CN105363352A - Method for synthesizing high acid resistant MOR zeolite molecular sieve membrane from fluorine-containing dilute solution - Google Patents
Method for synthesizing high acid resistant MOR zeolite molecular sieve membrane from fluorine-containing dilute solution Download PDFInfo
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- CN105363352A CN105363352A CN201510783570.7A CN201510783570A CN105363352A CN 105363352 A CN105363352 A CN 105363352A CN 201510783570 A CN201510783570 A CN 201510783570A CN 105363352 A CN105363352 A CN 105363352A
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Abstract
The present invention discloses a novel method for synthesizing a high acid resistant MOR zeolite molecular sieve membrane from a fluoride-containing dilute solution. The MOR zeolite molecular sieve membrane synthesized by the method uses a fluoride-containing dilute solution as a synthetic liquid to reduce the usage amount of chemicals, save cost of growing, and eliminate the problem of easy gelling and caking in the traditional preparation process of MOR zeolite molecular sieve membrane synthesis liquid. In addition, fluorinion is added as a mineralizer into the synthesis liquid to effectively promote the growth of the crystal and optimize the skeleton structure of MOR zeolite molecular sieve. The synthesized MOR zeolite molecular sieve membrane can be used in high concentration 90wt% acetic acid / water separation, also shows potential application possibility in dehydration of organic solvent or acidic organic solvent, and has important broad application prospect.
Description
Technical field
The invention belongs to inorganic material permeability and separation technical field, relate to a kind of synthesis and application of zeolite molecular sieve film, the method for the high acidproof MOR zeolite molecular sieve film of a kind of fluorine-containing weak solution synthesis is particularly provided.
Background technology
Acetic acid is a kind of very important organic chemical intermediates, its derivative is nearly hundreds of, be widely used in the fields such as organic chemical industry, food, agricultural, medicine, environmental protection, be the presoma of the ester class of ethyl acetate, terephthalic acids, fluoroacetic acid, cellulose esters and other types, it is one of maximum the first five ten kinds of chemical products of output.Usually containing a certain amount of water (being less than 20wt.%) in acetic acid production and application process.How to recycle from industrial production waste liquid or to reclaim acetic acid, and biomass-making acetic acid is also the hot issue of recycling economy and sustainable economic development.Acetic acid dehydration enrichment, the refining active demand becoming these industries.Traditional rectifying, to there is energy consumption to organics dehydration refining in azeotropic distillation method high, and equipment investment is large, produces the shortcomings such as secondary pollution.In acetic acid production, the energy that purification of acetic acid consumes is 98% of total energy consumption.UF membrane is as new and high technology, and its outstanding feature is energy-conservation, clean, efficiently, compatible strong, be particularly suitable for modern industry to energy-conservation, low-grade raw material recycling and the needs eliminating environmental pollution, become the important component part realizing Economic Sustainable Development Strategy.Development low energy consumption, efficient, green acetic acid dehydration membrane technology become the active demand of the related industry scientific developments such as acetic acid, are also that national energy-saving reduces discharging the active demand with sustainable development.
From the nineties in last century, high speed development has been got in the preparations and applicatio research of zeolite molecular sieve film, and zeolite molecular sieve film research becomes study hotspot and the forward position of membrane science and technology.So far, many researchers report the separation that MOR zeolite molecular sieve film is applied to water/acetic acid.2003, Japanese Matsukata etc. (SeparationandPurificationTechnology, 32 (2003) 199-206) utilized a H
2the synthesis liquid of O/Si than 12.2 has prepared MOR (Mordenite) zeolite molecular sieve film on alumina surface, and this film is applied to 90wt.% acetic acid dehydration, and separation factor is only 50.XiansenLi etc. (JournalofMembraneScience, 339 (2009) 224-232) use H respectively
2o/Si is than the fluorine-containing and H being 30
2o/Si be 11.2 free-floride synthesis liquid synthesize on mullite carrier and prepared permanent acidproof MOR zeolite molecular sieve film, but for 90wt.% acetic acid dehydration, permeation flux and separation factor are not high.Afterwards, ZanChen etc. (JournalofMembraneScience411-412 (2012) 182-192) also use H respectively
2o/Si has investigated the film preparation of MOR zeolite molecular sieve than the fluorine-containing and floride-free synthesis liquid being 26.7, and prepared film has permanent acid resistance, but permeation flux is lower.2014, Mei-HuaZhu etc. (IndustrialandEngineeringChemistryResearch53 (2014) 19168-19174) adopted a H
2o/Si is than being that the fluorine-containing synthesis liquid of 35 is under heating using microwave is auxiliary, MOR zeolite molecular sieve film has been prepared under the short hydrothermal crystallizing time (3h), greatly reducing the hydrothermal crystallizing time, but the MOR zeolite molecular sieve film of preparation only has 0.44kgm to separation of high-concentration 90wt.% acetic acid/water flux
-2h
-1.To sum up, above-mentioned synthesis liquid H
2o/Si ratio is up to 35, and synthesis liquid water content is low, and amount of chemicals used consumption is large.In the recent period, YaqiZhang etc. (MicroporousandMesoporousMaterials207 (2015) 39-45) H
2o/Si has prepared MOR zeolite molecular sieve film than the free-floride synthesis liquid being 111, but this film is under 100 DEG C of pervaporations, to high concentration 90wt.% acetic acid/water flux only 0.195kgm
-2h
-1, and separation factor only has 90, does not reach the requirement of commercial Application.
Summary of the invention
The object of the present invention is to provide the method for the high acidproof MOR zeolite molecular sieve film of a kind of fluorine-containing weak solution synthesis, with the MOR zeolite molecular sieve film of the method synthesis, there is extremely strong acid resistance and hydrophily simultaneously, superior separating property is demonstrated to the separation of high concentration 90wt% acetic acid/water.
The object of the invention is to adopt following technical scheme to realize:
A method for the high acidproof MOR zeolite molecular sieve film of fluorine-containing weak solution synthesis, comprises the steps:
(1) by the dispersion of MOR zeolite molecular sieve crystal seed in deionized water, MOR zeolite molecular sieve crystal seed liquid is obtained;
(2) the MOR zeolite molecular sieve crystal seed liquid obtained in step (1) is utilized to introduce crystal seed layer on porous carrier surface;
(3) Si source, Al source, NaOH, NaF are dissolved and prepare to obtain synthesis liquid in deionized water, in described synthesis liquid, the mol ratio of each component is:
Si source: Al source: NaOH:NaF:H
2o=1:0.005 ~ 0.5:0.05 ~ 0.8:0.05 ~ 2:100 ~ 400;
(4) the synthesis liquid having the porous carrier of MOR crystal seed layer and step (3) to obtain the load that step (2) obtains loads in metal reaction still, synthetic reaction 0.5 ~ 12h at 100 ~ 200 DEG C, after synthetic reaction terminates, take-off pipe spends deionized water to neutral, at 50 ~ 100 DEG C, dry 10 ~ 24h.
In technique scheme of the present invention, the conventional crystal seed introducing method in this area can be adopted with MOR zeolite molecular sieve crystal seed liquid in the method that crystal seed layer is introduced on described porous carrier surface in described step (2), as infusion process, hot submersion method, alternating temperature hot submersion method, vacuum crystal method, spraying process, swabbing process and spin-coating method, concrete grammar all can carry out according to this area conventional method, does not specifically state in the present invention.In described crystal seed introducing method, the present invention preferably can adopt hot submersion or alternating temperature hot submersion method.
In above-mentioned all technical schemes of the present invention, in the liquid of MOR zeolite molecular sieve crystal seed described in step (1), the content of MOR zeolite molecular sieve is 0.05 ~ 5wt%, is preferably 0.1 ~ 1.0wt%; In crystal seed liquid, MOR zeolite molecular sieve crystal granular size is 50nm ~ 3 μm, is preferably 0.05 ~ 0.8 μm.
In above-mentioned all technical schemes of the present invention, described in step (2), porous carrier material is aluminium oxide, zirconia, mullite, stainless steel or wire netting; The aperture of described porous carrier is 0.02 μm ~ 50 μm, is preferably 0.1 μm ~ 2 μm.
In above-mentioned all technical schemes of the present invention, described in step (2), the shape of porous carrier is sheet, flat board, tubulose, doughnut or multichannel carrier, is preferably tubulose.
In above-mentioned all technical schemes of the present invention, method MOR zeolite molecular sieve crystal seed being dispersed in deionized water in step (1) is: MOR zeolite molecular sieve crystal seed is placed in deionized water, and utilize magnetic stirring apparatus to make solution dispersed with stirring even, and placed separatelyly to shake in ultrasonic wave in the middle of process, obtain MOR zeolite molecular sieve crystal seed liquid.
In above-mentioned all technical schemes of the present invention, the mol ratio of synthesizing each component in liquid described in step (3) is preferably Si source: Al source: NaOH:NaF:H
2o=1:0.005 ~ 0.5:0.05 ~ 0.8:0.1 ~ 1:120 ~ 350.
In above-mentioned all technical schemes of the present invention, the Si source described in step (3) is white carbon (SiO
2nH
2o), Ludox (SiO
2nH
2o), ethyl orthosilicate (Si (OC
2h
5)
4) or sodium metasilicate (Na
2siO
3), more excellent is Ludox (SiO
2nH
2o).
In above-mentioned all technical schemes of the present invention, the Al source described in step (3) is Al (NO
3)
3(aluminum nitrate), Al
2(SO
4)
3(aluminum sulfate), AlCl
3(aluminium chloride), Al
2o
3(aluminium oxide) or Al (OCH (CH
3)
2)
3(aluminium isopropoxide), more excellent is Al
2(SO
4)
3.
In above-mentioned all technical schemes of the present invention, the preparation condition of the described synthesis liquid of step (3) is: at 20 ~ 40 DEG C, stir 1 ~ 12h.
In above-mentioned all technical schemes of the present invention, the synthesis temperature described in step (4) is preferably 120 ~ 180 DEG C, is more preferably 125 ~ 175 DEG C; Generated time is preferably 1 ~ 8h, is more preferably 2 ~ 6h.
In technical scheme of the present invention, H in synthesis liquid
2o/Si is 120 ~ 350, realizes the high-moisture of synthesis liquid, can not lump by gel, and more effectively can utilize chemicals, reduce costs in synthesis liquid process for preparation.
Adopt technical scheme of the present invention to synthesize the MOR zeolite molecular sieve film obtained and can be used for infiltration evaporation and Steam soak, operating temperature is 20 ~ 150 DEG C, can be used for ethanol, isopropyl alcohol, normal propyl alcohol, butanols, acetone solvent dehydration, can be used for the dehydration of acetic acid, acrylic acid and esters solvent, also can be used for high concentration 90wt% and above acetic acid or organic acid and dewater.
The MOR zeolite molecular sieve film synthesized in the present invention can be used for dehydration of organic solvent under sour environment.
MOR zeolite molecular sieve film of the present invention, adopts a fluorine-containing weak solution as synthesis liquid, decreases the use amount of chemicals, save production cost, and eliminates the problem of easily gel caking in traditional MOR zeolite molecular sieve film synthesis liquid layoutprocedure.In addition, fluorine ion adds synthesis liquid as mineralizer and effectively can promote crystal growth and optimize MOR zeolite molecular sieve skeleton structure.The MOR zeolite molecular sieve film of synthesis can be applicable to high concentration 90wt% acetic acid/water separation, and also shows potential application possibility to organic solvent or acidic organic solvent dehydration, has important broad prospect of application.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the MOR zeolite molecular sieve film taking Woelm Alumina as carrier;
Fig. 2 is the SEM figure of the MOR zeolite molecular sieve film taking Woelm Alumina as carrier.
Detailed description of the invention
Following non-limiting example can make those of ordinary skill in the art more fully understand the present invention, but does not limit the present invention in any way.In following embodiment, if no special instructions, the experimental technique used is conventional method, and material therefor, reagent etc. all can be bought from biological or chemical company.
Embodiment 1
Prepare MOR zeolite molecular sieve film as follows:
(1) process of porous carrier pipe: the porous carrier synthesizing MOR zeolite molecular sieve film used is α-Al
2o
3support tube, its average pore size is 2 ~ 3 μm, and porosity is 30% ~ 40%.α-Al
2o
3support tube painting crystalline substance before first with sand papering to flat smooth, then use deionized water ultrasonic cleaning, be finally placed on dried overnight in 80 DEG C of baking ovens.
(2) preparation of MOR zeolite molecular sieve crystal seed liquid: get 0.5gMOR zeolite molecular sieve (Shanghai Zhuoization) and add 100g deionized water to be mixed with mass fraction be that the 0.5wt%MOR zeolite molecular sieve aqueous solution is as crystal seed liquid, after each 30min of crystal seed liquid ultrasonic agitation, utilize hot submersion cladding process at α-Al
2o
3support tube is introduced above-mentioned MOR zeolite molecular sieve, for subsequent use as crystal seed pipe after 80 DEG C of dry 8h.
Utilize hot submersion cladding process at α-Al
2o
3concrete grammar support tube being introduced above-mentioned MOR zeolite molecular sieve is:
Get the dried α-Al of process
2o
3support tube, pipe two ends are tight with the sealing of polytetrafluoroethylene (PTFE) plug, subsequently by the α-Al of two ends sealing
2o
3support tube slowly puts people MOR crystal seed liquid, slowly takes out after 30s, takes off the polytetrafluoroethylene (PTFE) plug at pipe two ends afterwards immediately, after room temperature is dried, is placed in 80 DEG C of baking oven dried overnight, must be coated with the α-Al of MOR crystal seed
2o
3support tube.
(3) preparation of MOR zeolite molecular sieve film synthesis liquid: by Si source (Ludox, JN-25, Qingdao Haiyang chemical industry), Al source (Al
2(SO
4)
318H
2o, traditional Chinese medicines group chemical reagent), NaOH, NaF put into deionized water, at room temperature stir 2h, prepare and to obtain synthesis liquid, in described synthesis liquid, the mol ratio of each component is:
Si source: Al source: NaOH:NaF:H
2o=1:0.08:0.2:0.2:150.
(4) the above-mentioned α-Al being coated with MOR crystal seed
2o
3support tube is vertically placed in metal reaction still, and slow injection in metal reaction still synthesizes liquid subsequently, and last metal reaction still is placed in 170 DEG C, baking oven reaction 6h, after reaction terminates, film pipe is taken out, spend deionized water to neutral, 80 DEG C of dryings 12 hours, obtain MOR zeolite molecular sieve film.
Fig. 1 is that the MOR zeolite molecular sieve film XRD prepared schemes, and Fig. 2 is the SEM figure of this molecular screen membrane, wherein the cross section Electronic Speculum figure of Fig. 2 A to be surperficial Electronic Speculum figure, Fig. 2 B of the MOR zeolite molecular sieve film prepared be MOR zeolite molecular sieve film prepared.Visible in Fig. 1, there is the α-Al of typical MOR zeolite molecular sieve and support tube in XRD figure
2o
3characteristic diffraction peak, illustrate that the present invention has prepared MOR molecular screen membrane; Visible in Fig. 2, the MOR zeolite molecular sieve film surface prepared is without obvious intracrystalline pore, and thicknesses of layers is 3 ~ 4 μm, illustrates that the MOR molecular sieve rete that the present invention prepares is fine and close and thin.
Be applied to by prepared MOR zeolite molecular sieve film in infiltration evaporation experiment, be applied to the dehydration of 90wt% acetic acid aqueous solution, at 75 DEG C, permeation flux is 0.83kg/m
2h, separation factor is up to more than 10000.
Embodiment 2
By the operation that embodiment 1 is identical, just crystal seed liquid concentration (the MOR zeolite molecular sieve aqueous solution) is 0.2wt%, the Pervaporation Separation of the MOR zeolite molecular sieve film of synthesis gained slightly declines compared with embodiment 1, but separation factor still keeps up to more than 10000.To 90wt% acetic acid dehydration, at 75 DEG C, permeation flux is 0.64kg/m
2h.
Embodiment 3
By the operation that embodiment 1 is identical, just α-Al
2o
3support tube aperture is about 100nm, and the Pervaporation Separation of the MOR zeolite molecular sieve film of synthesis gained is better than embodiment 1.To 90wt% acetic acid dehydration, at 75 DEG C, permeation flux is 0.92kg/m
2h, separation factor is up to more than 10000.
Embodiment 4
By the operation that embodiment 1 is identical, just mole the consisting of of fluorine-containing weak solution configuration: Si source: Al source: NaOH:NaF:H
2o=1:0.08:0.2:0.2:200, the Pervaporation Separation of the MOR zeolite molecular sieve film of synthesis gained is inferior to embodiment 1.To 90wt% acetic acid dehydration, at 75 DEG C, permeation flux is 0.74kg/m
2h, separation factor is up to 850.
Claims (10)
1. a method for the high acidproof MOR zeolite molecular sieve film of fluorine-containing weak solution synthesis, is characterized in that, comprise the steps:
(1) by the dispersion of MOR zeolite molecular sieve crystal seed in deionized water, MOR zeolite molecular sieve crystal seed liquid is obtained;
(2) the MOR zeolite molecular sieve crystal seed liquid obtained in step (1) is utilized to introduce crystal seed layer on porous carrier surface;
(3) Si source, Al source, NaOH, NaF are dissolved and prepare to obtain synthesis liquid in deionized water, in described synthesis liquid, the mol ratio of each component is:
Si source: Al source: NaOH:NaF:H
2o=1:0.005 ~ 0.5:0.05 ~ 0.8:0.05 ~ 2:100 ~ 400.
(4) the synthesis liquid having the porous carrier of MOR crystal seed layer and step (3) to obtain the load that step (2) obtains loads in metal reaction still, synthetic reaction 0.5 ~ 12h at 100 ~ 200 DEG C, after synthetic reaction terminates, take-off pipe spends deionized water to neutral, at 50 ~ 100 DEG C, dry 10 ~ 24h.
2. the method for the high acidproof MOR zeolite molecular sieve film of synthesis according to claim 1, it is characterized in that, in the liquid of MOR zeolite molecular sieve crystal seed described in step (1), the content of MOR zeolite molecular sieve is 0.05 ~ 5wt%, and in crystal seed liquid, MOR zeolite molecular sieve crystal granular size is 50nm ~ 3 μm.
3. the method for the high acidproof MOR zeolite molecular sieve film of synthesis according to claim 1, it is characterized in that, described in step (2), the material of porous carrier is aluminium oxide, zirconia, mullite, stainless steel or wire netting; The aperture of described porous carrier is 0.02 μm ~ 50 μm.
4. the method for the high acidproof MOR zeolite molecular sieve film of synthesis according to claim 1, is characterized in that, the shape of porous carrier described in step (2) is tubulose, flat board, doughnut or multichannel carrier.
5. the method for the high acidproof MOR zeolite molecular sieve film of synthesis according to claim 1, it is characterized in that, be infusion process, hot submersion method, alternating temperature hot submersion method, vacuum crystal method, spraying process, swabbing process or spin-coating method with MOR crystal seed liquid in the method for porous carrier surface introducing crystal seed layer in the step (2).
6. the method for the high acidproof MOR zeolite molecular sieve film of synthesis according to claim 1, it is characterized in that, the mol ratio of synthesizing each component in liquid mol ratio described in step (3) is:
Si source: Al source: NaOH:NaF:H
2o=1:0.005 ~ 0.5:0.05 ~ 0.8:0.1 ~ 1:120 ~ 350.
7. the method for the high acidproof MOR zeolite molecular sieve film of synthesis according to claim 1, it is characterized in that, described in step (3), Si source is white carbon, Ludox, ethyl orthosilicate or sodium metasilicate.
8. the method for the high acidproof MOR zeolite molecular sieve film of synthesis according to claim 1, it is characterized in that, described in step (3), Al source is Al (NO
3)
3, Al
2(SO
4)
3, AlCl
3, Al
2o
3or Al (OCH (CH
3)
2)
3.
9. the method for the high acidproof MOR zeolite molecular sieve film of synthesis according to claim 1, it is characterized in that, described in step (4), synthesis temperature is 120 ~ 180 DEG C, and generated time is 1 ~ 8h.
10. the method for the high acidproof MOR zeolite molecular sieve film of synthesis according to claim 1, is characterized in that, in the preparation condition of the described synthesis liquid of step (3) is: at 20 ~ 40 DEG C, stir 1 ~ 12h.
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| CN109351206A (en) * | 2018-10-23 | 2019-02-19 | 黄山学院 | A kind of preparation method of nanofiltration zeolite molecular sieve film |
| CN109999676A (en) * | 2019-05-05 | 2019-07-12 | 大连理工大学 | The preparation method of T-type zeolite molecular sieve membrane |
| CN112933986A (en) * | 2021-02-02 | 2021-06-11 | 黄山学院 | Method for synthesizing molecular sieve membrane with high water permeability |
| CN117402034A (en) * | 2023-12-13 | 2024-01-16 | 淄博鲁华泓锦新材料集团股份有限公司 | Method for continuously producing norbornene |
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| CN109351206A (en) * | 2018-10-23 | 2019-02-19 | 黄山学院 | A kind of preparation method of nanofiltration zeolite molecular sieve film |
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