CN115818661A - Preparation method of multistage Kong Gaogui hydrophobic zeolite with FAU structure - Google Patents
Preparation method of multistage Kong Gaogui hydrophobic zeolite with FAU structure Download PDFInfo
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- 239000010457 zeolite Substances 0.000 title claims abstract description 122
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 117
- 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 117
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 62
- 239000002253 acid Substances 0.000 claims abstract description 33
- 238000010306 acid treatment Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 238000001179 sorption measurement Methods 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 25
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000001514 detection method Methods 0.000 claims description 18
- 238000011282 treatment Methods 0.000 claims description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001228 spectrum Methods 0.000 claims description 6
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- 229910021641 deionized water Inorganic materials 0.000 claims description 5
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- 238000000634 powder X-ray diffraction Methods 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
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- 239000000706 filtrate Substances 0.000 claims description 3
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- 238000003756 stirring Methods 0.000 claims description 3
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- 239000002994 raw material Substances 0.000 abstract description 20
- 239000000126 substance Substances 0.000 abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 description 34
- 239000000523 sample Substances 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 229910052710 silicon Inorganic materials 0.000 description 16
- 239000010703 silicon Substances 0.000 description 15
- 238000003795 desorption Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000012071 phase Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 6
- 239000005049 silicon tetrachloride Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000002149 hierarchical pore Substances 0.000 description 4
- 241000690776 Hassar Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
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- 239000013074 reference sample Substances 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000282376 Panthera tigris Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- GPFIZJURHXINSQ-UHFFFAOYSA-N acetic acid;nitric acid Chemical compound CC(O)=O.O[N+]([O-])=O GPFIZJURHXINSQ-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
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- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 238000002424 x-ray crystallography Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to the technical field of chemical industry, in particular to a preparation method of multistage Kong Gaogui hydrophobic zeolite with an FAU structure, which comprises the following steps of S1, calcining USY powder; s2, acid treatment; s3, cleaning and draining; and S4, drying to finish the preparation. According to the invention, the commercial USY powder is calcined at high temperature, and the USY powder calcined at high temperature is subjected to acid treatment by using a dilute acid solution and then washed, so that framework aluminum in the USY powder is removed, and the USY powder is made into the multistage Kong Gaogui hydrophobic FAU zeolite with fine structural micropores and rich mesopores, and meanwhile, the target products of different SAR can be adjusted and prepared according to the change of the type of the dilute acid solution, so that the prepared target products have different hydrophobic indexes, and the raw materials are cheap and easy to obtain, and only the commercial USY powder is adopted as the raw material, so that the preparation process is simple, and the industrial mass production of the multistage Kong Gaogui hydrophobic FAU zeolite is facilitated.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a preparation method of multistage Kong Gaogui hydrophobic zeolite with an FAU structure.
Background
FAU zeolite is the most widely used, the largest synthetic large-pore zeolite of consumption, its crystal framework structure is connected into the large cage namely alpha cage by the column that four oxygen-membered ring and six oxygen-membered ring form of beta cage that six oxygen-membered ring and eight oxygen-membered ring form, the 12 oxygen-membered ring window diameter of this cage is 0.74nm, the pore volume is 0.32ml/g; the X zeolite in the same FAU type zeolite has SAR of 2 to 3, belongs to low-silicon zeolite, and has high hydrophilic adsorption property and is commonly used in industrial dehydration desiccant and adsorbent; another zeolite of FAU type, Y zeolite, having SAR ranging from 3 to 6, is used in large quantities in crude oil cracking catalysts (FCC catalysts) in petroleum refining; a large number of researches prove that as the SAR of the FAU zeolite framework is improved, the structural hydrothermal stability is obviously improved, and the water adsorption quantity is correspondingly reduced; when the SAR of the FAU zeolite is more than 25, the FAU zeolite presents good hydrophobic and oleophilic adsorption property and can be used for adsorbing and removing Volatile Organic Compounds (VOC) in waste gas with the diameter of more than 0.7nm and organic compounds (TOC) in waste water; based on the fact that organic molecules with larger sizes in waste gas and waste water are adsorbed, in order to improve the dynamic adsorption efficiency (namely the adsorption efficiency of the organic molecules at higher space velocity) in actual use, the high-silicon hydrophobic FAU zeolite serving as the main material of the adsorbent needs to have a high BET surface area and also needs to have certain mesopores and mesopore spaces with larger pore diameters so as to be beneficial to the diffusion of the organic molecules in FAU zeolite crystals in the adsorption and desorption processes; therefore, the multi-stage Kong Gaogui hydrophobic FAU zeolite which can be industrially produced in a large scale is needed.
The method for improving the FAU zeolite framework SAR roughly comprises the following steps of synthesizing high-silicon FAU zeolite [ modified Syntheses of Zeolite Materials, second Revised Edition,2001, P159] of SAR 7.6 by directly carrying out hydro-thermal synthesis by adding crown ether into a reactant system consisting of silica sol and sodium aluminate; liquid phase modification, namely, taking fluosilicic acid and salts thereof as chemical modifiers, dealuminizing and replenishing silicon in a water phase, and improving SAR of a FAU zeolite framework to more than 20 through one-time reaction, wherein the method is used up to now, the catalyst factories of various large petrochemical companies in China produce the hydrocatalytic cracking agent by the method, but the method has the environmental problems of high cost and waste liquid treatment, and the method is difficult to carry out liquid phase treatment for multiple times to prepare the FAU zeolite with higher SAR; the vapor-solid phase reaction method uses silicon tetrachloride as raw material, powdered or formed NaY zeolite is used for preparing high-silicon and all-silicon FAU type molecular sieves with SAR >6 through vapor-solid phase dealumination and silicon supplementation reaction in nitrogen flow containing the silicon tetrachloride at 250-550 ℃; chem.soc.f, faraday trans.i,1986,82,1449-1469], [ CN103787353a, CN102451736A, CN101850239a, CN2016111723056]; the main reasons that industrial large-scale production of the silicon tetrachloride is difficult to realize by the vapor-solid phase reaction method of the silicon tetrachloride are that the silicon tetrachloride belongs to flammable, explosive, toxic and highly corrosive chemicals, in addition, the excessive silicon tetrachloride cannot be recovered and fully utilized, and a reaction byproduct, namely aluminum trichloride, is not easy to collect into a useful byproduct, which wastes resources and causes environmental pollution, and the preparation methods of most high-silicon FAU zeolites rarely involve endowing the prepared high-silicon FAU zeolite products with hydrophobic properties.
Chinese patent CN1151964C proposes that FAU zeolite powder with SAR of at least 20 can be calcined in the presence of water vapor at 650-1000 ℃ under turbulent condition in a flowing form for at least 15 minutes to 4 hours to obtain hydrophobic property; a method for preparing hierarchical pore low-silicon FAU zeolite is proposed by Amin Osatiashtiani et al: FAU zeolite purchased from SAR 60 of Zeolysite corporation of America was treated with a mixture of 0.1M NaOH and 0.1M tetrapropylammonium bromide (TPABr) at 60 ℃ to remove a part of framework silicon atoms on the zeolite framework to prepare low-silicon Na-FAU zeolite having a multipolar pore structure, and NH was added thereto 4 Cl solution exchange to remove sodium and bake to remove NH 3 The prepared multipolar pore H-FAU zeolite has SAR of 60, 12 and 5.2 respectively and is used as a catalyst for converting biological grease; the study found that the sample of H-FAU zeolite thus prepared had a measured low temperature nitrogen adsorption BET surface area of 670m 2 G to 800m 2 (g) its adsorption/desorption isotherm is P/P 0 When the desorption curve is more than 0.45, the desorption curve is obviously higher than the adsorption curve, and an obvious hysteresis loop appears between the adsorption curve and the desorption curve, which indicates that the sample prepared by the method is the hierarchical pore zeolite consisting of structural micropores and mesopores, and the surface area of the mesopores is 24m 2 G to 302m 2 /g，[Biomass Conv.Bioref.(2017)7:331–342]。
At present, environmental pressure at home and abroad makes a plurality of chemical enterprises urgently require to reduce and eliminate discharge of VOC in waste gas and TOC in waste water, although hydrophobic ZSM-5 can remove small molecular organic matters with the diameter less than 0.6nm, organic matters with larger molecular diameters can only use hydrophobic FAU or Beta zeolite with the structural pore diameter more than 0.7nm, wherein the hydrophobic FAU zeolite is the first choice; there is an urgent need in the market, but there is no domestic large supply except for the qualified products that few companies in the united states sell at high prices.
The hierarchical pore Gao Gui hydrophobic FAU zeolite is a novel high-silicon hydrophobic molecular sieve material which is provided for meeting the urgent needs of domestic markets and has fine structural micropores and rich mesopores, and a preparation method capable of realizing large-scale mass production is provided.
Disclosure of Invention
Therefore, the invention provides a preparation method of multistage Kong Gaogui hydrophobic zeolite with an FAU structure, which is used for overcoming the technical problem that high-silicon hydrophobic zeolite with fine structural micropores and rich mesopores is difficult to prepare in a large scale in the prior art.
In order to achieve the above object, the present invention provides a method for preparing a multi-stage Kong Gaogui hydrophobic zeolite having an FAU structure, comprising,
step S1, calcining USY powder, namely placing the USY powder in a muffle furnace to calcine for 1 to 10 hours at the temperature of 600 to 800 ℃;
step S2, acid treatment, namely mixing the calcined USY powder with a dilute acid solution, heating to 80-95 ℃ while stirring, and keeping for 1-8 h;
s3, cleaning, draining, cooling the mixture of the USY powder and the dilute acid solution to room temperature after the acid treatment is finished, performing vacuum suction filtration on a Buchner funnel to remove the waste acid solution to form a filter cake, and washing the filter cake with deionized water;
and S4, drying, namely placing the filter cake in an electric heating oven for heating and drying, wherein the heating temperature is 150-200 ℃, and after the heating and drying are finished, preparing powdery multistage Kong Gaogui hydrophobic zeolite with an FAU structure and detecting.
Further, in the step S1, the wide-angle powder XRD spectrum of the USY powder shows all characteristic diffraction spectra thereof having a typical pure FAU-type structure without any hetero-crystalline phase, and in the high-angle powder diffractogram thereof from 56 °/2 θ to 60 °/2 θ, the diffraction peak of the diffraction index (15 3) is located at 58.2 °/2 θ.
Further, in the step S2, the dilute acid solution is one of sulfuric acid, hydrochloric acid, nitric acid, acetic acid, oxalic acid and citric acid.
Further, the concentration of the dilute acid solution is 0.05M to 0.75M, the treatment temperature is 80 ℃ to 95 ℃, the treatment time is 1 hour to 8 hours, and the liquid/solid ratio is 5/1 to 10/1.
Further, in the step S3, when the filter cake is washed with deionized water, the PH of the washing filtrate is between 5.9 and 6.1, and the washing is completed.
Further, in the step S4, sampling is performed in the prepared multistage Kong Gaogui hydrophobic zeolite having the FAU structure, and XRD crystal phase detection, n-hexane vapor adsorption detection, and water vapor adsorption detection are performed.
Furthermore, when the manufactured multistage Kong Gaogui hydrophobic zeolite with the FAU structure is subjected to XRD crystal phase detection, an X-ray powder diffractometer is used, the set wide-angle scanning range is 5-35 degrees/2 theta, the scanning speed is 4 degrees/2 theta/min for detection, and the set high-angle scanning range is 55-60 degrees/2 theta, and the scanning speed is 1 degrees/2 theta/min for detection.
Furthermore, when the prepared multistage Kong Gaogui hydrophobic zeolite with the FAU structure is subjected to n-hexane vapor adsorption detection, the adsorption temperature is set to be 30 ℃ and the vapor pressure is set to be 5mmHg, and a detection sample is heated to 350 ℃, dehydrated and dried in vacuum and cooled to be 30 ℃.
Furthermore, when the prepared multistage Kong Gaogui hydrophobic zeolite with the FAU structure is subjected to water vapor adsorption, the detection temperature is set to be 35 ℃, and the multistage Kong Gaogui hydrophobic zeolite with the FAU structure and a saturated ammonium chloride salt solution are subjected to saturated vapor equilibrium for 24 hours.
Further, in the step S5, SAR of the multi-stage Kong Gaogui hydrophobic zeolite having FAU structure is in 14.1 to 414.
Compared with the prior art, the invention has the beneficial effects that the multistage Kong Gaogui hydrophobic zeolite with an FAU structure can be prepared by adopting the commercially available USY powder, the USY powder is subjected to high-temperature calcination treatment before preparation, the USY powder framework aluminum is removed by using a dilute acid solution, the USY powder framework aluminum can be removed by adjusting the type of the dilute acid solution and different treatment conditions, target products with different SAR are prepared, the prepared target products have different hydrophobicity indexes, the prepared high-silicon hydrophobic zeolite has an FAU type structure, fine structural micropores and rich mesopores, the preparation method is simple, the requirement on the USY powder for preparation is lower, the commercially available USY powder can be adopted, the raw materials are cheap and easy to obtain, and industrial mass production is facilitated.
Drawings
FIG. 1 is a broad angle diffraction pattern of the multi-stage Kong Gaogui hydrophobic FAU zeolite XRD powder described in this example;
FIG. 2 is the XRD powder high angle diffractogram of the multi-stage Kong Gaogui hydrophobic FAU zeolite of this example;
fig. 3 is a temperature contour diagram of low-temperature nitrogen adsorption and desorption of the multistage Kong Gaogui hydrophobic FAU zeolite according to this example.
Detailed Description
In order that the objects and advantages of the invention will be more clearly understood, the invention is further described below with reference to examples; it should be understood that the specific embodiments described herein are merely illustrative of the invention and do not delimit the invention.
Preferred embodiments of the present invention are described below with reference to the accompanying drawings. It should be understood by those skilled in the art that these embodiments are only for explaining the technical principle of the present invention, and do not limit the scope of the present invention.
It should be noted that in the description of the present invention, the terms of direction or positional relationship indicated by the terms "upper", "lower", "left", "right", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, which are only for convenience of description, and do not indicate or imply that the device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
The test method employed in this example was,
1, identifying the XRD crystal phase,
the invention relates to a method for identifying the crystal phase of a multi-stage Kong Gaogui hydrophobic FAU zeolite sample, which is tested by an XD 2X-ray powder diffractometer of Beijing Pujingyo general instrument company, wherein the wide-angle scanning range is 5-35 degrees/2 theta, and the scanning speed is 4 degrees/2 theta/min; the high-angle scanning range is 55-60 degrees/2 theta, and the scanning speed is 1 degree/2 theta/min.
2, determining the chemical composition of the raw materials,
the multi-stage Kong Gaogui hydrophobic FAU zeolite sample silicon aluminum chemical composition and SiO thereof were measured by S8 TIGER X-ray fluorescence spectrometer (XRF) of Bruker, germany 2 、Al 2 O 3 、Na 2 O、Fe 2 The percentage of O and the silica to alumina molar ratio (SAR) were calculated.
3, determination of adsorption/desorption Properties
3.1 Low temperature Nitrogen adsorption
The low-temperature nitrogen adsorption isotherm, the BET specific surface area, the total pore volume, the micropore volume, the mesopore volume, the pore diameter data and the like of the multistage Kong Gaogui hydrophobic FAU zeolite sample are tested by a 3H-2000PS2 static capacity method specific surface and pore diameter analyzer of Beijing Bei Shide instrument company. Wherein, the diameter of the micropore is measured by an H-K method, and the diameter of the mesopore is the average pore diameter (4V/A) calculated by adsorption (cylinder pore model) by a BJH method.
3.2 determination of hydrophobic adsorption Properties
A, n-hexane steam adsorption:
the n-hexane vapor adsorption amount on a multi-stage Kong Gaogui hydrophobic FAU zeolite sample is measured by a 3H-2000PW type multi-stage gravimetric vapor adsorption instrument of a domestic Bei Shide instrument company, the adsorption temperature is 30 ℃, and the vapor pressure is 5mmHg. The sample to be tested weighs 100 to 200mg. After a sample to be detected is loaded into a sample chamber, the instrument automatically heats the sample to 350 ℃ according to a preset program, carries out vacuum dehydration and drying, cools the sample to 30 ℃, and then introduces n-hexane steam which is degassed and purified in advance into the sample chamberControlling the vapor pressure to be 5mmHg to make the sample to be detected adsorb n-hexane vapor until the adsorption reaches balance, and automatically outputting the measured n-hexane vapor adsorption quantity W of the zeolite sample by the instrument H ；
B, water vapor adsorption:
the water vapor adsorption quantity W of the multistage Kong Gaogui hydrophobic FAU zeolite sample to be tested at 35 ℃ is determined according to the national standard method W Is calculated by the weight gain of the saturated ammonium chloride solution which is balanced with saturated steam of the saturated ammonium chloride solution for 24 hours;
c, hydrophobic coefficient H Z :
The hydrophobic coefficient H of the multistage Kong Gaogui hydrophobic FAU zeolite sample of the invention Z ＝W H /W W
E.g. H of the zeolite to be tested Z Less than 1.0, the zeolite is said to be hydrophilic;
e.g. H of the zeolite to be tested Z Above 1.0, the zeolite is said to be hydrophobic.
Referring to fig. 1 and fig. 2, fig. 1 is a broad-angle diffraction pattern of XRD powder of multi-stage Kong Gaogui hydrophobic FAU zeolite according to this embodiment; FIG. 2 is the XRD powder high angle diffractogram of the multi-stage Kong Gaogui hydrophobic FAU zeolite of this example;
for the characterization of the raw USY powder and its pre-treatment, the wide angle powder XRD spectrum of the USY available on the market (see fig. 1) shows all characteristic diffraction spectra with typical pure FAU-type structure, without any heterocrystal phase, and in its high angle powder diffractogram from 56 °/2 θ to 60 °/2 θ, the diffraction peak of the diffraction index (15 3) is located at 58.2 °/2 θ (see fig. 2), the sample has SAR of 6.51 and sodium oxide content of 3.2% by XRF compositional analysis; the BET specific area determined on the low-temperature nitrogen adsorption side of the sample was 872m 2 The above data demonstrate that commercially available USY powder meets the quality requirements for preparing the multistage Kong Gaogui hydrophobic FAU zeolite of the present invention.
The USY powder with qualified quality can be used for preparing the multistage Kong Gaogui hydrophobic FAU zeolite raw material powder after being calcined. About 1.2 kg of USY powder is put into a ceramic large crucible with a cover and a capacity of 2000mL, and the ceramic large crucible is placed in a muffle furnace to be calcined for 1h to 10h at 600 ℃ to 800 ℃, and the adsorption water and the crystal water contained in the ceramic large crucible are removed, so that the USY powder can be used for preparing the multistage Kong Gaogui hydrophobic FAU zeolite raw material powder.
Examples 1 to 12, see Table 1, for different types of acid treatment conditions for USY feedstock powders, including acid concentration, liquid/solid ratio, treatment temperature and treatment time, and product number,
the specific implementation conditions of the multistage Kong Gaogui hydrophobic FAU zeolite of the present invention are respectively prepared by treating calcined USY raw material powder with dilute aqueous solutions of sulfuric acid, hydrochloric acid, nitric acid, acetic acid, oxalic acid and citric acid; processing USY raw material powder in 70 g per batch, placing the USY raw material powder in a beaker with the capacity of 1000ml, measuring pre-prepared diluted acid solutions with different concentrations according to a pre-designed solid/liquid ratio, pouring the diluted acid solutions into the beaker, heating the diluted acid solutions to 80-95 ℃ under the condition of continuous stirring for 1-8 h, cooling the acid solution to room temperature after the acid treatment is finished, performing vacuum suction filtration on a Buchner funnel to remove waste acid solution, washing a filter cake with deionized water until the pH of the filtrate is close to 6, placing the washed and dried filter cake in a glass vessel, heating the filter cake in an electric heating oven at 150-200 ℃ overnight, and completely drying the filter cake to obtain the multistage Kong Fenzhuang Gao Gui hydrophobic FAU zeolite product with different SAR;
TABLE 1 treatment conditions for different kinds of acids for treating USY raw meal
With continued reference to table 2, which shows the chemical composition of the multi-stage Kong Gaogui hydrophobic FAU zeolite sample, it can be seen from the chemical composition data in table 2 that the NaY zeolite of the reference sample is SAR 5.68 low silica type zeolite and the USY raw powder is SAR 6.51H-Na type FAU zeolite. While dilute H at different concentrations 2 SO 4 、HCl、HNO 3 Acetic acid, oxalic acid or citric acid to obtain the multistage Kong Gaogui H type FAU zeolite of SAR 14.1 to 414 of the invention.
TABLE 2 multistage Kong Gaogui hydrophobic FAU zeolite sample chemical composition
With continued reference to fig. 1 and 2, the wide angle powder XRD diffractogram shown in fig. 1 indicates that the crystal phases of the products obtained by the dilute acid treatments with different concentrations all belong to the pure phase FAU structure with high crystallinity, while fig. 2 is a high angle powder diffractogram of 56 °/2 θ to 60 °/2 θ of the products S1, S2, S3, S4, S5, S6 obtained by the dilute acid treatments with different concentrations, and the reference samples NaY and USY raw powder, and the diffraction peak of the diffraction index (15 3) is in the range of 58.0 °/2 θ to 59.5 °/2 θ, it can be found that the NaY zeolite with 5.68 degree of diffraction is in 58.2 °/2 θ, the diffraction peak of the USY raw material fraction with SAR 6.51 (15 3) is gradually shifted to 59.2 °/2 θ from 59.2 °/2 θ, the SAR diffraction peak of the (15 3) is gradually shifted from 59.2 °/2 θ to 59.5 θ, and the SAR is shifted to the high angle of the Si — O bond due to the different bond length of the Al structure; si-O bonds are shorter than Al-O bonds, so that when the unit cell SAR is improved by removing the framework aluminum atoms with dilute acid, the aluminum atom content in the unit cell composition is reduced, the silicon atom content is relatively increased, the unit cell volume is shrunk, the crystal structure of the FAU zeolite belongs to a cubic symmetry type, and the unit cell parameters are only 1, namely the parameter a; unit cell volume V = a 3 。
The parameter a and the unit cell framework composition SAR have the following empirical formula:
SAR(SiO 2 /Al 2 O 3 ) = (=) (25.248-a) x8.1633.... Equation (1)
The practical range of the FAU zeolite unit cell parameter a determined by an XRD powder diffraction method and the calculation of the framework SAR according to the empirical formula (1) has certain limitation, namely, when the SAR is less than 30, the FAU zeolite unit cell parameter a is fashionable and feasible. In general, one chooses the formula given in X-ray crystallography for the d value of the strongest peak (1533) in the range of 56 °/2 θ to 60 °/2 θ and its 2 θ angle value in the test pattern of XRD diffraction of FAU zeolite powder:
Sin 2 θ＝λ 2 (h 2 +k 2 +l 2 )/4a 2 ..
a＝λ(h 2 +k 2 +l 2 ) 1/2 Formula (3) with 2Sin θ = K/Sin θ
In the formulas (2) and (3), lambda is the wavelength of the selected X-ray in the powder XRD diffraction pattern test, and constants h, k and l are diffraction indexes of diffraction peaks, namely 15, 3 and 3. If we use the characteristic X-ray K α radiation from the Cu target for our experiment with an average wavelength λ =1.5418A, K =12.01714 is calculated, the unit cell parameter a has a simple relationship with the diffraction angle θ of the (15 3) diffraction peak:
a =12.01714/Sin θ
As can be seen from equation (4), the diffraction angle θ of the (15) diffraction peak has an inverse relationship with the FAU zeolite unit cell parameter a, i.e., as the diffraction angle θ of the (15 3) diffraction peak increases (the diffraction peak moves to a large angle in the diffraction pattern), the unit cell parameter a decreases. And the value of the framework Si/Al molar ratio SAR is increased along with the reduction of the unit cell parameter a according to the formula (1).
The predictions of the above theoretical analysis of X-ray diffraction are consistent with the appearance of the experimental XRD powder diffraction pattern of FIG. 2.
Continuing with Table 3, which shows the adsorption properties of the multi-stage Kong Gaogui hydrophobic FAU zeolite samples, table 3 lists the adsorption properties of the NaY zeolite, USY feedstock powder, and the multi-stage Kong Gaogui hydrophobic FAU zeolite of the present invention prepared from the reference sample by dilute acid solution treatment. The NaY zeolite had a water vapor adsorption amount of 26.5% and an n-hexane adsorption amount of 16.8%, and its hydrophobicity index Hz =0.63, indicating that the NaY zeolite is a typical hydrophilic zeolite. The USY raw material powder available from the market still belongs to hydrophilic zeolite, and has the water vapor adsorption amount of 22.0 percent and the n-hexane vapor adsorption amount of 17.4 percent, and the hydrophobicity index Hz = 0.79. SAR of S1, S2, S3, S4, S5 and S6 samples prepared by treating USY raw material powder with different concentrations and different types of diluted acid under different conditions are respectively increased to 14.1, 42.0, 60.5, 106, 260 and 414, the water adsorption capacity is gradually reduced to 6.2% from 14.3% along with the increase of SAR, but the normal hexane adsorption capacity is maintained between 15% and 17%. The hydrophobicity indices Hz of the S1, S2, S3, S4, S5, S6 samples thus calculated are 1.09, 1.07, 2.08, 1.95, 2.40 and 2.71, respectively. This data demonstrates that the FAU zeolite sample of SAR 14.1 prepared when treated with dilute acid has primarily lipophilic and hydrophobic properties. When the SAR of the sample is increased to 60 or higher, the hydrophobicity index Hz of the sample is increased to be more than 2.0, and higher hydrophobic property is presented.
TABLE 3 Multi-stage Kong Gaogui hydrophobic FAU Zeolite samples adsorption Properties
Wherein the pore diameter is measured by the H-K method; * The BJH method takes the average pore diameter (4V/A) calculated by adsorption (cylinder pore model);
continuing to refer to fig. 3, which is a diagram of the low-temperature nitrogen adsorption and desorption isotherms of the multi-stage Kong Gaogui hydrophobic FAU zeolite of this example, fig. 3 is a diagram of the low-temperature nitrogen adsorption isotherms of the NaY zeolite, USY feedstock powder obtained from the nitrogen adsorption tester, and the high-silicon hydrophobic FAU zeolites S1, S2, S3, S4, S5 and S6 samples prepared by treatment with different concentrations of different types of dilute acids. It can be seen that the adsorption isotherm of NaY almost completely coincides with the desorption isotherm, which is a typical type I microporous adsorption isotherm. The adsorption isotherm of the USY raw material powder is still a typical I-type microporous adsorption isotherm, and the desorption isotherm is in P/P 0 After > 0.45, above the adsorption isotherm, a temperature profile as defined in [ Biomass conv.bioref. (2017) 7]The desorption curve reported here is higher than the adsorption curve, and a significant hysteresis loop appears between the adsorption and desorption curves. This phenomenon illustrates that the sample prepared by this method is a hierarchical pore zeolite consisting of structural micropores and disordered mesopores. For samples S1, S2, S3, S4, S5, and S6, the adsorption isotherm still belongs to the typical type I microporous adsorption isotherm, and the hysteresis loop interval between the adsorption isotherm and the desorption isotherm is significantly enlarged.
Software configured by a 3H-2000PS2 static capacity method specific surface and pore size analyzer of domestic Bei Shide instruments company automatically draws the low-temperature nitrogen adsorption isotherms and the desorption isotherms of all FAU zeolite samples tested in the patent shown in FIG. 3, and also outputs the data of BET specific surface area, total pore volume, micropore volume, mesopore volume, pore size and the like measured by the low-temperature nitrogen adsorption of each sample (see Table 3). It can be seen that the BET surface area of all FAU zeolite samples was substantially 810m 2 (ii) g to 880m 2 In the range of/g, and total pore volumeThe NaY zeolite accumulated in the solution is 0.356ml/g - The USY raw material powder is 0.317ml/g - In addition to the lower value, the total pore volume of the multi-stage Kong Gaogui hydrophobic FAU zeolite samples S1, S2, S3, S4, S5, S6 and the like prepared by dilute acid solution treatment is obviously improved to 0.470ml/g - Above 0.533ml/g - . While the pore volume matched to the volume of the macro-or alpha-cages in the FAU zeolite crystal structure, the NaY zeolite was 0.335ml/g - Close to its total pore volume, the mesopore volume of NaY zeolite is very small, only 0.021ml/g - . The USY raw material powder purchased from the market is produced by using NaY zeolite as a raw material through a secondary ammonium ion exchange Na removal method and a secondary roasting ammonia removal method, and the total pore volume, the micropore volume and the mesopore volume of the USY raw material powder are respectively 0.317ml/g - 、0.308ml/g - And 0.090ml/g - 。
The multistage Kong Gaogui hydrophobic FAU zeolite prepared by treating USY raw material powder with dilute acid solution removes almost all Na in NaY zeolite + Ions to increase the total pore volume of the prepared S1, S2, S3, S5 and S6 samples of different SAR to 0.470ml/g - To 0.533ml/g - . The dilute acid treatment dissolves most or even nearly all of the framework aluminum atoms, causing the unit cell to shrink and the micropore volume to be from 0.322ml/g - Reduced to 0.262ml/g - Meanwhile, more mesopores with large pore diameter are formed, and the volume of the mesopores reaches 0.169ml/g - To 0.238ml/g -1 。
From the pore size analysis data listed in Table 3, it can be seen that the H-K pore size of the NaY reference sample is 0.687nm, which is less than 0.74nm as determined by FAU zeolite crystallographic structure analysis, because a portion of Na + The ions are caused to be located near the 12 oxygen-membered ring apertures of the alpha cages in the FAU zeolite unit cell. The commercial USY raw powder is deprived of most of Na + Ions, the pore opening is completely opened, increasing the H-K pore size to 0.732nm, very close to a 0.74nm structural pore size. Whereas the H-K pore size of the S1, S2, S4, S5 and S6 samples produced by treating USY feedstock powder with dilute acid increased to the range of 0.75nm to 0.77nm, apparently due to the slight enlargement of the pore opening caused by the removal of most of the framework aluminum atoms by the dilute acid.
The average pore diameter (4V/a) data calculated by the BJH method using adsorption (cylindrical pore model) is considered to be due to the fact that most to almost all aluminum atoms in the FAU zeolite framework structure are dissolved by the dilute acid, and a large amount of disordered mesopores are formed. The pore size of the mesopores was estimated from 7.86 nm in the sample S1 of SAR 14.1, and from 10.72nm in the sample S6 of SAR 414 as the dealumination depth was increased.
In conclusion, the multistage Kong Gaogui hydrophobic FAU zeolite of the present invention can be prepared by a simple and easy process of treating with dilute acid and calcining commercial USY raw material powder at high temperature.
So far, the technical solutions of the present invention have been described in connection with the preferred embodiments shown in the drawings, but it is apparent to those skilled in the art that the scope of the present invention is not limited to these specific embodiments. Equivalent changes or substitutions of related technical features can be made by those skilled in the art without departing from the principle of the invention, and the technical scheme after the changes or substitutions can fall into the protection scope of the invention.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention; various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of multi-stage Kong Gaogui hydrophobic zeolite with FAU structure is characterized by comprising the following steps,
step S1, calcining USY powder, namely placing the USY powder in a muffle furnace to calcine for 1 to 10 hours at the temperature of 600 to 800 ℃;
step S2, acid treatment, namely mixing the calcined USY powder with a dilute acid solution, heating to 80-95 ℃ while stirring, and keeping for 1-8 h;
s3, cleaning, draining, cooling the mixture of the USY powder and the dilute acid solution to room temperature after the acid treatment is finished, performing vacuum suction filtration on a Buchner funnel to remove the waste acid solution to form a filter cake, and washing the filter cake with deionized water;
and S4, drying, namely placing the filter cake in an electric heating oven for heating and drying, wherein the heating temperature is 150-200 ℃, and after the heating and drying are finished, preparing the powdery multistage Kong Gaogui hydrophobic zeolite with the FAU structure and detecting.
2. The method for preparing a multi-stage Kong Gaogui hydrophobic zeolite with FAU structure as in claim 1, wherein in step S1, the wide angle powder XRD spectrum of the USY powder shows all the characteristic diffraction spectra of its typical pure FAU-type structure without any heterocrystal phase, and its high angle powder diffraction pattern from 56 °/2 θ to 60 °/2 θ has diffraction peak of diffraction index (15 3) at 58.2 °/2 θ.
3. The method for preparing a multi-stage Kong Gaogui hydrophobic zeolite with FAU structure of claim 1, wherein in said step S2, the diluted acid solution is one of sulfuric acid, hydrochloric acid, nitric acid, acetic acid, oxalic acid and citric acid.
4. The preparation method of the multi-stage Kong Gaogui hydrophobic zeolite with FAU structure of claim 3, wherein the diluted acid solution has concentration of 0.05M to 0.75M, treatment temperature of 80 ℃ to 95 ℃, treatment time of 1 hour to 8 hours, and liquid/solid ratio of 5/1 to 10/1.
5. The method for preparing the multi-stage Kong Gaogui hydrophobic zeolite with FAU structure of claim 1, wherein in step S3, when the filter cake is washed with deionized water, the PH of the washing filtrate is between 5.9 and 6.1, and the washing is completed.
6. The method for preparing the multistage Kong Gaogui hydrophobic zeolite with FAU structure as claimed in claim 1, wherein in the step S4, sampling is performed on the prepared multistage Kong Gaogui hydrophobic zeolite with FAU structure, and XRD crystal phase detection, n-hexane vapor adsorption detection and water vapor adsorption detection are performed.
7. The method for preparing the multistage Kong Gaogui hydrophobic zeolite with FAU structure according to claim 6, wherein when the prepared multistage Kong Gaogui hydrophobic zeolite with FAU structure is subjected to XRD crystal phase detection, an X-ray powder diffractometer is used, a wide-angle scanning range of 5-35 °/2 theta and a scanning speed of 4 °/2 theta/min are set for detection, and a high-angle scanning range of 55-60 °/2 theta and a scanning speed of 1 °/2 theta/min are set for detection.
8. The method for preparing the multistage Kong Gaogui hydrophobic zeolite with the FAU structure as claimed in claim 6, wherein when n-hexane vapor adsorption detection is performed on the prepared multistage Kong Gaogui hydrophobic zeolite with the FAU structure, the adsorption temperature is set to be 30 ℃ and the vapor pressure is set to be 5mmHg, and a detection sample is heated to 350 ℃ and cooled to 30 ℃ after vacuum dehydration and drying.
9. The method for preparing the multistage Kong Gaogui hydrophobic zeolites with FAU structure according to claim 6, wherein when the prepared multistage Kong Gaogui hydrophobic zeolite with FAU structure is subjected to water vapor adsorption, the detection temperature is set to 35 ℃, the multistage Kong Gaogui hydrophobic zeolite with FAU structure is subjected to saturated vapor equilibrium with saturated ammonium chloride salt solution for 24 hours.
10. The method for preparing the multistage Kong Gaogui hydrophobic zeolites with FAU structure as claimed in claim 1, wherein in step S5, SAR of the multistage Kong Gaogui hydrophobic zeolite with FAU structure is in the range of 14.1 to 414.
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| CN1179400A (en) * | 1996-10-15 | 1998-04-22 | 中国石油化工总公司 | Super-hydrophobic Y zeolite and its preparing process |
| US20230159342A1 (en) * | 2020-04-16 | 2023-05-25 | Jgc Catalysts And Chemicals Ltd. | Faujasite type zeolite and method for producing same |
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| CN1179400A (en) * | 1996-10-15 | 1998-04-22 | 中国石油化工总公司 | Super-hydrophobic Y zeolite and its preparing process |
| US20230159342A1 (en) * | 2020-04-16 | 2023-05-25 | Jgc Catalysts And Chemicals Ltd. | Faujasite type zeolite and method for producing same |
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