CN104857862B - The method that Ge ZSM 5 molecular screen membrane is used for acetic acid aqueous systems separation water component - Google Patents
The method that Ge ZSM 5 molecular screen membrane is used for acetic acid aqueous systems separation water component Download PDFInfo
- Publication number
- CN104857862B CN104857862B CN201510232609.6A CN201510232609A CN104857862B CN 104857862 B CN104857862 B CN 104857862B CN 201510232609 A CN201510232609 A CN 201510232609A CN 104857862 B CN104857862 B CN 104857862B
- Authority
- CN
- China
- Prior art keywords
- crystal seed
- liquid
- acetic acid
- zsm
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention is a kind of method that Ge ZSM 5 molecular screen membrane is used for acetic acid aqueous systems separation water component, specifically refer to be used for pervaporation separating acetic acid in high-concentration acetic acid aqueous solution mixed with ZSM 5 zeolite molecular sieve film of germanium atom, separation factor can reach infinity, and flux exceeds prior art.This zeolite molecular sieve facial film synthetic method is Template-free method method, greatly reduces production cost, simplifies production technology, is conducive to environmental conservation;Raw material is domestic cheap products, is conveniently easy to get, low cost.In terms of selectivity, per-meate side water concentration can reach 100%, and separation factor can be infinity;Flux aspect, with long-time stable in 600g/m2.h, and can have good temperature dependency and concentration interdependence.
Description
Technical field
The present invention is the application that a kind of zeolite molecular sieve film isolates water component in acetic acid and aqueous solution, specifically refers to mix
The ZSM-5 zeolite molecular screen membrane having germanium atom is used for pervaporation separating acetic acid in high-concentration acetic acid aqueous solution, and separation factor can
Reach infinity, flux exceeds prior art.
Background technology
The side reaction occurring in high-purity acetic acid production process can produce a certain amount of water, now normal for removing the water in product
Using method be rectification method, and the boiling point of acetic acid and water is closer to, the method for common industrial rectification separating acetic acid and water,
Power consumption is high, and cost is big and is unfavorable for environmental conservation, and pervaporation is as a kind of emerging membrane separation technique, have power consumption low,
Many advantages such as performance height, environmental friendliness.Inoranic membrane swelling resistance, good stability, the feature of acid and alkali-resistance are highly suitable for oozing
A small amount of water component in evaporation separating acetic acid thoroughly.The research of ZSM-5 molecular sieve film is ripe, can be acidproof by adjusting its silica alumina ratio
Property and hydrophilic aspect coordinate, and take into account both.
Infiltration evaporation technique is a kind of new membrane separation technique progressively growing up in the last few years, has efficiency high, energy
The little, equipment investment of consumption is few and the advantage such as environmental friendliness, and the selectivity due to the film for infiltration can be very high, so being directed to certain
A little azeotropics, the separation of the mixture of nearly boiling, pervaporation technology can play very big advantage.At present food, medicine and
The existing relatively broad application of chemical field, pervaporation is one kind side of separation that distillation technique is combined with membrane separation process
Method, it is different from conventional membrane separation process, is a kind of gas membrane Seperation Technology with phase transformation, and the charging before film is liquid mixing
Thing, the transmission side after film is steam phase, therefore also needs to certain energy in separation process, to promote the carrying out of process, it
Separation mechanism is:Firstly, it is necessary to the material isolated is in the selective absorption on film surface, secondly, separated object matter is in film
Dissolving diffusion, finally, on rear side of film, material becomes gas phase desorption.
Existing zeolite embrane method separating acetic acid water:Li Gang et al. has prepared silicon in porous alumina carrier surface
Aluminum ratio is 50 ZSM-5 molecular sieve film and is applied to mass fraction and is 50% in the middle of acetic acid aqueous solution and makees oozing of acetic acid water
Evaporation characterizes to membrane material thoroughly, and permeation flux has reached 0.65kg/m2H, but its separation factor only has 25.Li S,
TVAN.A et al. is prepared for Ge-substituted-ZSM-5 perforated membrane.Using rustless steel as carrier, from acetic acid aqueous systems
Separating acetic acid, acetic acid feed concentration increases to 5wt% from 0.33wt%, and separation selectivity reduces half.In 363K condition
Under, the total flux 0.43kg/m of film2H, acetic acid/water separation selectivity is 14.Tsuneji Sano etc. adopts hydro-thermal method not
Obtain total silicon zeolite membrane on rust bracing members body, carry out pervaporation sign with acetic acid-water mixture as charging.Xiansen
Li etc. [72] has synthesized the ZSM-5 molecular sieve film that silica alumina ratio is 7.5 and mordenite membrane, under conditions of 75 degree, using matter
Measure the acetic acid aqueous solution that fraction is 90% and carry out pervaporation, its permeation flux can reach 0.67kg/m2H, its separate because
Number is 180.
Content of the invention
The present invention provides a kind of cheap one-tenth to produce mode, including Template-free method, domestic cheap raw material etc..Using size crystal seed
Cooperation applies brilliant mode, modifies carrier with big crystal seed, with the method for little crystal seed induction filming, with Template-free method formula commercially available honest and clean
The Ge-ZSM-5 zeolite molecular sieve film that a layer thickness is about 2.5 μm is synthesized on valency macropore α-Al2O3 earthenware carrier, has solved
Zeolite molecular sieve membrane flux and two main aspects of selectivity.All obtain good application effect.
Prepare Ge-ZSM-5 molecular sieve acidproof and that flux is high by controlling silica alumina ratio, the incorporation of Ge and synthesis condition
Film, all has a lot of phases by the use of Ge element as the element of the same clan with silicon in terms of chemical property and physical arrangement with element silicon
Like part so that its be more prone to enter in the middle of framing structure, the key of the Ge-O-Si that its larger atomic radius also makes
Angle is greater than the bond angle of Si-O-Si, thus leading to the change of duct radius and structure.Reach flux and selective raising.
Permeation evaporating device is assembled by room designed, designed, is heated by material liquid, and end vacuum pumping pump provides the side of power
Formula is carried out, and rear side is provided with cold hydrazine, is cooled down in the way of liquid nitrogen.Schematic device as shown in figure 1, using glacial acetic acid with go
Ionized water is configured to certain density acetic acid aqueous solution, this aqueous solution is poured in wide mouthed bottle, puts in water-bath and heated,
Membrane tube is shut using membrane separator one end above-mentioned, and rubber tube and cold hydrazine UNICOM are passed through in one end.Cold hydrazine is placed in and is placed with liquid
In the thermos cup of nitrogen.Material liquid is stirred using magnetic stirring apparatuss, reduces spreading effect and concentration polarization phenomenon is divided to film
Produce impact from performance.The other end of cold hydrazine is connected with vacuum equipment, and vacuum equipment is by vacuum pump, surge tank, pressure gauge and pressure
Power induction apparatuss are constituted.Open the valve of vacuum pump, magnetic agitation, water-bath and device, carry out pervaporation operation, material liquid
Carry out selecting to separate by film layer through overflash, the water component of material liquid preferentially passes through, and is enriched with the rear side of film layer, by true
Gas is constantly evacuated in cold hydrazine empty device, and low temperature can make gas condense.Change cold hydrazine every one section, condensed fluid is through weighing
Afterwards, using sampling probe sample introduction, by the beautiful GC7890-T type gas chromatograph producing in Shanghai sky, the content of each component is surveyed
Fixed.The setting temperature of gas chromatogram is 150 degree of column temperature, detection temperature and sample introduction is 180 degree, range 120 for temperature.
A kind of method that Ge-ZSM-5 molecular screen membrane is used for acetic acid-water solution separation water component, step is as follows:
(1) Vehicle element:With sand paper to α-Al2O3Carrier is polished, then with being cleaned by ultrasonic in the acetic acid of 30wt.%,
Then the sodium hydroxide solution using 1mol/L is cleaned by ultrasonic, and is finally washed to neutrality;By the α cleaning up-Al2O3Carrier is dried,
Calcining, standby;
(2) big crystal seed preparation
ZSM-5 molecular sieve is sufficiently mixed with water, compound concentration be 2.5wt.% big crystal seed liquid, then repeatedly ultrasonic and
Stirring, until the particle diameter of big crystal seed is 2-4 μm;
(3) preparation of little crystal seed
ZSM-5 molecular sieve is carried out with ball milling, adds water, repeat to stir and ultrasonic;Standing a period of time, ZSM-5 molecular sieve
It is placed in bottom of bottle, intermediate layer is white opacity liquid, upper strata is clear liquid;The clear liquid taking upper strata is dried under the conditions of 50 DEG C, device after drying
One layer of white solid is attached on wall and is little crystal seed;The particle diameter of little crystal seed is 300-500nm;
(4) crystal seed applies crystalline substance
Compound concentration is the little crystal seed liquid of 0.25wt.%, to α-Al2O3Carrier applies the side that crystal type adopts alternating temperature hot submersion
Formula, the α-Al obtaining in step (1)2O3Carrier surface introduces one layer of thin and compact crystal seed layer, the coating procedure of crystal seed, adopts
Apply brilliant twice, the mode of size crystal seed cooperation carries out applying crystalline substance;
1) big crystal seed applies crystalline substance
With Teflon stopper by α-Al2O3Carrier two ends seal, and dry, and are placed on standing 20s in big crystal seed liquid,
Big crystal seed liquid concentration is mass fraction 4%, slowly lifts out α-Al2O3Carrier, Teflon stopper is taken off, in atmosphere
Dry, be dried, be finally placed in solidification in more than 150 DEG C baking ovens;Then by α-Al2O3The blocked up crystal seed layer erasing of carrier surface, makes
Obtain α-Al2O3Carrier surface recovers smooth;
2) little crystal seed applies crystalline substance
The painting crystalline substance step of little crystal seed, applies brilliant process similar to big crystal seed, and being distinguished as little crystal seed liquid concentration is mass fraction
0.25% and do not need crystal seed layer erasing operation;
(4) Synthesis liquid is prepared
Prepare sodium hydrate aqueous solution, under mechanical stirring, Deca Ludox, mixed liquor assumes milky milk shape, protects
Hold 35 DEG C of heating in water bath and stirring more than 16h;
In above ratio, by aluminum sulfate and sodium fluoride, it is added in above-mentioned mixed liquor, continues stirring reaction 2h;Above-mentioned each
Mol ratio 17NaOH of material:26SiO2:1Al2(SO4)3:25NaF:1037H2O;
Above-mentioned mixed liquor is placed in 0 DEG C and continues stirring, ethyoxyl germanium is placed in enough isopropanols and is diluted, then pass through
Unnecessary isopropanol is removed by 80 DEG C of heating in water bath, and carries out a certain amount of moisturizing, isopropanol by volume:Water is 1:28, so
Add it in above-mentioned mixed liquor afterwards, in molar ratio for SiO2:Ge(OC2H5)4=50-200, had both obtained Synthesis liquid;
By step 1) and step 2) Tu Jinghou crystal seed pipe two ends sealing be placed in reactor, add Synthesis liquid to height do not have
Cross crystal seed pipe, be placed in heating 24h in 175 DEG C of baking ovens;Take out, cooling, cleaning, dry.
Beneficial effects of the present invention:This zeolite molecular sieve facial film synthetic method is Template-free method method, greatly reduces and produces into
Originally, simplify production technology, be conducive to environmental conservation;Raw material is domestic cheap products, is conveniently easy to get, low cost.In selectivity side
Face, per-meate side water concentration can reach 100%, and separation factor can be infinity;Flux aspect, can be existed with long-time stable
600g/m2H, and there is good temperature dependency and concentration interdependence.
Brief description
Fig. 1 is the infiltration evaporation schematic device of the present invention.
Fig. 2 is 90% acetic acid pervaporation performance map.
Fig. 3 is synthesized molecular screen membrane surface electromicroscopic photograph.
Fig. 4 is synthesized molecular screen membrane section electromicroscopic photograph.
In figure:(a) magnetic stirring apparatuss;(b) water-bath;C () separates membrane tube;(d) material liquid;(e) separator;
(f) rubber tube;(g) cold hydrazine;(h) true surge tank;(i) pressure vacuum ga(u)ge;(j) vacuum pump.
Specific embodiment
Below in conjunction with accompanying drawing and technical scheme, further illustrate the specific embodiment of the present invention.
First by 800 mesh sand paper to α-Al2O3Support tube is polished, and is cleaned with tap water in polishing, treats polishing relatively
For smooth when carry out secondary polishing using the sand paper of 1500 mesh, until support tube surfaces slippery enough.
The support tube polished is put in the tank filling tap water, is placed in ultrasonic middle concussion washing 30min, removes and carry
Residue in body surface face and duct, changes tap water and continues concussion washing, cleaning is till the water in tank is clear water.
Then support tube is placed in ultrasonic vibration 30min in the tank fill deionized water, then support tube is put into mass fraction and is about
In the middle of 30% acetic acid solution, ultrasonic vibration 30min, subsequently takes out, acetic acid solution is changed to supersound washing in deionized water, phase
Between constantly change deionized water, until being changed into neutral.Subsequently support tube is put into ultrasonic in the sodium hydroxide solution of 1mol/L washing
Wash 30min, be then replaced by deionized water, constantly wash to neutrality.
The support tube washing is put in crucible, is first placed into 80 degrees Celsius of oven drying 4h, is subsequently placed into 550 in Muffle furnace
Calcining 4h is standby for degree.
(1) big crystal seed preparation
Take a certain amount of ZSM-5 molecular sieve to be sufficiently mixed with a certain amount of deionized water, prepare the big crystal seed of desired concn
Liquid, then puts it into Vltrasonic device concussion 10min, is then again stirring for 10min, constantly repeats to stir and concussion operation is some
Secondary.Scanned electron microscopic observation, the crystal seed size that the method is obtained is 2-4 μm.
(2) preparation of little crystal seed
The made ZSM-5 molecular sieve of Dalian University of Technology's catalyst chamber, puts in high speed ball mill and carries out abundant ball milling operation,
Powder body after ball milling is placed in 1000ml wide mouthed bottle, fills it up with deionized water.Put into rotor, be placed in high-speed stirred on magnetic stirring apparatuss
10min, then puts it into Vltrasonic device concussion 10min, is then again stirring for 10min, constantly repeat to stir and shake operation
Several times.
The mixed liquor of the crystal seed handled well water is stood a period of time, progressively decreases to bottle bottom under gravity,
Intermediate layer is shallower white opacity liquid, and upper strata is clear liquid, and we take the clear liquid on appropriate upper strata, put in clean beaker, put
Enter in 50 degree of baking ovens and be dried, behind some skies, treat that the liquid in beaker is evaporated, be attached to one layer of white solid at cup bottom, this is just
It is the little crystal seed that we prepare.Scanned electron microscopic observation, the crystal seed size that the method is obtained is 300-500nm.
Take this crystal seed a certain amount of, add different amounts of deionized water by calculating, the variable concentrations required for being configured to
Crystal seed liquid.
Support tube applies crystal type by the way of alternating temperature hot submersion, in the α-Al handling well2O3Carrier pipe surface introduces one layer
Thin and compact crystal seed layer.The coating procedure of crystal seed, we are brilliant using applying twice, and the mode of size crystal seed cooperation carries out applying brilliant behaviour
Make.
(1) big crystal seed applies crystalline substance
Concrete operation step is to be sealed support tube two ends using Teflon stopper, is positioned over 120 degrees Celsius of baking ovens
Middle heating a period of time, (big crystal seed liquid have passed through weight in advance then rapidly support tube to be put into the good big crystal seed liquid of configured in advance
Multiple stirring and supersound process, to ensure the uniform of whole system, stand 20s, big crystal seed liquid concentration used is mass fraction
4%, slowly lift out support tube afterwards, subsequently, take off the sealing-plug at support tube two ends, after drying a period of time in atmosphere,
Put into 50 degree of oven dryings.Put into 80 degree of baking ovens after 2h is dried and continue heating 4h, be finally placed in 175 degree of baking oven high temperature solidifications,
To improve the adhesion between crystal seed layer and carrier.
175 degree solidification 4h after, take out be painted with greatly crystalline substance in support tube, using absorbent cotton careful will be blocked up for carrier pipe surface
Crystal seed layer wipe so that carrier pipe surface recovers smooth degree again.During need the surface clashing using hair-dryer
Dust blows off out carrier pipe surface.
Primarily to modifying uneven aperture in support tube, we use and carrier aperture size for the coating of big crystal seed
Similar crystal seed blocks the macropore of carrier surface, prevents when we coat little crystal seed, and crystal grain is directly entered inside duct not
It is carrier surface
(2) little crystal seed applies crystalline substance
The painting crystalline substance step of little crystal seed, applies brilliant process similar to big crystal seed above, will coat the support tube of big crystal seed first,
Two ends seal, and put in 80 degree of baking ovens heating 2h, and the mass fraction preparing in advance is that 2.5% little crystal seed is fully stirred
With ultrasound procedure it is ensured that system uniform enough.After the completion of heating, quickly support tube is put in little crystal seed liquid, stands 20s,
Crystal seed pipe is taken out in slow lifting afterwards, and in the air is dried 15min, is then placed in being dried 2h in 50 degree of baking ovens, subsequent 80 degree
Baking oven 4h, last 175 degree of baking oven for drying solidification 4h.Take out coolant seal to save backup.
In Synthesis liquid process for preparation, weigh sodium hydroxide first in proportion and put in there-necked flask, add part deionization
Water dissolution, covers stopper, adjusts the stirring paddle of flask, connects mechanical stirring device, and water bath heating temperature is 35 degrees Celsius, treats
After sodium hydroxide is completely dissolved, weigh the Ludox that a certain amount of mass fraction is 25%, using glue head dropper, in mechanical agitation
Under, Deca Ludox is in sodium hydroxide while stirring.Mixed liquor now assumes milky milk shape, continues after completion of dropping
Keep heating in water bath and stirring operation, maintain more than 16h.
After 16h, solution has turned into clarification system, weighs a certain amount of aluminum sulfate, adds deionized water to be dissolved, is
Ensure that dissolving is abundant enough, be typically stirred in ultrasonic so that aluminum sulfate is fully dissolved.Sulphuric acid after fully dissolving
Aluminum is added dropwise in flask, continues stirring.After a period of time, weigh a certain amount of sodium fluoride, add deionized water abundant
Dissolving, drops in mixed liquor.After the completion of addition, we continue to stir 2h, and this process is referred to as digestion time.
Subsequently, there-necked flask is transferred to low temperature thermostat bath, continue stirring, temperature setting is 0 degrees centigrade, weighs one
Quantitative ethyoxyl germanium ethyoxyl germanium is due to using consumption less every time, and easily hydrolyzes, so noting using (1ml) is disposable
Emitter carries out taking of medicine.Connect nitrogen cylinder using Schlenk bottle glass nose end, adjust pressure, slowly open bottle upper end
Tetrafluoro plug, need during this period constantly to raise nitrogen pressure it is ensured that bottle under the protection of blanket of nitrogen, rapidly by syringe needle
Head depth enters in bottle, has converted by volume and has drawn ethyoxyl germanium after consumption.
Ethyoxyl germanium was to need to carry out certain dilution before incorporation system, and we select isopropanol to carry out ethyoxyl germanium
Dilution operation, but because our synthetic system is not need the addition of alcohols, so needing after successfully mixing ge source
Isopropanol is removed, 80 degree of water-bath has been higher than the boiling point of isopropanol, so will be many by 80 degree of heating in water bath before dress kettle
Remaining isopropanol removes, and carries out a certain amount of moisturizing.2h laggard luggage kettle operates, slow by applying the brilliant support tube finishing first
Put in the inner liner of reaction kettle that politef is made, Synthesis liquid is poured slowly into liner, tighten lid, put into rustless steel high pressure
In reactor, it is subsequently placed at heating 24h in 175 degree of baking ovens.
After 24h, take out reactor, put into and cool down in tank from the beginning, when being cooled to room temperature, kettle inner mold tube is taken out, from
Water rinses pipe surface, removes the stopper at two ends, membrane tube is immersed in tap water, changes water and continues to soak 6h, subsequently will after 6h
Membrane tube is taken out, and puts into 80 degree of baking ovens and fully dries.
Table 1 drug dosage and condition
Table 2 pervaporation data
Table 3 pervaporation data
Claims (1)
1. a kind of preparation method of the Ge-ZSM-5 molecular screen membrane for acetic acid-water solution separation water component is it is characterised in that walk
Suddenly as follows:
(1) Vehicle element:With sand paper to α-Al2O3Earthenware carrier is polished, then is cleaned by ultrasonic with the acetic acid of 30wt%,
Then the sodium hydroxide solution using 1mol/L is cleaned by ultrasonic, and is finally washed to neutrality;By the α cleaning up-Al2O3Earthenware carries
Body is dried, calcining, standby;
(2) big crystal seed preparation
ZSM-5 molecular sieve is sufficiently mixed with water, compound concentration is the big crystal seed liquid of 2.5wt%, then repeatedly ultrasonic and stirring,
Until the particle diameter of big crystal seed is 2-4 μm;
(3) preparation of little crystal seed
ZSM-5 molecular sieve is carried out with ball milling, adds water, repeat to stir and ultrasonic;Standing a period of time, ZSM-5 molecular sieve is placed in
Bottom of bottle, intermediate layer is white opacity liquid, and upper strata is clear liquid;The clear liquid taking upper strata is dried, on wall after drying under the conditions of 50 DEG C
It is attached to one layer of white solid and be little crystal seed;The particle diameter of little crystal seed is 300-500nm;
(4) crystal seed applies crystalline substance
Compound concentration is the little crystal seed liquid of 0.25wt%, to α-Al2O3Earthenware carrier applies the side that crystal type adopts alternating temperature hot submersion
Formula, the α-Al obtaining in step (1)2O3Earthenware carrier surface introduce one layer of thin and compact crystal seed layer, crystal seed coated
Journey, using applying crystalline substance twice, it is brilliant that the mode that size crystal seed coordinates carries out painting;
1) big crystal seed applies crystalline substance
With Teflon stopper by α-Al2O3Earthenware carrier two ends seal, and dry, and are placed on standing in big crystal seed liquid
20s, big crystal seed liquid concentration is mass fraction 4%, slowly lifts out α-Al2O3Earthenware carrier, Teflon stopper is taken
Under, dry in atmosphere, be dried, be finally placed in solidification in more than 150 DEG C baking ovens;Then by α-Al2O3Earthenware carrier surface mistake
Thick crystal seed layer erasing is so that α-Al2O3Earthenware carrier surface recovers smooth;
2) little crystal seed applies crystalline substance
The painting crystalline substance step of little crystal seed, with Teflon stopper by α-Al2O3Earthenware carrier two ends seal, and dry, are placed on
20s is stood, little crystal seed liquid concentration is mass fraction 0.25%, slowly lifts out α-Al in little crystal seed liquid2O3Earthenware carrier, will
Teflon stopper takes off, and dries in atmosphere, is dried, and is finally placed in solidification in more than 150 DEG C baking ovens;
3) Synthesis liquid is prepared
Prepare sodium hydrate aqueous solution, under mechanical stirring, Deca Ludox, mixed liquor assumes milky milk shape, keeps water
35 DEG C of bath heating and stirring more than 16h;
Aluminum sulfate and sodium fluoride are added in above-mentioned mixed liquor, continue stirring reaction 2h;Mol ratio NaOH of above-mentioned each material:
SiO2:Al2(SO4)3:NaF:H2O=17:26:1:25:1037;
Above-mentioned mixed liquor is placed in 0 DEG C and continues stirring, ethyoxyl germanium is placed in enough isopropanols and is diluted, then pass through 80
Unnecessary isopropanol is removed by DEG C heating in water bath, and carries out a certain amount of moisturizing, isopropanol by volume:Water is 1:28, then
Add it in above-mentioned mixed liquor, in molar ratio for SiO2:Ge(OC2H5)4=50-200, had both obtained Synthesis liquid;
By step 1) and step 2) Tu Jinghou crystal seed pipe two ends sealing be placed in reactor, add Synthesis liquid to height excessively unbrilliant
Plant pipe, be placed in heating 24h in 175 DEG C of baking ovens;Take out, cooling, cleaning, dry.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510232609.6A CN104857862B (en) | 2015-05-08 | 2015-05-08 | The method that Ge ZSM 5 molecular screen membrane is used for acetic acid aqueous systems separation water component |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510232609.6A CN104857862B (en) | 2015-05-08 | 2015-05-08 | The method that Ge ZSM 5 molecular screen membrane is used for acetic acid aqueous systems separation water component |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104857862A CN104857862A (en) | 2015-08-26 |
CN104857862B true CN104857862B (en) | 2017-03-08 |
Family
ID=53904287
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510232609.6A Active CN104857862B (en) | 2015-05-08 | 2015-05-08 | The method that Ge ZSM 5 molecular screen membrane is used for acetic acid aqueous systems separation water component |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104857862B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105797597A (en) * | 2016-04-01 | 2016-07-27 | 周俊静 | Preparation method for chabasite molecular sieve membrane |
CN112426891B (en) * | 2020-10-09 | 2022-05-13 | 大连理工大学 | Preparation method of CHA type zeolite molecular sieve membrane |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1786540A4 (en) * | 2004-08-03 | 2008-05-07 | Univ Colorado | Membranes for highly selective separations |
CN101654260A (en) * | 2009-09-11 | 2010-02-24 | 太原理工大学 | Method for preparing orientation molecular sieve membrane |
CN101823725B (en) * | 2010-04-29 | 2012-01-11 | 吉林大学 | Method for preparing height-oriented molecular sieve membrane |
CN102500243A (en) * | 2011-11-17 | 2012-06-20 | 常州大学 | Preparation method for molecular sieve/organic composite permeable vaporization membrane |
CN102701327B (en) * | 2012-06-14 | 2014-02-26 | 太原理工大学 | Application of hydrophilic Ge-ZSM-5 molecular sieve membrane to separation of organics/water system |
-
2015
- 2015-05-08 CN CN201510232609.6A patent/CN104857862B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN104857862A (en) | 2015-08-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU2019467669B2 (en) | A composite thermal insulation material and its preparation method | |
CN103933871A (en) | Preparation method of all-silicon MFI type molecular sieve membrane with high stability | |
CN103803934A (en) | Nanosized silica thermal insulation material and preparation method based on normal-temperature drying wet process thereof | |
CN104108722A (en) | Preparation method for ZIF-8 membrane supported by porous alumina carrier | |
CN104857862B (en) | The method that Ge ZSM 5 molecular screen membrane is used for acetic acid aqueous systems separation water component | |
CN102580568B (en) | Method for preparing hollow fiber molecular sieve membranes in batches | |
CN109019614B (en) | Rare earth toughened silicon aerogel precursor | |
CN103130241A (en) | Synthesis method of low-silicon nano SAPO-34 molecular sieve | |
CN106145132B (en) | A method of ordered mesoporous material Al-MCM-41 is prepared using attapulgite | |
CN106185976A (en) | A kind of multi-stage porous mordenite molecular sieve and preparation method thereof | |
CN104334517B (en) | For the solvent-replacement solvent of aerogel manufacture and use the hydrophobization aerogel manufacture method of described solvent-replacement solvent | |
CN107778488A (en) | A kind of de- low molecule device and the method that production viscosity is 30 1000000cs methyl-silicone oils | |
CN105056769B (en) | The preparation method and device of a kind of NaA molecular sieve membrane | |
CN103318906A (en) | Preparation of AFI structure aluminophosphate molecular sieve membrane supported by porous alumina carrier | |
CN110382096A (en) | The manufacturing method of seperation film and seperation film | |
CN106675151A (en) | Preparation method of hierarchical mesoporous silica flatting agent | |
CN106186013B (en) | A kind of method that use rheological phase reaction method synthesizes flower ball-shaped meso-porous alumina | |
CN109970075B (en) | Method for synthesizing A-type molecular sieve membrane at low temperature | |
CN103318916B (en) | Preparation of LTA structure aluminophosphate molecular sieve membrane supported by porous alumina carrier | |
CN105800624A (en) | Synthesis method of all-silicon beta molecular sieve | |
CN104058426A (en) | Method for preparing SAPO-34 zeolite membrane in temperature changing mode | |
CN106276967A (en) | A kind of synthetic method of mesoporous zeolite | |
CN104760972B (en) | A kind of preparation method of same crystalline phase core shell structure beta-molecular sieve | |
CN106283187A (en) | A kind of ordered big hole-mesoporous multi-stage porous Si-Al molecular sieve ZSM-5 monocrystalline with opal structural and synthetic method thereof | |
CN102502685B (en) | Preparation method of mesoporous LTA zeolite |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
EXSB | Decision made by sipo to initiate substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
CB02 | Change of applicant information |
Address after: 124221 Liaoning city of Panjin Province in the Liaodong Bay Area Road No. 2 Applicant after: Dalian University of Technology Address before: The Liaodong Bay area large road Dalian City, Liaoning province 124221 No. 2 Applicant before: Dalian University of Technology |
|
COR | Change of bibliographic data | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |