CN107601525A - A kind of preparation method and applications of double hemispherical W zeolites - Google Patents
A kind of preparation method and applications of double hemispherical W zeolites Download PDFInfo
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- CN107601525A CN107601525A CN201710942956.7A CN201710942956A CN107601525A CN 107601525 A CN107601525 A CN 107601525A CN 201710942956 A CN201710942956 A CN 201710942956A CN 107601525 A CN107601525 A CN 107601525A
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- 239000010457 zeolite Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 39
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 39
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical group [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 30
- 239000013535 sea water Substances 0.000 claims abstract description 23
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 22
- 239000011591 potassium Substances 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000004088 simulation Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 30
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 238000002425 crystallisation Methods 0.000 claims description 26
- 230000008025 crystallization Effects 0.000 claims description 26
- 239000012065 filter cake Substances 0.000 claims description 23
- 229910001868 water Inorganic materials 0.000 claims description 19
- 239000010703 silicon Substances 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000000376 reactant Substances 0.000 claims description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 239000010935 stainless steel Substances 0.000 claims description 11
- 239000007790 solid phase Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 238000005342 ion exchange Methods 0.000 abstract description 25
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 15
- 239000013078 crystal Substances 0.000 description 13
- 239000011521 glass Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 6
- -1 silicon aluminate Chemical class 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 239000000701 coagulant Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- KMNWCNNLFBCDJR-UHFFFAOYSA-N [Si].[K] Chemical compound [Si].[K] KMNWCNNLFBCDJR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a kind of preparation method and applications of double hemispherical W zeolites, a kind of double hemispherical W zeolites are prepared first, is then applied in manual simulation's seawater and carries potassium.The present invention prepares a kind of reaction of double hemispherical W zeolites and carried out at a lower temperature, mild condition, meets the demand for development of Green Chemistry；Synthesis procedure is simple, and raw material is cheap and easy to get, and time-consuming short, cost is low；Product good crystallinity, purity are high.The W zeolites of synthesis have double hemispherical patterns, and its is modified for carrying potassium in manual simulation's seawater, reach 58.42mg/g to potassium ion exchange capacity, have preferable application prospect.
Description
Technical field
The invention belongs to zeolitic material preparation and application technical field, is related to a kind of preparation method of double hemispherical W zeolites
And its application.
Background technology
W zeolites are a kind of silicon aluminate crystals with the main pore passage structure of octatomic ring.It is by Breck in nineteen fifty-three first
It is synthesized, there is octatomic ring pore passage structure, is observed along (100) crystal face, octatomic ring pore size is 0.31nm × 0.35nm；
Observed along (010) crystal face, octatomic ring pore size is 0.27nm × 0.36nm；Observed along (001) crystal face, octatomic ring pore size
For 0.34nm × 0.51nm and 0.33nm × 0.33nm.Due to the particularity of pore passage structure, slight acid and higher stabilization
Property, W zeolites are paid close attention in the application of adsorption cleaning, separation and catalysis etc. by researcher.Especially after W Zeolite modifyings to potassium from
Son has preferable selectivity, and the potassium ion exchange capacity to seawater is about 50~60mg/g, higher than in general natural zeolite.China
As sylvite country of consumption maximum in the world, seawater development puies forward potassium technology for making up the present situation of China's potassium resource critical shortage,
With highly important economic benefit and strategic importance.
W zeolite generally uses hydro-thermal method synthesizes, i.e., raw material is configured into a certain proportion of coagulant liquid, is placed on reactor
In, crystallization generates at high temperature.Hydro-thermal method, which prepares W zeolites, has the advantages that simple to operate, product crystallinity is high, but its
Crystallization temperature height needed for synthesis, energy consumption are big, and the requirement to pressure, temperature and equipment is high.Meanwhile study report and also indicate that synthesis
During system composition, aging temperature and ageing time etc. be also the factor for influenceing W zeolite crystal patterns, and crystal morphology pair
Its performance plays vital effect.Such as Yeong-Hui Seo (Microporous and Mesoporous
Materials, 2010,128 (1-3), 108-114) in 165 DEG C of crystallization 72h W zeolites are prepared, research finds synthetic system without second
In the presence of glycol, the W zeolite morphologies of synthesis are spherical；And using ethylene glycol as decentralized medium, the crystal morphology of synthesis W zeolites is
Prismatic.(artificial lens journal, 2014,43 (1) such as Du Cuihua：Full potassium W 153-162) is prepared using KOH alkali fusions activation potassium feldspar
Zeolite, research are found as the extension of coagulant liquid ageing time, the W zeolite grains both ends degree of scattering of synthesis diminish, and are gradually become
Carefully, its pattern from fiber dumbbell shaped gradually to the bar-shaped transition of fiber.It is that increase ageing time is advantageous to crystal seed to conclude its reason
It is a large amount of to be formed, so as to cause crystal grain in later stage crystallization process to be grown in crowded space；And with the increase of aging temperature, portion
Crystal grain is divided to start structural break occur, crystal grain distribution becomes uneven.(Guangdong chemical industry, 2015,42 (304) such as Li Tongtong：42-
44) report that 150 DEG C of crystallization 24h prepare W zeolites, investigate influence of the coagulant liquid composition to synthesis product morphology, the results showed that when solidifying
Glue aluminium silicon mol ratio is 0.052 and 0.134, and the W zeolite morphologies of synthesis are bar-shaped and fusiform mixture, fusiform, zeolite
It is respectively after modified 38mg/g and 57mg/g to potassium ion exchange capacity in manual simulation's seawater；When aluminium silicon mol ratio is
When 0.216, the fusiform crystal grain both ends degree of scattering diminishes, crystal grains fine, potassium ion exchange capacity 31mg/g；Coagulant liquid water silicon
Mol ratio is 35,45 and 55, and the W zeolites of synthesis are in long fusiform, fusiform and petal-shaped respectively, and corresponding zeolite is right after modified
Potassium ion exchange capacity is respectively 51mg/g, 57mg/g and 45mg/g in manual simulation's seawater.In order to further improve raw material
(artificial lens journal, 2016,45 (12) such as utilization rate, Guo Juhua：2871-2877) use sial xerogel and potassium hydroxide for
Raw material synthesizes W zeolites under water vapour subsidiary conditions, and research finds that crystallization temperature is 150 DEG C, and product morphology is mainly that cross is handed over
It is forked；Crystallization temperature is 170 DEG C, and product is easily reunited.The optimum condition of synthesis is：160 DEG C of crystallization temperature, crystallization time
48h, potassium silicon mol ratio 0.772, water silicon mol ratio 11.2, the ratio of the water made an addition in solid reaction raw material and bottom water
For 2.85.Obtained the fusiform W zeolites that pattern is homogeneous, bar-shaped material is more scattered on this condition, it is modified its to artificial
Potassium ion exchange capacity is 52.4mg/g in simulated seawater, and the value is suitable with conventional hydrothermal method.The method is due to the limitation of water, greatly
Nucleus aggregation is measured, the pattern for being easily caused synthesized zeolite is uneven.To sum up narrate, W zeolites prepared by existing report are all more general
Time bar-shaped, fusiform and the pattern such as petal-shaped, there is the shortcomings of temperature is high, energy consumption is big, cost is higher for synthetic method.Cause
This, it is necessary to find it is a kind of can reduce cost and product is modified the synthetic method compared with High-K+ exchange capacity, with
Just laid the foundation in terms of potassium from sea water can be better utilized in for W zeolites.
The content of the invention
For above-mentioned technical problem present in prior art, it is an object of the invention to provide a kind of double hemispherical W zeolites
Preparation method, the preparation method crystallization temperature is low, and the time is short, and operating procedure is simple, and the W zeolites of synthesis are in double hemispherical shapes
Looks.
Carried it is a further object to provide the modification of double hemispherical W zeolites and its in manual simulation's seawater
The application of potassium, modified double hemispherical W zeolites reach 58.42mg/g to potassium ion exchange capacity, have preferable application prospect.
The technical solution adopted in the present invention is, a kind of preparation method of double hemispherical W zeolites, this method be specifically according to
What following steps were carried out：
(1) weigh potassium hydroxide and silicon source is respectively put into container, add deionized water, heating stirring makes raw material complete
Dissolving, is made solution A；
(2) silicon source is slowly added into solution A under stirring, continues 0.5~2h of stirring after addition, forms silica-alumina gel
Mixture；
(3) above-mentioned silica-alumina gel mixture is transferred in the stainless steel synthesis reactor with polytetrafluoroethyllining lining and sealed,
It is placed on 12~72h of crystallization in 90~120 DEG C of baking oven；
(4) after the completion of reacting, synthesis reactor is taken out, reactant mixture is filtered, and filter cake is carried out with deionized water
Washing, until the pH to 8~9 of wash solution；
(5) filter cake is dried into 12~36h at 80~120 DEG C and produces double hemispherical W zeolites.
Further, the silicon source in step (1) is one kind in sodium aluminate, aluminium hydroxide, aluminum sulfate.
Further, the silicon source in step (2) is Ludox, its SiO2Mass fraction is 30%.
Further, in step (1) solution A chemical composition silicon source amount with Al2O3Meter, potassium hydroxide dosage is with K2O is counted, molten
Each material mol ratio is Al in liquid A2O3:K2O:H2O=1.0:6.8~15.0:292~626.
Further, the silica-alumina gel mixing chemical constituent silicon source amount in step (2) is with SiO2Meter, silicon source amount is with Al2O3
Meter, base amount is with K2O is counted, and each material mol ratio of silica-alumina gel mixture is SiO2:Al2O3:K2O:H2O=6.2~13.4:1.0:
6.8~15.0:340~730.
Further, the temperature of baking oven is 90 DEG C in step (3), and crystallization time is 36~72h.
Further, the temperature of baking oven is 120 DEG C in step (3), and crystallization time is 12~24h.
Further, filtration cakes torrefaction temperature is 100 DEG C in step (5), drying time 24h.
Above-mentioned double hemispherical W zeolites propose the application of potassium in manual simulation's seawater, it is characterised in that comprise the following steps：
Double hemispherical W zeolites of above-mentioned synthesis are placed in container, add the NH that 100mL concentration is 4mol/L4Cl solution,
6h is stirred at room temperature；It is placed in after solid phase is separated in container, adds 100mL saturation NaCl solutions, stir 6h at room temperature, finally
Solid phase separation is obtained into modified zeolite after dry 24h at 100 DEG C；
Weigh modified zeolite 0.2g to be placed in container, add manual simulation's seawater that 500mL is prepared, be stirred at room temperature
1h, after Solid-Liquid Separation, the concentration of potassium ion in liquid phase is determined, new simulated seawater is added again in solid phase, stirs at room temperature
1h is mixed, separation of solid and liquid is repeated and new simulated seawater and the process stirred is added into solid phase, when potassium in process liquid phase twice
Stop adding new manual simulation's seawater when ion concentration is basically unchanged.
The beneficial effects of the invention are as follows：(1) reaction is carried out at a lower temperature, mild condition, meets Green Chemistry
Demand for development；(2) synthesis procedure is simple, and raw material is cheap and easy to get, and time-consuming short, cost is low；(3) product good crystallinity, purity are high；
(4) the W zeolites of synthesis have double hemispherical patterns, and its is modified for carrying potassium in manual simulation's seawater, and potassium ion is exchanged
Capacity reaches 58.42mg/g, has preferable application prospect.
Brief description of the drawings
Fig. 1 is X-ray diffraction (XRD) spectrogram of the W zeolite powders obtained by embodiment 1；
Fig. 2 is ESEM (SEM) picture of the W zeolite powders obtained by embodiment 1.
Embodiment
Technical scheme is described further with reference to specific embodiment, it is to be understood that the guarantor of the present invention
Shield scope is not limited by specific embodiment.
Embodiment 1
(1) weigh 8.42g potassium hydroxide and 1.22g sodium aluminates be respectively put into glass container, add 57.80g go from
Sub- water, heating stirring are completely dissolved raw material, and solution A is made；
(2) 10.28g Ludox is weighed, Ludox is slowly added into solution A under stirring, continues to stir after addition
0.5h, form silica-alumina gel mixture；
(3) above-mentioned silica-alumina gel mixture is transferred in the stainless steel synthesis reactor with polytetrafluoroethyllining lining and sealed,
It is positioned in baking oven, sets oven temperature as 90 DEG C, crystallization 48h；
(4) after the completion of reacting, synthesis reactor is taken out, reactant mixture is filtered, and filter cake is carried out with deionized water
Washing, until wash solution pH to 8~9；
(5) filter cake is dried into 24h at 100 DEG C, you can obtain double hemispherical W zeolites of the present invention；
Double hemispherical W zeolites that the present embodiment is prepared, its is modified to have higher potassium ion exchange capacity.Weigh
Double hemispherical W zeolites 1.0g that the present embodiment is prepared are placed in glass container, and it is 4mol/L's to add 100mL concentration
NH4Cl solution, stirs 6h at room temperature；It is placed in after solid phase is separated in glass container, adds 100mL saturation NaCl solutions, room
The lower stirring 6h of temperature, finally solid phase is separated and obtains modified zeolite after dry 24h at 100 DEG C.Modified zeolite 0.2g is weighed to put
In glass container, manual simulation's seawater that 500mL is prepared is added, 1h is stirred at room temperature, after Solid-Liquid Separation, determine liquid
The concentration of potassium ion in phase, new simulated seawater is added again in solid phase, 1h is stirred at room temperature, this process is repeated several times, when two
Potassium concentration is basically unchanged in secondary process liquid phase, is exchanged and is reached balance.Potassium ion in liquid phase after ICP measure exchanges every time
Concentration, the potassium ion exchange capacity for calculating corresponding modified zeolite are 58.42mg/g.
Wherein, Fig. 1 is X-ray diffraction (XRD) spectrogram of the W zeolite powders obtained by embodiment 1.Can be with from Fig. 1
Find out, the standard card of XRD characteristic peaks and W zeolites corresponds, it may be determined that the product of synthesis is w-type zeolite.Synthetic sample W
Type crystallization of zeolites is fine, almost high without impurity peaks, purity.
Fig. 2 is ESEM (SEM) photo of the W zeolite powders obtained by embodiment 1.Figure it is seen that W boils
Stone particle has double hemispherical patterns, and grain size is homogeneous, is evenly distributed.
Embodiment 2
(1) weigh 8.98g potassium hydroxide and 0.78g aluminium hydroxides are respectively put into glass container, add 65.24g and go
Ionized water, heating stirring are completely dissolved raw material, and solution A is made；
(2) 11.34g Ludox is weighed, Ludox is slowly added into solution A under stirring, continues to stir after addition
0.5h, form silica-alumina gel mixture；
(3) above-mentioned silica-alumina gel mixture is transferred in the stainless steel synthesis reactor with polytetrafluoroethyllining lining and sealed,
It is positioned in baking oven, sets oven temperature as 90 DEG C, crystallization 48h；
(4) after the completion of reacting, synthesis reactor is taken out, reactant mixture is filtered, and filter cake is carried out with deionized water
Washing, until wash solution pH to 8~9；
(5) filter cake is dried into 24h at 100 DEG C, you can obtain double hemispherical W zeolites of the present invention；
Double hemispherical W zeolites that the present embodiment is prepared, its is modified to have higher potassium ion exchange capacity.It is modified
And the step of carrying potassium, with embodiment 1, the potassium ion exchange capacity of corresponding modified zeolite is 57.64mg/g.
Embodiment 3
(1) weigh 9.78g potassium hydroxide and 3.22g aluminum sulfate be respectively put into glass container, add 65.56g go from
Sub- water, heating stirring are completely dissolved raw material, and solution A is made；
(2) 12.30g Ludox is weighed, Ludox is slowly added into solution A under stirring, continues to stir after addition
0.5h, form silica-alumina gel mixture；
(3) above-mentioned silica-alumina gel mixture is transferred in the stainless steel synthesis reactor with polytetrafluoroethyllining lining and sealed,
It is positioned in baking oven, sets oven temperature as 90 DEG C, crystallization 48h；
(4) after the completion of reacting, synthesis reactor is taken out, reactant mixture is filtered, and filter cake is carried out with deionized water
Washing, until wash solution pH to 8~9；
(5) filter cake is dried into 24h at 100 DEG C, you can obtain double hemispherical W zeolites of the present invention；
Double hemispherical W zeolites that the present embodiment is prepared, its is modified to have higher potassium ion exchange capacity.It is modified
And the step of carrying potassium, with embodiment 1, the potassium ion exchange capacity of corresponding modified zeolite is 58.20mg/g.
Embodiment 4
(1) weigh 9.12g potassium hydroxide and 1.68g sodium aluminates be respectively put into glass container, add 66.68g go from
Sub- water, heating stirring are completely dissolved raw material, and solution A is made；
(2) 11.08g Ludox is weighed, Ludox is slowly added into solution A under stirring, continues to stir after addition
0.5h, form silica-alumina gel mixture；
(3) above-mentioned silica-alumina gel mixture is transferred in the stainless steel synthesis reactor with polytetrafluoroethyllining lining and sealed,
It is positioned in baking oven, sets oven temperature as 90 DEG C, crystallization 48h；
(4) after the completion of reacting, synthesis reactor is taken out, reactant mixture is filtered, and filter cake is carried out with deionized water
Washing, until wash solution pH to 8~9；
(5) filter cake is dried into 24h at 100 DEG C, you can obtain double hemispherical W zeolites of the present invention；
Double hemispherical W zeolites that the present embodiment is prepared, its is modified to have higher potassium ion exchange capacity.It is modified
And the step of carrying potassium, with embodiment 1, the potassium ion exchange capacity of corresponding modified zeolite is 58.28mg/g.
Embodiment 5
(1) weigh 9.20g potassium hydroxide and 0.98g aluminium hydroxides are respectively put into glass container, add 70.24g and go
Ionized water, heating stirring are completely dissolved raw material, and solution A is made；
(2) 11.34g Ludox is weighed, Ludox is slowly added into solution A under stirring, continues to stir after addition
0.5h, form silica-alumina gel mixture；
(3) above-mentioned silica-alumina gel mixture is transferred in the stainless steel synthesis reactor with polytetrafluoroethyllining lining and sealed,
It is positioned in baking oven, sets oven temperature as 90 DEG C, crystallization 48h；
(4) after the completion of reacting, synthesis reactor is taken out, reactant mixture is filtered, and filter cake is carried out with deionized water
Washing, until wash solution pH to 8~9；
(5) filter cake is dried into 24h at 100 DEG C, you can obtain double hemispherical W zeolites of the present invention；
Double hemispherical W zeolites that the present embodiment is prepared, its is modified to have higher potassium ion exchange capacity.It is modified
And the step of carrying potassium, with embodiment 1, the potassium ion exchange capacity of corresponding modified zeolite is 57.92mg/g.
Embodiment 6
(1) weigh 10.68g potassium hydroxide and 3.80g aluminum sulfate be respectively put into glass container, add 70.56g go from
Sub- water, heating stirring are completely dissolved raw material, and solution A is made；
(2) 12.85g Ludox is weighed, Ludox is slowly added into solution A under stirring, continues to stir after addition
0.5h, form silica-alumina gel mixture；
(3) above-mentioned silica-alumina gel mixture is transferred in the stainless steel synthesis reactor with polytetrafluoroethyllining lining and sealed,
It is positioned in baking oven, sets oven temperature as 90 DEG C, crystallization 48h；
(4) after the completion of reacting, synthesis reactor is taken out, reactant mixture is filtered, and filter cake is carried out with deionized water
Washing, until wash solution pH to 8~9；
(5) filter cake is dried into 24h at 100 DEG C, you can obtain double hemispherical W zeolites of the present invention；
Double hemispherical W zeolites that the present embodiment is prepared, its is modified to have higher potassium ion exchange capacity.It is modified
And the step of carrying potassium, with embodiment 1, the potassium ion exchange capacity of corresponding modified zeolite is 58.34mg/g.
Embodiment 7
(1) weigh 10.32g potassium hydroxide and 2.03g sodium aluminates be respectively put into glass container, add 62.20g go from
Sub- water, heating stirring are completely dissolved raw material, and solution A is made；
(2) 11.54g Ludox is weighed, Ludox is slowly added into solution A under stirring, continues to stir after addition
0.5h, form silica-alumina gel mixture；
(3) above-mentioned silica-alumina gel mixture is transferred in the stainless steel synthesis reactor with polytetrafluoroethyllining lining and sealed,
It is positioned in baking oven, sets oven temperature as 120 DEG C, crystallization 12h；
(4) after the completion of reacting, synthesis reactor is taken out, reactant mixture is filtered, and filter cake is carried out with deionized water
Washing, until wash solution pH to 8~9；
(5) filter cake is dried into 24h at 100 DEG C, you can obtain double hemispherical W zeolites of the present invention；
Double hemispherical W zeolites that the present embodiment is prepared, its is modified to have higher potassium ion exchange capacity.It is modified
And the step of carrying potassium, with embodiment 1, the potassium ion exchange capacity of corresponding modified zeolite is 58.05mg/g.
Embodiment 8
(1) weigh 10.24g potassium hydroxide and 1.15g aluminium hydroxides are respectively put into glass container, add 65.24g and go
Ionized water, heating stirring are completely dissolved raw material, and solution A is made；
(2) 11.82g Ludox is weighed, Ludox is slowly added into solution A under stirring, continues to stir after addition
2h, form silica-alumina gel mixture；
(3) above-mentioned silica-alumina gel mixture is transferred in the stainless steel synthesis reactor with polytetrafluoroethyllining lining and sealed,
It is positioned in baking oven, sets oven temperature as 120 DEG C, crystallization 12h；
(4) after the completion of reacting, synthesis reactor is taken out, reactant mixture is filtered, and filter cake is carried out with deionized water
Washing, until wash solution pH to 8~9；
(5) filter cake is dried into 12h at 120 DEG C, you can obtain double hemispherical W zeolites of the present invention；
Double hemispherical W zeolites that the present embodiment is prepared, its is modified to have higher potassium ion exchange capacity.It is modified
And the step of carrying potassium, with embodiment 1, the potassium ion exchange capacity of corresponding modified zeolite is 58.31mg/g.
Embodiment 9
(1) weigh 9.12g potassium hydroxide and 3.46g aluminum sulfate be respectively put into glass container, add 66.16g go from
Sub- water, heating stirring are completely dissolved raw material, and solution A is made；
(2) 13.05g Ludox is weighed, Ludox is slowly added into solution A under stirring, continues to stir after addition
2h, form silica-alumina gel mixture；
(3) above-mentioned silica-alumina gel mixture is transferred in the stainless steel synthesis reactor with polytetrafluoroethyllining lining and sealed,
It is positioned in baking oven, sets oven temperature as 120 DEG C, crystallization 12h；
(4) after the completion of reacting, synthesis reactor is taken out, reactant mixture is filtered, and filter cake is carried out with deionized water
Washing, until wash solution pH to 8~9；
(5) filter cake is dried into 36h at 80 DEG C, you can obtain double hemispherical W zeolites of the present invention；
Double hemispherical W zeolites that the present embodiment is prepared, its is modified to have higher potassium ion exchange capacity.It is modified
And the step of carrying potassium, with embodiment 1, the potassium ion exchange capacity of corresponding modified zeolite is 57.46mg/g.
Disclosed above is only the specific embodiment of the present invention, and still, the embodiment of the present invention is not limited to this, Ren Heben
What the technical staff in field can think change should all fall into protection scope of the present invention.
Claims (10)
1. a kind of preparation method of double hemispherical W zeolites, it is characterised in that this method is specifically what is followed the steps below：
(1) weigh potassium hydroxide and silicon source is respectively put into container, add deionized water, heating stirring makes raw material completely molten
Solution, is made solution A；
(2) silicon source is slowly added into solution A under stirring, continues 0.5~2h of stirring after addition, forms silica-alumina gel mixing
Thing；
(3) above-mentioned silica-alumina gel mixture is transferred in the stainless steel synthesis reactor with polytetrafluoroethyllining lining and sealed, by it
It is positioned over 12~72h of crystallization in 90~120 DEG C of baking oven；
(4) after the completion of reacting, synthesis reactor is taken out, reactant mixture is filtered, and filter cake is washed with deionized water,
Until the pH to 8~9 of wash solution；
(5) filter cake is dried into 12~36h at 80~120 DEG C and produces double hemispherical W zeolites.
A kind of 2. preparation method of double hemispherical W zeolites as claimed in claim 1, it is characterised in that aluminium described in step (1)
Source is one kind in sodium aluminate, aluminium hydroxide, aluminum sulfate.
A kind of 3. preparation method of double hemispherical W zeolites as claimed in claim 1, it is characterised in that silicon described in step (2)
Source is Ludox, its SiO2Mass fraction is 30%.
A kind of 4. preparation method of double hemispherical W zeolites as claimed in claim 1, it is characterised in that step (1) described solution
Chemical composition silicon source amount is with Al in A2O3Meter, potassium hydroxide dosage is with K2O is counted, and each material mol ratio is Al in solution A2O3:K2O:
H2O=1.0:6.8~15.0:292~626.
A kind of 5. preparation method of double hemispherical W zeolites as claimed in claim 1, it is characterised in that step (2) described sial
Gel mixture chemical composition silicon source amount is with SiO2Meter, silicon source amount is with Al2O3Meter, base amount is with K2O is counted, silica-alumina gel mixture
Each material mol ratio is SiO2:Al2O3:K2O:H2O=6.2~13.4:1.0:6.8~15.0:340~730.
6. the preparation method of a kind of double hemispherical W zeolites as claimed in claim 1, it is characterised in that step is dried described in (3)
The temperature of case is 90 DEG C, and crystallization time is 36~72h.
A kind of 7. preparation method of double hemispherical W zeolites as claimed in claim 1, it is characterised in that step (3) described baking oven
Temperature be 120 DEG C, crystallization time is 12~24h.
A kind of 8. preparation method of double hemispherical W zeolites as claimed in claim 1, it is characterised in that step (5) described filter cake
Drying temperature is 100 DEG C, drying time 24h.
9. double hemispherical W zeolites obtained by the preparation method as described in claim 1-8 any one are in manual simulation's seawater
In propose the application of potassium.
10. double hemispherical W zeolites obtained by preparation method as claimed in claim 9 carry answering for potassium in manual simulation's seawater
With, it is characterised in that comprise the following steps：
Double hemispherical W zeolites of above-mentioned synthesis are placed in container, add the NH that 100mL concentration is 4mol/L4Cl solution, room temperature
Lower stirring 6h；It is placed in after solid phase is separated in container, adds 100mL saturation NaCl solutions, stir 6h at room temperature, finally will be solid
It is to obtain modified zeolite to be separated after drying 24h at 100 DEG C；
Weigh modified zeolite 0.2g to be placed in container, add manual simulation's seawater that 500mL is prepared, 1h is stirred at room temperature, will
After Solid-Liquid Separation, the concentration of potassium ion in liquid phase is determined, new simulated seawater is added again in solid phase, stirs 1h at room temperature,
Repeat separation of solid and liquid and new simulated seawater and the process stirred are added into solid phase, when potassium ion is dense in process liquid phase twice
Stop adding new manual simulation's seawater when degree is basically unchanged.
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| CN112850739A (en) * | 2021-03-12 | 2021-05-28 | 许昌学院 | Large-grain LTJ zeolite and preparation method thereof |
| CN113149025A (en) * | 2021-03-12 | 2021-07-23 | 许昌学院 | Spherical LTJ zeolite, and preparation method and application thereof |
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| CN104176744A (en) * | 2014-08-26 | 2014-12-03 | 河北工业大学 | Method for preparing total potassium W type molecular sieve by activating potassium feldspar via KOH sub-molten salt |
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| MX2009014260A (en) * | 2009-12-21 | 2011-06-21 | Ct Investig Y Estudios Del Ipn | Hydrothermal method for the direct synthesis of zeolites from fly ash. |
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| CN104176744A (en) * | 2014-08-26 | 2014-12-03 | 河北工业大学 | Method for preparing total potassium W type molecular sieve by activating potassium feldspar via KOH sub-molten salt |
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| CN113149025A (en) * | 2021-03-12 | 2021-07-23 | 许昌学院 | Spherical LTJ zeolite, and preparation method and application thereof |
| CN113149025B (en) * | 2021-03-12 | 2023-04-18 | 许昌学院 | Spherical LTJ zeolite, and preparation method and application thereof |
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