CN102992341A - Hydrophobic modification treatment method for zeolite molecular sieve - Google Patents
Hydrophobic modification treatment method for zeolite molecular sieve Download PDFInfo
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Abstract
The invention belongs to the technical field of zeolite molecular sieve modification, and particularly relates to a hydrophobic modification treatment method for a zeolite molecular sieve. According to the method, firstly a molecular sieve is subjected to high temperature activation at the activation temperature of 400-600 DEG C; and toluene fully dried is used, an appropriate amount of coupling agent is added, reflux reaction is carried out at 110-120 DEG C for 10-20 hours, and the hydrophobic molecular sieve is obtained by cooling, filtering, washing with ethanol and fully drying. According to the method, molecular sieves of different hydrophobic capacities are obtained by carrying out hydrophobic modification on the surface of the molecular sieve using coupling agents of different substituents; the method is suitable for almost all zeolite molecular sieves, and the molecular sieve modified has no great changes in the aperture structure and still keeps good pore property; and the method is simple and easily implemented, and is suitable for large-scale industrial production.
Description
Technical field
The invention belongs to zeolite molecular sieve hydrophobically modified technical field, be specifically related to a kind of high-temperature activation and utilize hydrophobic coupling agent to carry out the method for hydrophobically modified on the zeolite molecular sieve surface.
Technical background
The hydrophobic type research of zeolite molecular sieve concentrates on the polarity ion of eliminating in the skeleton structure usually, and such as its aluminium content of reduction, or employing does not add the zeolite molecular sieve that pure silicon is synthesized in the aluminium source.At present the method that adopts of report all is to eliminate polarity ion in the skeleton structure by reducing crystalline aluminium content, mainly contains following methods:
Hydro-thermal generates and the acid extraction combined method, is in the situation that more than 500 ℃, in the acid vapour coexistence, the aluminium atom in ammonium ion type or the cationic zeolite is come off from skeleton, replaces to improve the Si/Al ratio by the Siliciumatom of other parts simultaneously.
The silicon tetrachloride method is under the high temperature more than 400 ℃, and with anhydrous zeolite and silicon tetrachloride gas reaction, the aluminium atom in the skeleton is replaced by Siliciumatom, prepares supersiliceous zeolite.
The ammonium hexafluorosilicate method is that ammonium type zeolite is added in the hexafluorosilicic acid aqueous ammonium, and the aluminium atom in the zeolite is directly replaced by Siliciumatom.
The CVD method is that volatile metallic compound is deposited on zeolite surface, again through processing the compound hydrophobic material of preparation.
Can find out from the treating processes of above method, currently used method has a lot of limitation mostly, such as complex disposal process, pollutes greatly, and cost is high, and is poor far from the industrial application of reality.
Summary of the invention
The purpose of this invention is to provide a kind of simplely, almost be applicable to the hydrophobically modified treatment process of all zeolite molecular sieves, namely select different hydrophobic coupling agents, carry out coupling at zeolite surface, obtain the zeolite molecular sieve of different hydrophobic types.Method of the present invention is simple, and treatment temp is low.
The hydrophobically modified treatment process of a kind of zeolite molecular sieve of the present invention is carried out in toluene solution, and its concrete steps are as follows:
(1) high-temperature activation of molecular sieve: molecular sieve is washed till neutrality with deionized water, at 130～180 ℃, dried by the fire 10～24 hours; Again the molecular sieve of oven dry is put into retort furnace, 400～600 ℃ of activation 3～6 hours, then be cooled to room temperature, the molecular sieve that obtains activating, taking-up is put into moisture eliminator and is preserved;
(2) connection of coupling agent: the molecular sieve 50～100g of activation is added in the toluene of 300mL drying, to wherein adding 5～80mL coupling agent, then be warming up to 110～120 ℃, back flow reaction 10～20 hours; Be cooled at last room temperature, filter, fully wash with ethanol, 100～200 ℃ of oven dry namely get the hydrophobic molecule sieve.
Molecular sieve described in the above-mentioned steps comprises: A type zeolite molecular sieve (comprising LiA, NaA, KA, CaA, HA type zeolite), X-type zeolite molecular sieve (comprising NaX, LiX, HX, CaX), y-type zeolite molecular sieve (MgY, NaY, CaY, HY), using natural clinoptilolite molecular sieve, natural mordenite zeolite molecular sieve (MOR) and synthetic [" molecular sieve and porous material chemistry " Xu Ruren, Pang Wenqin etc.] Science Press, 2004) the Si-Al zeolite molecular sieve (molecular composition is 0.5～15mol Na
2O:0.5～14mol SiO
2: 0.5～10molAl
2O
3: 0.1～20mol H
2O), (molecular composition is 0.5～10mol Na to aluminium phosphate molecular sieve
2O:0.5～14mol P
2O
5: 0.5～10mol Al
2O
3: 0.1～30mol H
2O), (molecular composition is 0.5～14mol SiO to mesopore molecular sieve
2: 0.1～30mol H
2O).
Used coupling agent structural formula is R
1-Si-(R
2)
3, R wherein
1That carbonatoms is 1～19 alkyl, or halogen (F, Cl, Br, I), amino-NH
2, the carbonatoms that replaces of sulfydryl-SH is 1～19 alkyl; Further, the carbonatoms of alkyl is 1～7.R
1Can also be phenyl or substituted-phenyl, further, be alkyl, halogen, amino-NH
2, nitro-NO
2, the phenyl that replaces such as sulfydryl-SH, the carbonatoms in the alkyl is 1～20; Further again, the carbonatoms in the alkyl is 1～5; The phenyl that halogen replaces comprises a fluorine substituted benzene, difluoro substituted benzene, trifluoro substituted benzene, tetrafluoro substituted benzene, five fluorine substituted benzenes, a chlorine substituted benzene, dichloro substituted benzene, trichlorine substituted benzene, tetrachloro substituted benzene, pentachloro-substituted benzene, monobromo substituted benzene, dibromo substituted benzene, tribromo substituted benzene, tetrabromo substituted benzene, pentabromo-substituted benzene, an iodine substituted benzene, diiodo-substituted benzene, triiodo substituted benzene, tetraiodo substituted benzene, pentaiodo substituted benzene.R
2Be halogeno-group (F, Cl, Br, I) or alkoxyl group, further, alkoxyl group is methoxyl group, oxyethyl group, propoxy-etc.
The hydrophobic effect of the hydrophobic molecule sieve that the coupling agent coupling of the toluene solution of the zeolite molecular sieve that wherein, activated with 50～80g, 300mL drying, 10～60mL obtains is best.
High-temperature activation described in the above-mentioned steps is to remove the water molecules that adsorbs in the molecular sieve, and the existence of water can make coupling agent decompose, and reduces reactive behavior, so that hydrophobicity is not good.
Fully washing with ethanol described in the above-mentioned steps is in order to remove surface adsorption and responseless coupling agent.
This method is applicable to nearly all zeolite molecular sieve, and by the not too large variation of its pore passage structure of the molecular sieve after the modification, has still kept its good pore properties, and this method is simple, is fit to large-scale industrial production.
Description of drawings
Fig. 1: the SEM photo of [Fig. 1 (b)] behind [Fig. 1 (a)], the hydrophobization before the embodiment of the invention 1 described NaY zeolite molecular sieve hydrophobization;
Therefrom can find out, the pattern of sample does not have considerable change before and after the hydrophobization, has well kept the pattern of crystal.
Fig. 2: the XRD figure of [Fig. 2 (b)] behind [Fig. 2 (a)], the hydrophobization before the NaY zeolite molecular sieve hydrophobization, can find out that therefrom hydrophobization front and back sample has well kept crystalline structure.
Embodiment
Embodiment 1:
The high-temperature activation of nanoporous zeolite molecular sieve:
(imperial chemical industry is built in Luoyang to get NaY type zeolite, fine powder dress, the 25kg industrial packaging) 500g puts into ceramic crucible, molecular sieve is washed till neutrality with deionized water, at 150 ℃, dried by the fire 15 hours, the molecular sieve of oven dry is put into retort furnace, 500 ℃ of activation 5 hours, then be cooled to room temperature, the molecular sieve that obtains activating, taking-up is put into moisture eliminator and is preserved.Molecular sieve after the activation has very strong water absorbability, need not preserve in moisture eliminator for a long time.
The drying of toluene:
Toluene is added CaH under condition of nitrogen gas
2Stirring is spent the night, both dry toluene.
The link of coupling agent:
Get the zeolite 50g after the activation, join in the 500mL single port flask, add the toluene of 300mL drying, pipette the 10mL methyltrimethoxy silane with transfer pipet and add in the single port flask, lower 115 ℃ of condition of nitrogen gas refluxed 12 hours.
Aftertreatment:
Reaction solution in the single port flask that preceding step is obtained is cooled to room temperature, filters, and then uses 100mL ethanol agitator treating 3 times, suction filtration, and 150 ℃ of oven dry 10 hours obtain the hydrophobic molecule sieve.
The measurement of contact angle is dripped drop in the solid sample surface by the profile image analytical method, obtains the outside view picture of drop by microlens and camera, and the contact angle of the drop in the image calculates.By the measurement of contact angle experiments, the contact angle that does not have the sample of hydrophobization is 65 degree, and the contact angle of the sample after the hydrophobization is 130 degree, belongs to the sample of hydrophobic type.
Embodiment 2:
Prepare hydrophobic molecule sieve, added coupling agent methyltrimethoxy silane 60mL by embodiment 1 method.The contact angle that records sample is 146 degree.
Embodiment 3:
Prepare the hydrophobic molecule sieve by embodiment 1 method.Added methyltrimethoxy silane 30mL.The contact angle that records sample is 140 degree.
Embodiment 4:
Prepare the hydrophobic molecule sieve by embodiment 1 method.The high-temperature activation of zeolite molecular sieve was 130 ℃ of bakings 24 hours, 600 ℃ of activation 3 hours; Aftertreatment is 100 ℃ of oven dry 15 hours; Selected coupling agent is perfluor nonadecyl Trimethoxy silane.The contact angle that records sample is 159 degree.
Embodiment 5:
Prepare the hydrophobic molecule sieve by embodiment 1 method.The high-temperature activation of zeolite molecular sieve was 180 ℃ of bakings 10 hours, 400 ℃ of activation 6 hours; Aftertreatment is 200 ℃ of oven dry 5 hours; Selected coupling agent is Union carbide A-162.The contact angle that records sample is 133 degree.
Embodiment 6:
Prepare the hydrophobic molecule sieve by embodiment 1 method.The zeolite of getting after the activation is 80g, adds 60mL coupling agent chloromethyl Trimethoxy silane.The contact angle that records sample is 125 degree.
Embodiment 7:
Prepare the hydrophobic molecule sieve by embodiment 1 method.Selected coupling agent is the brooethyl Trimethoxy silane.110 ℃ of back flow reaction 20 hours, the contact angle that records sample are 123 degree.
Embodiment 8:
Prepare the hydrophobic molecule sieve by embodiment 1 method.Selected coupling agent is the aminomethyl Trimethoxy silane.120 ℃ of back flow reaction 10 hours, the contact angle that records sample are 120 degree.
Embodiment 9:
Prepare the hydrophobic molecule sieve by embodiment 1 method.Selected coupling agent is the thiopurine methyltransferase Trimethoxy silane.The contact angle that records sample is 122 degree.
Embodiment 10:
Prepare the hydrophobic molecule sieve by embodiment 1 method.Selected coupling agent is methyl tripropoxy silane.The contact angle that records sample is 128 degree.
Embodiment 11:
Prepare the hydrophobic molecule sieve by embodiment 1 method.Selected coupling agent is phenyltrimethoxysila,e.The contact angle that records sample is 135 degree.
Embodiment 12:
Prepare the hydrophobic molecule sieve by embodiment 1 method.Selected coupling agent is the eicosyl phenyltrimethoxysila,e.The contact angle that records sample is 156 degree.
Embodiment 13:
Prepare the hydrophobic molecule sieve by embodiment 1 method.Selected coupling agent is the fluorophenyl Trimethoxy silane.The contact angle that records sample is 136 degree.
Embodiment 14:
Prepare the hydrophobic molecule sieve by embodiment 1 method.Selected coupling agent is the pentafluorophenyl group Trimethoxy silane.The contact angle that records sample is 165 degree.
Embodiment 15:
Prepare the hydrophobic molecule sieve by embodiment 1 method.Selected coupling agent is the chloro-phenyl-Trimethoxy silane.The contact angle that records sample is 130 degree.
Embodiment 16:
Prepare the hydrophobic molecule sieve by embodiment 1 method.Selected coupling agent is the five chlorophenyl Trimethoxy silane.The contact angle that records sample is 160 degree.
Embodiment 17:
Prepare the hydrophobic molecule sieve by embodiment 1 method.Selected coupling agent is the bromophenyl Trimethoxy silane.The contact angle that records sample is 125 degree.
Embodiment 18:
Prepare the hydrophobic molecule sieve by embodiment 1 method.Selected coupling agent is the penta-bromophenyl Trimethoxy silane.The contact angle that records sample is 154 degree.
Embodiment 19:
Prepare the hydrophobic molecule sieve by embodiment 1 method.Selected coupling agent is the iodophenyl Trimethoxy silane.The contact angle that records sample is 114 degree.
Embodiment 20:
Prepare the hydrophobic molecule sieve by embodiment 1 method.Selected coupling agent is the pentaiodo phenyltrimethoxysila,e.The contact angle that records sample is 145 degree.
Embodiment 21:
Prepare the hydrophobic molecule sieve by embodiment 1 method.Selected coupling agent is phenyl triethoxysilane.The contact angle that records sample is 133 degree.
Embodiment 22:
Prepare the hydrophobic molecule sieve by embodiment 1 method.Selected coupling agent is the chloro-phenyl-triethoxyl silane.The contact angle that records sample is 131 degree.
Embodiment 23:
Prepare the hydrophobic molecule sieve by embodiment 1 method.Selected coupling agent is the bromophenyl Trimethoxy silane.The contact angle that records sample is 131 degree.
Embodiment 24:
Prepare the hydrophobic molecule sieve by embodiment 1 method.Selected coupling agent is phenyl-trichloro-silicane.The contact angle that records sample is 131 degree.
Embodiment 25:
Prepare the hydrophobic molecule sieve by embodiment 1 method.Selected coupling agent is METHYL TRICHLORO SILANE.The contact angle that records sample is 130 degree.
Embodiment 26:
Prepare the hydrophobic molecule sieve by embodiment 1 method.Selected coupling agent is ethyl trichlorosilane.The contact angle that records sample is 133 degree.
Embodiment 27:
Prepare the hydrophobic molecule sieve by embodiment 1 method.Selected coupling agent is the tolyl trichlorosilane.The contact angle that records sample is 134 degree.
Embodiment 28:
Prepare the hydrophobic molecule sieve by embodiment 1 method.Selected coupling agent is chlorophenyl trichlorosilane.The contact angle that records sample is 128 degree.
Embodiment 29:
Prepare the hydrophobic molecule sieve by embodiment 1 method.Selected coupling agent is the nitrophenyl trichlorosilane.The contact angle that records sample is 133 degree.
Embodiment 30:
Prepare the hydrophobic molecule sieve by embodiment 1 method.Selected coupling agent is the tolyl tribromosilane.The contact angle that records sample is 134 degree.
Embodiment 31:
Prepare the hydrophobic molecule sieve by embodiment 1 method.Selected coupling agent is the tolyl silicofluoroform.The contact angle that records sample is 134 degree.
Embodiment 32:
Carry out coupling by embodiment 1 method with methyltrimethoxy silane.Selected molecular sieve is NaX type zeolite.The contact angle that records sample is 133 degree.
Embodiment 33:
Carry out coupling by embodiment 1 method with methyltrimethoxy silane.Selected molecular sieve is H-X.The contact angle that records sample is 128 degree.
Embodiment 34:
Carry out coupling by embodiment 1 method with methyltrimethoxy silane.Selected molecular sieve is ZSM-5.The contact angle that records sample is 132 degree.
Embodiment 35:
Carry out coupling by embodiment 1 method with methyltrimethoxy silane.Selected molecular sieve is NaA.The contact angle that records sample is 133 degree.
Embodiment 36:
Carry out coupling by embodiment 1 method with methyltrimethoxy silane.Selected molecular sieve is KA.The contact angle that records sample is 134 degree.
Embodiment 37:
Carry out coupling by embodiment 1 method with methyltrimethoxy silane.Selected molecular sieve is NaL type zeolite.The contact angle that records sample is 126 degree.
Embodiment 38:
Carry out coupling by embodiment 1 method with methyltrimethoxy silane.Selected molecular sieve is CaA.The contact angle that records sample is 125 degree.
Embodiment 39:
Carry out coupling by embodiment 1 method with methyltrimethoxy silane.The molecular sieve of selecting is mesoporous SBA-15.The contact angle that records sample is 124 degree.
Embodiment 40:
Carry out coupling by embodiment 1 method with methyltrimethoxy silane.The molecular sieve of selecting is mesoporous SBA-16.The contact angle that records sample is 123 degree.
Embodiment 41:
Carry out coupling by embodiment 1 method with methyltrimethoxy silane.The molecular sieve of selecting is mesoporous SBA-2.The contact angle that records sample is 125 degree.
Embodiment 42:
Carry out coupling by embodiment 1 method with methyltrimethoxy silane.Selected molecular sieve is mesoporous MCM-41.The contact angle that records sample is 130 degree.
Embodiment 43:
Carry out coupling by embodiment 1 method with methyltrimethoxy silane.Selected molecular sieve is mesoporous MCM-48.The contact angle that records sample is 132 degree.
Embodiment 44:
Carry out coupling by embodiment 1 method with methyltrimethoxy silane.Selected molecular sieve is mesoporous MCM-44.The contact angle that records sample is 133 degree.
Claims (8)
1. the hydrophobically modified treatment process of a zeolite molecular sieve, its step is as follows:
(1) high-temperature activation of molecular sieve: molecular sieve is washed till neutrality, 130～180 ℃ of bakings 10～24 hours; Molecular sieve with oven dry activates 3～6 hours at 400～600 ℃ again, then is cooled to room temperature, the molecular sieve that obtains activating;
(2) connection of coupling agent: the molecular sieve 50～100g of activation is joined in the toluene of 300mL drying, to wherein adding 5～80mL coupling agent, then be warming up to 110～120 ℃ again, back flow reaction 10～20 hours; Be cooled at last room temperature, filter, fully wash with ethanol, 100～200 ℃ of oven dry namely get the hydrophobic molecule sieve.
2. the hydrophobically modified treatment process of a kind of zeolite molecular sieve as claimed in claim 1, it is characterized in that: molecular sieve is A type zeolite molecular sieve, X-type zeolite molecular sieve, y-type zeolite molecular sieve, using natural clinoptilolite molecular sieve, natural mordenite zeolite molecular sieve, consists of 0.5～15mol Na
2O:0.5～14molSiO
2: 0.5～10mol Al
2O
3: 0.1～20mol H
2The Si-Al zeolite molecular sieve of O, consist of 0.5～10mol Na
2O:0.5～14mol P
2O
5: 0.5～10mol Al
2O
3: 0.1～30mol H
2The aluminium phosphate molecular sieve of O or consist of 0.5～14mol SiO
2: 0.1～30mol H
2The mesopore molecular sieve of O.
3. the hydrophobically modified treatment process of a kind of zeolite molecular sieve as claimed in claim 1, it is characterized in that: the structural formula of coupling agent is R
1-Si-(R
2)
3, R wherein
1That phenyl, substituted-phenyl, carbonatoms are 1～19 alkyl or halogen, amino-NH
2, the carbonatoms that replaces of sulfydryl-SH is 1～19 alkyl; R
2Be halogeno-group or alkoxyl group.
4. the hydrophobically modified treatment process of a kind of zeolite molecular sieve as claimed in claim 3 is characterized in that: be alkyl, halogen, amino-NH
2, nitro-NO
2Or the phenyl of sulfydryl-SH replacement, the carbonatoms in the alkyl is 1～20.
5. the hydrophobically modified treatment process of a kind of zeolite molecular sieve as claimed in claim 4, it is characterized in that: the carbonatoms in the alkyl is 1～5.
6. the hydrophobically modified treatment process of a kind of zeolite molecular sieve as claimed in claim 3, it is characterized in that: alkoxyl group is methoxyl group, oxyethyl group or propoxy-.
7. the hydrophobically modified treatment process of a kind of zeolite molecular sieve as claimed in claim 3 is characterized in that: the phenyl that halogen replaces is a fluorine substituted benzene, difluoro substituted benzene, trifluoro substituted benzene, tetrafluoro substituted benzene, five fluorine substituted benzenes, a chlorine substituted benzene, dichloro substituted benzene, trichlorine substituted benzene, tetrachloro substituted benzene, pentachloro-substituted benzene, monobromo substituted benzene, dibromo substituted benzene, tribromo substituted benzene, tetrabromo substituted benzene, pentabromo-substituted benzene, an iodine substituted benzene, diiodo-substituted benzene, triiodo substituted benzene, tetraiodo substituted benzene or pentaiodo substituted benzene.
8. the hydrophobically modified treatment process of a kind of zeolite molecular sieve as claimed in claim 1 is characterized in that: be that the zeolite molecular sieve that 50～80g activated is joined in the toluene of 300mL drying in the step (2), again to the coupling agent that wherein adds 10～60mL.
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| CN103819944A (en) * | 2014-03-03 | 2014-05-28 | 上海绿强新材料有限公司 | Preparation method for molecular sieve reactive powder suitable for polyurethane system |
| CN106540662A (en) * | 2016-11-24 | 2017-03-29 | 陕西科技大学 | A kind of amino functional hydrophobic zeolite and its preparation method and application |
| CN107262043A (en) * | 2017-06-27 | 2017-10-20 | 陕西科技大学 | A kind of phenyl functionalization hydrophobic zeolite and its preparation method and application |
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| CN113166302A (en) * | 2018-10-26 | 2021-07-23 | 中国石油化工股份有限公司 | Polyolefin catalyst component containing mesoporous material and preparation method and application thereof |
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