CN115806299A - Multistage Kong Gaogui hydrophobic zeolite with FAU structure - Google Patents
Multistage Kong Gaogui hydrophobic zeolite with FAU structure Download PDFInfo
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 239000010457 zeolite Substances 0.000 title claims abstract description 162
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 159
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 99
- 238000001179 sorption measurement Methods 0.000 claims abstract description 49
- 239000000843 powder Substances 0.000 claims abstract description 43
- 239000011148 porous material Substances 0.000 claims abstract description 42
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 22
- 239000012013 faujasite Substances 0.000 claims description 98
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000003795 desorption Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 10
- 238000010306 acid treatment Methods 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 238000001228 spectrum Methods 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 230000003247 decreasing effect Effects 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 11
- 239000010703 silicon Substances 0.000 abstract description 10
- 239000002699 waste material Substances 0.000 abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 239000002808 molecular sieve Substances 0.000 abstract description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 4
- 230000009469 supplementation Effects 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000000034 method Methods 0.000 description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 238000011282 treatment Methods 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 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 5
- 239000000047 product Substances 0.000 description 5
- 239000005049 silicon tetrachloride Substances 0.000 description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000013074 reference sample Substances 0.000 description 3
- 238000012360 testing method Methods 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
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- 239000000463 material Substances 0.000 description 2
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- 235000006408 oxalic acid Nutrition 0.000 description 2
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- 230000004584 weight gain Effects 0.000 description 2
- 235000019786 weight gain Nutrition 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000282376 Panthera tigris Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910002796 Si–Al 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
- 150000007513 acids Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 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
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 235000012054 meals Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 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
- 229920006395 saturated elastomer Polymers 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide 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
- 238000003746 solid phase reaction Methods 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000002424 x-ray crystallography Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to the field of zeolite molecular sieves, in particular to a multistage Kong Gaogui hydrophobic zeolite with an FAU structure, wherein multistage Kong Gaogui hydrophobic FAU zeolites of different SAR are prepared by treating USY raw material powder with different kinds of dilute acid solutions, so that the total pore volume of the prepared multistage Kong Gaogui hydrophobic zeolite samples of different SAR is increased, and the SAR of a zeolite framework is increased to a range of 14-400; the zeolite is hierarchical porous zeolite formed by structural micropores and disordered mesopores, has hydrophobic and oleophilic adsorption characteristics, the SAR of a zeolite framework is improved from 14 to 400, the hydrophobic property of the zeolite is gradually improved, and the (15 3) diffraction peak of a USY raw material moves from 59.20/2 theta to 59.50/2 theta in a high diffraction angle direction; the preparation of the multistage Kong Gaogui hydrophobic zeolite avoids the problems of resource waste and environmental pollution when the zeolite framework SAR is improved by chemical dealuminization and silicon supplementation, and the zeolite has fine structural micropores and rich mesopores, and can effectively adsorb large-diameter organic molecules.
Description
Technical Field
The invention relates to the field of zeolite molecular sieves, in particular to a multistage Kong Gaogui hydrophobic zeolite with an FAU structure.
Background
FAU zeolite is the most widely used and most used artificially synthesized large-pore zeolite, and is characterized in that a beta cage formed by a six-oxygen-membered ring and an eight-oxygen-membered ring is connected into a large cage, namely an alpha cage, through a column formed by a four-oxygen-membered ring and the six-oxygen-membered ring, the window diameter of a 12-oxygen-membered ring of the cage is 0.74nm, and the pore volume is 0.32mL/g. Zeolite X in the FAU type zeolite, wherein the SAR of the zeolite is 2 to 3, the zeolite belongs to low-silicon zeolite, has high hydrophilic adsorption property and is commonly used as an industrial dehydration desiccant and an adsorbent; another FAU-type zeolite, the Y zeolite, has a SAR of 3 to 6, and is widely used in crude oil cracking catalysts (FCC catalysts) in petroleum refining.
A large number of researches prove that as the FAU zeolite framework SAR is improved, the structural hydrothermal stability of the FAU zeolite framework SAR is obviously improved, the water adsorption capacity is correspondingly reduced, and the methods for improving the FAU zeolite framework SAR mainly comprise the following steps:
(1) Direct synthesis: the high-silicon FAU zeolite of SAR 7.6 can be directly synthesized by hydro-thermal synthesis by adding crown ether into a reactant system consisting of silica sol and sodium aluminate [ Verified synthesizers of Zeolite Materials, second Revised Edition,2001, P159].
(2) Chemical dealuminization and silicon supplement:
i liquid phase method: fluosilicic acid and salts thereof are used as chemical modifiers, dealumination and silicon supplementation are carried out in a water phase, and the SAR of the FAU zeolite framework can be improved to more than 20 through one-time reaction. This method has been used to date. The catalyst factories of various large petrochemical companies in China produce the hydrogenation catalytic cracking agent by using the method. However, it is difficult to perform liquid phase treatment several times to prepare FAU zeolite of higher SAR because it causes high cost and environmental problem of disposing waste liquid.
ii gas phase process: using silicon tetrachloride as raw material, preparing high-silicon and all-silicon FAU type molecular sieve with SAR >6 by dealuminizing and silicon-supplementing reaction of powdery or formed NaY zeolite in nitrogen flow containing 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 gas-solid phase reaction method is difficult to realize are that the silicon tetrachloride belongs to flammable, explosive, toxic and highly corrosive chemicals, in addition, the silicon tetrachloride which is excessive in reaction 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 of the multipolar pore hydrophobic FAU zeolite in the prior art is difficult to realize.
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, and 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. This has been an urgent need in the market, but there is not yet a large supply.
Disclosure of Invention
Therefore, the invention provides the multistage Kong Gaogui hydrophobic zeolite with the FAU structure, which can solve the technical problems of resource waste and environmental pollution caused by the traditional improvement of the FAU zeolite framework SAR.
In order to achieve the above object, the present invention provides a multi-stage Kong Gaogui hydrophobic zeolite having FAU structure, said multi-stage Kong Gaogui hydrophobic zeolite having FAU (faujasite) crystal structure and its characteristic XRD diffraction spectrum.
Further, the multistage Kong Gaogui hydrophobic zeolite with FAU structure is high-silica zeolite, and the mole ratio SAR of silica to alumina of the framework is in the range of 14 to 400.
Further, when the mole ratio SAR of the silicon oxide to the aluminum oxide of the multistage Kong Gaogui hydrophobic zeolite framework with the FAU structure is more than 14, the zeolite has hydrophobic and oleophilic adsorption characteristics.
Furthermore, the desorption curve of the multistage Kong Gaogui hydrophobic zeolite with the FAU structure is higher than the adsorption curve, an obvious hysteresis loop appears between the two adsorption and desorption curves, and the multistage Kong Gaogui hydrophobic zeolite with the FAU structure is a multistage pore zeolite consisting of structural micropores and disordered mesopores.
Further, the mesoporous aperture of the multistage Kong Gaogui hydrophobic zeolite with the FAU structure is 7.9nm to 10.7nm.
Further, when the framework SAR of the multistage Kong Gaogui hydrophobic zeolite with the FAU structure is gradually increased from 14 to 400, the water adsorption capacity of the zeolite is gradually reduced from 14.3% to 6.2%, the hydrophobicity index Hz is gradually increased from 0.79 to 2.71, and the hydrophobic property of the zeolite is gradually increased.
Further, FAU zeolite samples with zeolite framework SAR =14.1 prepared by treatment with dilute acid already have oleophilic hydrophobic properties and as the SAR of the zeolite samples increases to 60 or higher, the hydrophobicity index Hz rises above 2.0, presenting higher hydrophobic properties.
Furthermore, the USY raw material powder is prepared by using NaY zeolite as a raw material, and the multistage Kong Gaogui hydrophobic FAU zeolite is prepared by treating the USY raw material powder by using a dilute acid solution, so that Na in the NaY zeolite is removed + When in ion, the total pore volume of the prepared multistage Kong Gaogui hydrophobic zeolite samples of different SAR is increased to 0.470 ml/g-to 0.533ml/g-.
Further, the multistage Kong Gaogui hydrophobic zeolite with FAU structure has an H-K pore size of 0.75nm to 0.77nm.
Furthermore, after the multistage Kong Gaogui hydrophobic zeolite with the FAU structure is subjected to dilute acid treatment dealumination, the SAR of a zeolite framework is improved, and a (15 3) diffraction peak of the USY raw material moves from 59.20/2 theta to 59.50/2 theta in a high diffraction angle direction.
Compared with the prior art, the invention has the beneficial effects that the invention provides the multistage Kong Gaogui hydrophobic zeolite with an FAU structure, and the multistage Kong Gaogui hydrophobic zeolite has the crystal structure of FAU (faujasite) and the characteristic XRD diffraction spectrum thereof; the multistage Kong Gaogui hydrophobic FAU zeolite with SAR 14 to 400 range can be prepared by treating USY raw material powder with different kinds of dilute acid solution, and the total pore volume of the prepared multistage Kong Gaogui hydrophobic zeolite samples with different SAR is increased; the multistage Kong Gaogui hydrophobic zeolite provided by the invention has fine structural micropores and rich mesopores, and can effectively adsorb large-diameter molecular organic matters; according to the invention, USY powder is used as raw material powder, and a diluted acid solution with a certain concentration is treated at a certain temperature for a certain time to prepare the multistage Kong Gaogui hydrophobic zeolite with an FAU structure, so that the problems of resource waste and environmental pollution caused by chemical dealuminization and silicon supplementation for improving the zeolite framework SAR are solved;
the zeolite is hierarchical porous zeolite formed by structural micropores and disordered mesopores, has hydrophobic and oleophilic adsorption characteristics, when SAR of a zeolite framework is gradually increased from 14 to 400, the hydrophobic property of the zeolite is gradually increased, and a (15 3) diffraction peak of a USY raw material moves from 59.20/2 theta to 59.50/2 theta in a high diffraction angle direction; the high-silicon hydrophobic FAU zeolite is used as an adsorbent main material, not only has high BET surface area, but also has mesopores and mesopore spaces with larger pore diameters, so that organic molecules can be favorably diffused in FAU zeolite crystals in the adsorption and desorption processes;
the novel high-silicon hydrophobic molecular sieve material provided by the invention has fine structural micropores and rich mesopores, can realize large-scale mass production, and meets the urgent needs of the domestic market.
Drawings
FIG. 1 is a framework structure diagram of the multistage Kong Gaogui hydrophobic FAU zeolite described in this example;
FIG. 2 is a broad angle diffraction pattern of the multi-stage Kong Gaogui hydrophobic FAU zeolite XRD powder described in this example;
FIG. 3 is the XRD powder high angle diffractogram of the multi-stage Kong Gaogui hydrophobic FAU zeolite of this example;
fig. 4 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 are not intended to limit 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 framework structure of the multistage Kong Gaogui hydrophobic zeolite with FAU structure described in this example is shown in figure 1;
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 scanning range is 5-35 degrees/2 theta, and the scanning speed is 4 degrees/2 theta/min; the 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 Si-Al chemical composition of the multi-stage Kong Gaogui hydrophobic FAU zeolite sample of the present invention was determined by S8 TIGER X-ray fluorescence spectrometer (XRF) of Bruker, germany, and the SiO thereof was determined 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 and the pore diameter data 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 multi-stage Kong Gaogui hydrophobic FAU zeolite sample is measured by a 3H-2000PW type multi-station gravimetric steam adsorber of domestic Bei Shide instrumentsThe product is adsorbed by n-hexane vapor at 30 deg.C under 5mmHg. The sample to be tested weighs 100 to 200mg. After a sample to be detected is loaded into a sample chamber, the sample is automatically heated to 350 ℃ according to a preset program, vacuum dehydration drying and cooling are carried out to 30 ℃, n-hexane steam which is degassed and purified in advance is introduced into the sample chamber, the steam pressure is controlled to be 5mmHg, the sample to be detected absorbs the n-hexane steam until the absorption reaches balance, and the measured n-hexane steam absorption amount W of the zeolite sample is automatically output 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 The weight gain is calculated by balancing the weight gain with saturated steam of 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. 2 and fig. 3, fig. 2 is a broad-angle diffraction pattern of XRD powder of multi-stage Kong Gaogui hydrophobic FAU zeolite according to this embodiment; FIG. 3 is the XRD powder high angle diffractogram of the multi-stage Kong Gaogui hydrophobic FAU zeolite of this example;
for characterization of the starting USY powder and its pretreatment, the wide angle powder XRD spectrum (see FIG. 2) of the USY from the market shows all the characteristic diffraction spectra of the typical pure FAU-type structure without any heterocrystal phase, and in the high angle powder diffraction pattern of 56 °/2 theta to 60 °/2 theta, the diffraction peak of the diffraction index (15 3) is located at 58.2 °/2 theta (see FIG. 3), the SAR of the XRF compositional analysis of this sample is 6.51, and the sodium oxide content is 3.2%; 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; the USY raw material powder is processed by 70 g in each batch, the USY raw material powder is placed in a beaker with the volume of 1000ml, diluted acid solutions with different concentrations, which are prepared in advance, are measured according to the pre-designed solid/liquid ratio and poured into the beaker, the temperature is heated to 80 ℃ to 95 ℃ under the condition of continuous stirring for 1h to 8h, after the acid treatment is finished and the temperature is cooled to the room temperature, the waste acid liquid is removed by vacuum suction filtration on a Buchner funnel, deionized water is used for washing a filter cake until the PH of the filtrate is close to 6, the filter cake after cleaning and drying is placed in a glass vessel, and the multistage Kong Gaogui hydrophobic FAU zeolite products of different SAR are prepared after being heated overnight and thoroughly dried in an electric heating oven at the temperature of 150 ℃ to 200 ℃;
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 productInvented multistage Kong Gaogui H type FAU zeolite of SAR 14.1 to 414.
TABLE 2 multistage Kong Gaogui hydrophobic FAU zeolite sample chemical composition
With continued reference to fig. 2 and 3, the wide angle powder XRD diffractogram shown in fig. 2 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. 3 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 ) Equation (1) = (25.248-a) x8.1633.. Times
The practical range of the framework SAR calculation according to the empirical formula (1) by using the FAU zeolite unit cell parameter a determined by an XRD powder diffraction method has certain limitation, namely, when the SAR is less than 30, the method is feasible. In general, one chooses the formula given by X-ray crystallography for the d value of the strongest peak (153 3) 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 Equation (3) is provided as a rule, i.e., a/2 Sin 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 ka radiation from the Cu target for our experiments with an average wavelength λ =1.5418A, K =12.01714 is calculated, and 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. 3.
Continuing with table 3, it is the adsorption properties of the multi-stage Kong Gaogui hydrophobic FAU zeolite sample, table 3 lists the adsorption properties of the NaY zeolite of the reference sample, USY raw powder and the multi-stage Kong Gaogui hydrophobic FAU zeolite of the present invention prepared by treating with dilute acid solution, the water vapor adsorption capacity of the NaY zeolite is 26.5%, the n-hexane adsorption capacity is 16.8%, and the 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);
with continued reference to fig. 4, which is a plot of the low temperature nitrogen adsorption and desorption isotherms of the multi-stage Kong Gaogui hydrophobic FAU zeolite of this example, fig. 4 is a plot of the low temperature nitrogen adsorption isotherms of the NaY zeolite, USY feedstock powder obtained from nitrogen adsorption testing, and the high-silica hydrophobic FAU zeolites S1, S2, S3, S4, S5 and S6 samples prepared by treatment with different concentrations of different types of dilute acid. 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 such as [ 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 aperture analyzer of a domestic Bei Shide instrument company automatically sets low-temperature nitrogen adsorption isotherms, desorption and the like of all FAU zeolite samples tested by the patent shown in FIG. 4Wen Xianwai, and also outputs the data of BET specific surface area, total pore volume, micropore volume and mesopore volume, pore diameter and the like measured by 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 a total pore volume excluding NaY zeolite of 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 of 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 0.7nmA structural pore size of 4 nm. 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 easily understood by those skilled in the art that the scope of the present invention is obviously 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. The multi-stage pore Gao Gui hydrophobic zeolite is characterized in that the multi-stage Kong Gaogui hydrophobic zeolite has a FAU (faujasite) crystal structure and a characteristic XRD diffraction spectrum thereof.
2. The multi-stage Kong Gaogui hydrophobic zeolite with FAU structure of claim 1, wherein the multi-stage Kong Gaogui hydrophobic zeolite with FAU structure is a high silica zeolite with framework silica to alumina mole ratio SAR ranging from 14 to 400.
3. The multi-stage Kong Gaogui hydrophobic zeolite having the FAU structure of claim 1, wherein when the multi-stage Kong Gaogui hydrophobic zeolite framework having the FAU structure has a silica to alumina mole ratio SAR of greater than 14, the zeolite has hydrophobic oleophilic adsorption characteristics.
4. The multi-stage Kong Gaogui hydrophobic zeolite with FAU structure of claim 1, wherein the desorption curve of the multi-stage Kong Gaogui hydrophobic zeolite with FAU structure is higher than the adsorption curve, a significant hysteresis loop appears between the adsorption curve and the desorption curve, and the multi-stage Kong Gaogui hydrophobic zeolite with FAU structure is a multi-stage pore zeolite composed of structural micropores and disordered mesopores.
5. The multi-stage Kong Gaogui hydrophobic zeolite having a FAU structure of claim 1, wherein the multi-stage Kong Gaogui hydrophobic zeolite having a FAU structure has a mesoporous pore size of 7.9nm to 10.7nm.
6. The multi-stage Kong Gaogui hydrophobic zeolite with FAU structure of claim 1, wherein when the framework SAR of the multi-stage Kong Gaogui hydrophobic zeolite with FAU structure is gradually increased from 14 to 400, the water adsorption amount is gradually decreased from 14.3% to 6.2%, the hydrophobicity index Hz is gradually increased from 0.79 to 2.71, and the hydrophobic property of the zeolite is gradually increased.
7. The multistage Kong Gaogui hydrophobic zeolite with FAU structure of claim 1, wherein the FAU zeolite sample with zeolite framework SAR =14.1 prepared by dilute acid treatment already has lipophilic hydrophobic properties and exhibits higher hydrophobic properties as the zeolite sample SAR increases to 60 or higher, its hydrophobicity index Hz rises above 2.0.
8. The multi-stage Kong Gaogui hydrophobic zeolite with FAU structure of claim 1, wherein USY raw powder is made from NaY zeolite, multi-stage Kong Gaogui hydrophobic FAU zeolite made by treating USY raw powder with dilute acid solution is removed Na from NaY zeolite + When ionized, the total pore volume of the prepared multi-stage Kong Gaogui hydrophobic zeolite samples of different SAR is increased to 0.470 ml/g-to 0.533ml/g-.
9. The multi-stage Kong Gaogui hydrophobic zeolite with FAU structure of claim 1, wherein the H-K pore size of the multi-stage Kong Gaogui hydrophobic zeolite with FAU structure is 0.75nm to 0.77nm.
10. The multi-stage Kong Gaogui hydrophobic zeolite with FAU structure of claim 1, wherein after dilute acid treatment dealumination, the multi-stage Kong Gaogui hydrophobic zeolite with FAU structure has increased zeolite framework SAR and the (15 3) diffraction peak of USY raw material is shifted from 59.20/2 theta to 59.50/2 theta high diffraction angle direction.
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