. As process catalysts, they are used for fuel upgrading, production of petrochemical intermediates, and processing chemicals. BEA zeolites, for example, are also useful for adsorption purposes, such as odor removal and active carbon replacement. Growing demand for new catalytic chemical processing has led to a rise in the need for more reactive and selective catalysts. Nanotechnology for the production of catalytic material is essential to overcoming catalytic reaction limitations by allowing for greater dispersion of reactive catalysts, which leads to higher turnover of hydrocarbon conversion.
- The TON zeolite framework consists of 5-, 6- and 10-membered rings. The TON zeolite framework group includes ZSM-22, Theta-1, Nu-10, KZ-2, and ISI-1 zeolites. The pore structure of the TON framework is known to be linear, one-dimensional, with 10-membered ring pore openings and effective pore sizes of about 0.45 nm by 0.55 nm.
- Pores of ZSM-22 are smaller than the pores of ZSM-5, and are classified as a medium-pore on the zeolite size scale. ZSM-22 zeolite crystals synthesized by conventional hydrothermal synthesis include crystals that are needle-like with a crystal size in the range of about 1μm to 20 μm. Conventional hydrothermal synthesis of ZSM-22 zeolite is known.
- ZSM-22 zeolite has been shown to be a weak catalyst or catalyst support when applied as a steam cracker catalyst, and when applied in various reactions such as hydroisomerization, hydrocarbon upgrading, naphtha cracking, methanol conversion to gasoline, methanol conversion to propylene, butane conversion to olefins, and hexane conversion to olefins.
- Micro-sized ZSM-22 zeolite is catalytically deactivated rapidly due to exhibiting pore sizes that can be easily blocked by coke from hydrocarbon conversion reactions. Prior art systems and processes for producing ZSM-22 zeolite catalyst crystals are insufficient for producing consistently-sized crystals without impurities and without agglomeration, particularly in the nano-size scale.
- Applicant has recognized a need for systems and methods which apply microwave heating to a zeolite solution comprising non-ionic surfactant for producing consistently-sized ZSM-22 zeolite catalyst crystals, particularly in the nano-scale less than 1 μm. Prior art technical problems include agglomeration during zeolite production and catalyst deactivation when used in hydrocarbon conversion reactions with steam.
- Embodiments of systems and methods disclosed here allow for several size ranges of nano-scale ZSM-22 zeolite crystals to be consistently produced without agglomeration and without impurities. There is presently no suitable industrial process to make nano-scale ZSM-22. Here, ZSM-22 zeolite crystals of three unique size ranges are produced with lengths varying from about 50 nm to about 600 nm, and with widths ranging from about 55 nm to about 75 nm. In some embodiments of the process, one or more non-ionic surfactant and microwave heating is applied in four isothermal steps. Nonionic surfactants suitable in embodiments here include those nonionic surfactants based on polyoxyethylene. Systems and methods can be scaled to an industrial scale to manufacture nano zeolites for oil upgrading and hydrocarbon conversion reactions. By reducing crystals size, catalytic activity of the ZSM-22 crystals is surprisingly and unexpectedly enhanced.
- In ZSM-22 zeolite crystals produced here, it is believed, without being bound by any theory or practice, that by increasing mesoporous pore-mouth openings to access larger hydrocarbon molecules, better catalytic activity is obtained because reaction diffusional length is shortened. Shortened diffusional length assists hydrocarbon molecules in contacting acidic sites of nano ZSM-22 for primary cracking reactions of hydrocarbons and reduces possible agglomeration of hydrocarbons and coking rates on the ZSM-22.
- The nano-crystals of ZSM-22 zeolite framework start forming in a process of nucleation followed by crystallization. Systems and methods disclosed here produce nano-scale ZSM-22 crystals at smaller sizes without agglomeration, and produce uniform crystals both in terms of length and width. Crystal growth is uniquely controlled during manufacturing processes of the nano-scale ZSM-22 zeolite crystals.
- Specifically controlled surfactant concentration of one or more nonionic surfactant in the processes reduces agglomeration of nano-scale ZSM-22 zeolite crystals during production.
- Thus, disclosed here is a method for producing consistently-sized ZSM-22 zeolite catalyst crystals, the method including preparing an aluminate solution; preparing a silica solution; mixing the aluminate solution and the silica solution to form a zeolite-forming solution; heating the zeolite-forming solution with microwave irradiation in a first, a second, a third, and a fourth distinct isothermal stage to produce the consistently-sized ZSM-22 zeolite catalyst crystals within a pre-selected nano-scale crystal size range using a non-ionic surfactant.
- In some embodiments, the step of preparing the aluminate solution comprises mixing deionized water, a hydroxide-containing compound, and an aluminum-containing compound. In other embodiments, the hydroxide-containing compound comprises at least one compound selected from the group consisting of: NaOH, CsOH, LiOH, Ca(OH)2, and KOH, and the aluminum-containing compound comprises at least one compound selected from the group consisting of: of aluminum sulfate octadecahydrate, aluminum oxide, aluminum hydroxide, and aluminum metal. Still in other embodiments, the step of preparing an aluminate solution comprises mixing an organic template with the aluminate solution. In certain other embodiments, the organic template comprises at least one compound selected from the group consisting of: 1,6-diaminohexane, N-ethylpyridine, 1,4-diaminohexane, and diethylamine. Still in other embodiments, the step of preparing the silica solution comprises mixing a silica colloidal solution and water.
- Still in yet other embodiments, the silica colloidal solution is about 40 wt. % silica in water. In certain embodiments, the step of mixing the aluminate solution and the silica solution to form the zeolite-forming solution comprises controlling a ratio of silicon to aluminum to produce the consistently-sized ZSM-22 zeolite catalyst crystals within a pre-selected crystal size range using the non-ionic surfactant. In certain embodiments, in the first isothermal stage microwave irradiation is applied to heat the zeolite solution to between about 35° C. and about 65° C. for between about 3 minutes and about 7 minutes, with stirring applied at a speed between about 200 rpm and about 300 rpm. In some embodiments, in the second isothermal stage microwave irradiation is applied to heat the zeolite solution to between about 90° C. and about 120° C. for between about 5 and about 15 minutes, with stirring applied at a speed between about 200 rpm and about 300 rpm. In certain embodiments, the non-ionic surfactant is added after the second isothermal stage. Still in yet other embodiments, the non-ionic surfactant includes a polyoxyethylene-based compound selected from the group consisting of: polyoxyethylene (2) stearly ether, polyoxyethylene (2) olleyl ether, polyoxyethylene (2) cetyl ether, sorbitan monopalmirate, sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monooleate, polyoxyethylene (4,5) p-tert-octylphenol, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, polyoxyethylene (6) tridecyl ether, polyoxyethylene (10) stearyl ether, polyoxyethylene (10) oleyl ether, polyoxyethylene (7-8) p-tert-octylphenol, polyoxyethylene (10) cetyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene (9) p-tert-octylphenol, polyoxyethylene sorbitan monolaurate, polyoxyethylene (9-10) nonyl ohenol, polyoxyethylene (9-10) p-tert-octyl phenol, polyoxyethylene esters of mixed fatty acids, polyoxyethylene (12) tridecyl ether, polyoxyethylene (12-13) p-tert-octylphenol, polyoxyethylene sorbitan monostearate, polyoxyethylene (17) cetyl-stearyl alcohl, polyoxyethylene (20) stearyl ether, polyoxyethylene (20) oleyl ether, polyoxyethylene (15) tridecyl ether, polyoxyethylene sorbitan monopalmitate, polyoxyethylene (20) cetyl ether, polyoxyethylene (16) p-tert-octylphenol, polyoxyethylene sorbitan monolaurate, polyoxyethylenelauryl ether, and combinations of the same.
- In other embodiments of the method, the third isothermal stage microwave irradiation is applied to heat the zeolite solution to between about 35° C. and about 65° C. for between about 60 and about 80 hours, with stirring applied at a speed between about 350 rpm and about 450 rpm. Still in other embodiments, in the fourth isothermal stage microwave irradiation is applied to heat the zeolite solution to between about 155° C. and about 205° C. for between about 8 and about 16 hours. In certain embodiments, the method includes the steps of neutralizing pH of the produced consistently-sized ZSM-22 zeolite catalyst crystals, water washing the produced consistently-sized ZSM-22 zeolite catalyst crystals, drying the produced consistently-sized ZSM-22 zeolite catalyst crystals, and calcining the produced consistently-sized ZSM-22 zeolite catalyst crystals.
- Still in other embodiments, the step of calcining is carried out under static atmospheric air at a temperature of between about 500° C. and about 550° C. for between about 6 and about 12 hours. In certain embodiments, the method includes the step of applying the produced consistently-sized ZSM-22 zeolite catalyst crystals in a hydrocarbon conversion process.
- Additionally disclosed here is a system for carrying out the various methods disclosed, the system including an aluminate solution mixing chamber; a silica solution mixing chamber; and a microwave-application mixing unit, the microwave-application mixing unit in fluid communication with both the aluminate solution mixing chamber and the silica solution mixing chamber. In some embodiments, the system comprises controllable stirring means in the aluminate solution mixing chamber, the silica solution mixing chamber, and the microwave-application mixing unit. In other embodiments, the microwave-application mixing unit is configured to carry out heating the zeolite solution with microwave irradiation in the first, the second, the third, and the fourth distinct isothermal stages to produce the consistently-sized ZSM-22 zeolite catalyst crystals within a pre-selected crystal size range. In embodiments of the systems and methods disclosed, a majority of the consistently-sized ZSM-22 zeolite catalyst crystals within the pre-selected nano-scale crystal size range exhibit lengths varying from about 50 nm to about 600 nm, and widths ranging from about 55 nm to about 75 nm.
- These and other features, aspects, and advantages of the present disclosure will become better understood with regard to the following descriptions, claims, and accompanying drawings. It is to be noted, however, that the drawings illustrate only several embodiments of the disclosure and are therefore not to be considered limiting of the disclosure's scope as it can admit to other equally effective embodiments.
-
FIG. 1 is a schematic diagram for a system and process to produce consistently-sized ZSM-22 catalyst crystals without agglomeration or impurities using microwave heating and non-ionic surfactant. -
FIG. 2 shows a scanning electron microscope (SEM) image for crystals of nano-sized ZSM-22 zeolite produced at a surfactant to aluminum oxide molar ratio of 2.5. -
FIG. 3 shows a SEM image for crystals of nano-sized ZSM-22 zeolite produced at a surfactant to aluminum oxide molar ratio of 5.0. -
FIG. 4 shows a SEM image for crystals of nano-sized ZSM-22 zeolite produced at a surfactant to aluminum oxide molar ratio of 7.5. -
FIG. 5 shows X-ray diffraction (XRD) patterns confirming ZSM-22 structured zeolite was produced. - So that the manner in which the features and advantages of the embodiments of systems and methods that apply microwave heating to a zeolite solution comprising non-ionic surfactant for producing consistently-sized ZSM-22 zeolite catalyst crystals, as well as others, which will become apparent, may be understood in more detail, a more particular description of the embodiments of the present disclosure briefly summarized previously may be had by reference to the embodiments thereof, which are illustrated in the appended drawings, and which form a part of this specification. It is to be noted, however, that the drawings illustrate only various embodiments of the disclosure and are therefore not to be considered limiting of the present disclosure's scope, as it may include other effective embodiments as well.
- Referring first to
FIG. 1 , a schematic diagram is shown for a system and process to produce consistently-sized nano-scale ZSM-22 catalyst crystals without agglomeration or impurities using microwave heating and non-ionic surfactant.FIG. 1 is described with respect to an example process for production of ZSM-22 zeolite crystals. Surfactant-microwave application system 100 includes an aluminatesolution mixer unit 200 and a separate silicatesolution mixer unit 300.System 100 also includes surfactant-microwave mixing unit 400, which is fluidly coupled to both aluminatesolution mixer unit 200 and silicatesolution mixer unit 300. Surfactant-microwave mixing unit 400 carries out controlled hydrothermal treatment for nucleation growth and crystallization of ZMS-22 nano-crystals. - In one example embodiment, a process operates as follows. In aluminate
solution mixer unit 200, 88.4 kg of deionized water and 3.8 kg of potassium hydroxide (KOH) (purity: 99%) are introduced vialine 210 and stirred at about between 270 rpm and about 330 rpm, preferably about 300 rpm, via stirringrod 220 at a temperature between about 15° C. and about 35° C. for between about 25 minutes and about 35 minutes, preferably about 30 minutes. Other suitable hydroxide-containing alkali and alkaline earth compounds can be used alternatively to or in addition to KOH, including, but not limited to, NaOH, CsOH, LiOH, or Ca(OH)2. - Next, 1.8 kg of aluminum sulfate octadecahydrate (formula: Al2(SO4)3.18H2O) is introduced via
line 210 to aluminatesolution mixer unit 200 and mixed with the solution for between about 25 minutes and about 35 minutes, preferably about 30 minutes, with stirring via stirringrod 220 at between about 270 rpm and about 330 rpm, preferably about 300 rpm, at a temperature between about 15° C. and about 35° C. Other aluminum-containing compounds can be used in addition to or alternative to aluminum sulfate octadecahydrate including, but not limited to, aluminum oxide (Al2O3), aluminum hydroxide (Al(OH)3), and aluminum metal (Al). - Next, 8.2 kg of 1,6-diaminohexane (DAH) (purity: 99.5%) is added to aluminate
solution mixer unit 200 as an organic template vialine 210 and stirred by stirringrod 220 at between about 270 rpm and about 330 rpm, preferably about 300 rpm, for between about 25 minutes and about 35 minutes, preferably about 30 minutes. In some embodiments, heating is not applied in aluminatesolution mixer unit 200, and temperature is in the range of about 15° C. to about 35° C. Finally, the solution in aluminatesolution mixer unit 200 is evacuated viaoutlet 230 to be introduced to surfactant-microwave mixing unit 400 viainlet 405. Other suitable organic templates can be used in addition to or alternative to DAH, including, but not limited to, N-ethylpyridine, 1,4-diaminohexane, or diethylamine. - Separately in silicate
solution mixer unit 300, 36 kg of silica colloidal solution (40 wt. % in water) and 62 kg of water are introduced to the compartment vialine 310. Stirring is applied via stirringrod 320 for between about 25 minutes and about 35 minutes, preferably about 30 minutes at a speed of between 270 rpm and about 330 rpm, preferably about 300 rpm. In some embodiments, heating is not applied in silicatesolution mixer unit 300, and temperature is in the range of about 18° C. to about 35° C. The solution is evacuated viaoutlet 330 and sent to surfactant-microwave mixing unit 400 viainlet 410. - Surfactant-
microwave mixing unit 400 operates after the separate solutions of aluminate and silica are introduced to the unit viainlets electrical heater 440 producingmicrowave irradiation 450 to synthesize the nano-sized ZSM-22. In a first isothermal stage,electrical heater 440 operates to heat the solution mixture in surfactant-microwave mixing unit 400 to between about 35° C. and about 65° C., or to between about 45° C. and about 55° C., for between about 3 minutes and about 7 minutes, preferably about 5 minutes. Mixing via stirringrod 420 is applied when microwave application begins viaelectrical heater 440 at a speed between about 200 rpm and about 300 rpm, preferably about 250 rpm. - In a second isothermal stage, a selected quantity of non-ionic surfactant is added via
line 430. First,electrical heater 440 is set at a temperature of between about 90° C. and about 120° C., or between about 100° C. and about 110° C., and stirring is applied via stirringrod 420 at between about 200 rpm and about 300 rpm, preferably about 250 rpm, for between about 5 and about 15 minutes. Then, the selected weight of nonionic surfactant, for example a nonionic surfactant including poly-oxyethylene groups, is added to surfactant-microwave mixing unit 400 vialine 430. In one embodiment, if polyoxyethylene(10)oleyl ether (molecular weight 709 g/mole) is used as surfactant, suitable surfactant to aluminium oxide molar ratios are from about 0.1:1 to 10:1, or from about 1:1 to about 7.5:1, or about 2.5:1, 5:1, or 7.5:1, for example. - Optional nonionic surfactants based on polyoxyethylene surfactants include, but are not limited to, any one of or any combination of: polyoxyethylene (2) stearly ether, polyoxyethylene (2) olleyl ether, polyoxyethylene (2) cetyl ether, sorbitan monopalmirate, sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monooleate, polyoxyethylene (4,5) p-tert-octylphenol, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, polyoxyethylene (6) tridecyl ether, polyoxyethylene (10) stearyl ether, polyoxyethylene (10) oleyl ether, polyoxyethylene (7-8) p-tert-octylphenol, polyoxyethylene (10) cetyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene (9) p-tert-octylphenol, polyoxyethylene sorbitan monolaurate, polyoxyethylene (9-10) nonyl ohenol, polyoxyethylene (9-10) p-tert-octyl phenol, polyoxyethylene esters of mixed fatty acids, polyoxyethylene (12) tridecyl ether, polyoxyethylene (12-13) p-tert-octylphenol, polyoxyethylene sorbitan monostearate, polyoxyethylene (17) cetyl-stearyl alcohl, polyoxyethylene (20) stearyl ether, polyoxyethylene (20) oleyl ether, polyoxyethylene (15) tridecyl ether, polyoxyethylene sorbitan monopalmitate, polyoxyethylene (20) cetyl ether, polyoxyethylene (16) p-tert-octylphenol, polyoxyethylene sorbitan monolaurate, and polyoxyethylenelauryl ether.
- The use of nonionic surfactants has several advantages versus long chain alcohols as there are no electronic charge groups or limited charge in the nonionic molecules. The utilization of surfactant helps control the sizes of nano-scale crystals of ZSM-22 without negatively affecting the zeolite framework and crystallinity. Systems and processes adapt the use of one or more nonionic surfactant to ZSM-22 zeolite crystal production under controlled microwave irradiation in order to meet the crystallinity of the ZSM-22 framework and synthesize different size scales of nano-sized of ZSM-22.
- The weight of nonionic surfactant is adjusted, in part, according to the weight of aluminum oxide applied in the process. The molar ratio of the nonionic surfactant to aluminum oxide can vary from about 0.05:1 to 30:1.
- For nano-scale ZSM-22 crystal size of length of about 80-95 nm by a width of about 55-65 nm, the surfactant to aluminum oxide molar ratio is between about 2.4 and about 2.6, preferably about 2.5 (See
FIG. 2 ). For ZSM-22 crystal size of length of about 125-140 nm by a width of about 55-65 nm, the surfactant to aluminum oxide molar ratio is between about 4.9 and about 5.1, preferably about 5 (SeeFIG. 3 ). For nano-scale ZSM-22 crystal size of length of about 280-300 nm by a width of about 65-75 nm, the surfactant to aluminum oxide molar ratio is between about 7.4 and about 7.6, preferably about 7.5 (SeeFIG. 4 ). - In a third isothermal stage, zeolite aging is applied and
electrical heater 440 is set such that the temperature of surfactant-microwave mixing unit 400 is between about 35° C. and about 65° C., or is between about 45° C. and about 55° C., and stirring is applied via stirringrod 420 at a speed of between about 350 rpm and about 450 rpm, preferably 400 rpm, for about 60 to about 80 hours, preferably about 72 hours. - In a fourth isothermal stage, zeolite crystallization is carried out, and microwave irradiation is applied to surfactant-
microwave mixing unit 400 for heating, and the temperature increases to between about 155° C. and about 205° C., or between about 165° C. and about 195° C., or between about 170° C. and about 190° C., and stirring is applied via stirringrod 420 at a speed of between about 350 rpm and about 450 rpm, preferably 400 rpm, for between about 8 and about 16 hours, or between about 10 hours and about 14 hours. - At the end of crystallization of nano-sized ZSM-22, the fourth isothermal stage, surfactant-
microwave mixing unit 400 is cooled down to between about 18° C. and about 40° C. Zeolite solution is evacuated vialine 460 for further treatment in a separate container (not pictured). In the separate container, the acidity of the solution is adjusted to between about pH 6.5 and about pH 7.5, preferably about pH 7 (neutralized), by addition of HCl in water solution (concentration of about 0.1 mol/L), with the volume to be added from about 5 mL to about 200 mL, depending on the scale of the system and process. - After pH neutralization, a centrifuge is applied to collect the powder comprising nano-sized ZSM-22 zeolite crystals. The centrifuge is run at a speed between about 2000 rpm and about 4000 rpm and a temperature between about 18° C. and about 40° C. Next, distilled water washing is carried out 2-3 times to wash the zeolite powder, and the washed zeolite powder is retrieved via filtration. Drying is applied to nano-sized ZSM-22 zeolite powder at a temperature of between about 90° C. and about 100° C. for between about 12 and about 24 hours. Calcination of dried nano-sized ZSM-22 zeolite is carried out under static atmospheric air and at a temperature of between about 500° C. and about 550° C., preferably 525° C. for between about 6 and about 12 hours. The oven ramping rate can be set at between about 1 and about 3° C./min.
- In some embodiments, the resulting zeolite has a framework crystal of nano-size ZSM-22 zeolite, and this is shown in
FIG. 5 .FIG. 5 shows X-ray diffraction (XRD) patterns of ZSM-22 zeolite. ZSM-22 is characterized via the 2-theta angle peaks at 20.4°, 24.4°, 24.6°, and 25.8°. - Thus, the surfactant-microwave system and process of
FIG. 1 synthesizes nano-sized ZSM-22 zeolite with pre-selected recipes and process steps, which control sizes of nano-scale crystals produced in order to use ZSM-22 as catalyst. The ZSM-22 zeolite crystals produced can be used as material for catalyst support, and can be used for gas adsorption and catalyst applications in chemical and hydrocarbon conversion reactions, including those involving steam cracking. -
FIG. 2 shows a scanning electron microscope (SEM) image for crystals of nano-sized ZSM-22 zeolite produced at a surfactant to aluminum oxide molar ratio of 2.5. The ratio of surfactant to aluminum oxide can vary for example between about 2.4 and about 2.6. InFIG. 2 , the length of the zeolite crystals is between about 80 nm and about 95 nm, and the width is between about 55 nm and about 65 nm. In various embodiments a wide molar ratio range of Si:Al can be used, varying between about 10 and about 200. -
FIG. 3 shows a SEM image for crystals of nano-sized ZSM-22 zeolite produced at a surfactant to aluminum oxide molar ratio of 5.0. The ratio of surfactant to aluminum oxide can vary for example between about 4.9 and about 5.1. InFIG. 3 , the length of the zeolite crystals is between about 125 nm and about 140 nm, and the width is between about 55 nm and about 65 nm. -
FIG. 4 shows a SEM image for crystals of nano-sized ZSM-22 zeolite produced at a surfactant to alumina oxide molar ratio of 7.5. The ratio of surfactant to aluminum oxide can vary for example between about 7.4 and about 7.6. InFIG. 4 , the length of the zeolite crystals is between about 280 nm and about 320 nm, and the width is between about 65 nm and about 75 nm. - The term “about” when used with respect to a value or range refers to values including plus and minus 5% of the given value or range.
- The singular forms “a,” “an,” and “the” include plural referents, unless the context clearly dictates otherwise.
- In the drawings and specification, there have been disclosed embodiments of systems and methods which apply microwave heating to a zeolite solution comprising non-ionic surfactant for producing consistently-sized ZSM-22 zeolite catalyst crystals, and although specific terms are employed, the terms are used in a descriptive sense only and not for purposes of limitation. The embodiments of the present disclosure have been described in considerable detail with specific reference to these illustrated embodiments. It will be apparent, however, that various modifications and changes can be made within the spirit and scope of the disclosure as described in the foregoing specification, and such modifications and changes are to be considered equivalents and part of this disclosure.
Claims (10)
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US5254770A (en) | 1982-09-01 | 1993-10-19 | Mobil Oil Corp. | Isomerization of aromatic compounds over ZSM-22 zeolite |
US4481177A (en) | 1982-12-09 | 1984-11-06 | Mobil Oil Corporation | Synthesis of zeolite ZSM-22 with a heterocyclic organic compound |
US4556477A (en) | 1984-03-07 | 1985-12-03 | Mobil Oil Corporation | Highly siliceous porous crystalline material ZSM-22 and its use in catalytic dewaxing of petroleum stocks |
AU576030B2 (en) | 1984-12-31 | 1988-08-11 | Mobil Oil Corporation | Process for producing high boiling jet fuel |
US5063038A (en) | 1985-10-21 | 1991-11-05 | Mobil Oil Corp. | Zeolite synthesis using an alcohol or like molecule |
US4778666A (en) * | 1986-12-04 | 1988-10-18 | Mobil Oil Corporation | Crystallization method employing microwave radiation |
US5157194A (en) | 1991-12-20 | 1992-10-20 | Mobil Oil Corporation | Highly selective n-olefin isomerization process using microcrystalline ZSM-22 |
CA2137071C (en) | 1992-06-05 | 2001-12-04 | Johannes P. Verduijn | Zsm-22 zeolite |
CA2161875C (en) | 1993-05-28 | 2006-02-14 | Jeffrey Scott Beck | Process for modifying the shape selectivity of a zeolite catalyst and use of the modified catalyst |
US7119245B1 (en) | 2001-10-25 | 2006-10-10 | Sandia Corporation | Synthesis of an un-supported, high-flow ZSM-22 zeolite membrane |
US7238636B2 (en) | 2003-07-23 | 2007-07-03 | Exxonmobil Chemical Patents Inc. | High temperature calcination of selectivated molecular sieve catalysts for activity and diffusional modification |
US20110201861A1 (en) * | 2008-06-06 | 2011-08-18 | Total Petrochemicals Research Feluy | Process for Making Crystalline Metallosilicates |
CN103101924B (en) | 2013-02-01 | 2014-09-03 | 浙江大学 | Method for preparing ZSM-22 molecular sieve by using seed crystal synthesis method |
US9561477B2 (en) * | 2013-02-28 | 2017-02-07 | Ohio State Innovation Foundation | Methods for synthesizing microporous crystals and microporous crystal membranes |
WO2015021611A1 (en) | 2013-08-14 | 2015-02-19 | 中国科学院大连化学物理研究所 | Zsm-22 molecular sieve and synthesis method for me-zsm-22 |
US9186659B2 (en) * | 2014-01-09 | 2015-11-17 | King Fahd University Of Petroleum And Minerals | Controlled growth of MTT zeolite by microwave-assisted hydrothermal synthesis |
CN104211080B (en) | 2014-09-01 | 2016-07-06 | 中科合成油技术有限公司 | A kind of preparation method of Fe isomorphous substitution ZSM-22 molecular sieve |
CN104671253B (en) | 2015-02-16 | 2017-01-04 | 黑龙江大学 | A kind of preparation method of ZSM-22 molecular sieve nanometer sheet |
CN105668582A (en) | 2016-03-25 | 2016-06-15 | 中国科学院大连化学物理研究所 | Preparation method of nano ZSM-22 molecular sieve |
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Non-Patent Citations (1)
Title |
---|
Khedri, Behzad, et al. "A review on Microwave-Assisted biodiesel Production". Energy Sources, Part A: Recovery, Utilization and Environmental Effects. 1556-7230. (2018) (Year: 2018) * |
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