CN105080358B - A kind of reverse osmosis composite membrane and preparation method containing organically-modified attapulgite - Google Patents
A kind of reverse osmosis composite membrane and preparation method containing organically-modified attapulgite Download PDFInfo
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Abstract
The invention discloses a kind of reverse osmosis composite membrane containing organically-modified attapulgite and preparation method.It is to be prepared by comprising the following steps method：(1) porous support layer is contacted with the aqueous phase solution containing two or more reactive amino compounds；(2) porous support layer after aqueous phase infiltrates removes unnecessary aqueous phase solution；(3) organic phase solution of the porous support layer after step (2) processing with the chloride compounds containing two or more acid chloride groups and by purification, organically-modified attapulgite, which is contacted, is made composite membrane；(4) reverse osmosis composite membrane is made after dry, heat treatment, washing.Process is simple, reaction condition is gentle, simultaneously, the peculiar property in the nanometer porous road of attapulgite can lift the separating property of composite membrane again, so that the salt-stopping rate of reverse osmosis composite membrane keeps suitable, and flux is improved significantly, the application operating cost of reverse osmosis composite membrane greatly reduces.
Description
Technical field
The present invention relates to technical field of membrane, furtherly, it is related to a kind of counter-infiltration containing organically-modified attapulgite
Composite membrane and preparation method.
Background technology
In recent years, as global water resources shortage increasingly serious, water pollution is increasingly aggravated, reverse osmosis technology is in desalinization
Wider application and attention have been obtained with Water circulation field.The core technology of counter-infiltration is the manufacturing technology of reverse osmosis membrane, no
Symmetrical reverse osmosis membrane and reverse osmosis composite membrane are the two class high-performance reverse osmosis membranes for having been commercialized application at present.Wherein, counter-infiltration
Composite membrane can make every layer to reach optimum performance by optimization, and ultrathin functional layer can be optimized to preferable selective penetrated property, branch
Support layer can reach optimal intensity and pressure tightness.In addition, reverse osmosis composite membrane can make to be difficult to the material to form asymmetric membrane
Material forms ultrathin membrane, such as because solvent is limited, or crosslinking polymer, can be formed by in-situ polymerization or interfacial polymerization
Composite membrane.Therefore, reverse osmosis composite membrane turns into the main product in current reverse osmosis membrane field.
The performance of reverse osmosis composite membrane mainly includes water flux and rejection.In order to which the equipment for reducing reverse osmosis composite membrane is thrown
Money and operation energy consumption, improve its efficiency, and film industry is directed to improving anti-by various methods while rejection is ensured always
The water flux of permeable membrane.Answered as patent US4643829 further improves counter-infiltration by preparing or synthesizing new function monomer
Close the performance of film.Patent US4872984, US6245234 are mutually turned with CN101381125 by being added in the aqueous solution of polyamine
The water flux for improving composite membrane can also be reached by moving agent.Patent US6337018 and CN1195576 passes through in multifunctional acyl halide
Additive is added in organic phase solution can improve the water flux of composite membrane to some extent.Patent US4812270, US4983291
The water flux of film can also be improved by different physical chemistry post-processing technologies with US7598296.At present, by basement membrane
Auxiliary agent is added when preparing fine and close ultrathin functional layer or appropriate processing is carried out after composite membrane manufacture, water penetration and rejection are not
Preferable level can be reached.
In recent years, with the development of nanometer technology, the research of porous nano particle is added in composite membrane turns into raising instead
The focus of osmosis composite membrane flux.Received as Chinese patent CN101791522A adds carbon in the monomer solution of synthesizing polyamides film
Mitron, the hybridized composite reverse osmosis membrane of carbon nanotubes is prepared by infusion process, and the flux for the reverse osmosis membrane prepared is significantly
Increase, but rejection relative reduction.Chinese patent CN101940883A mixes silane coupler, molecular sieve of Nano zeolite and toluene
Close, prepare surface by modified molecular sieve of Nano zeolite；Then, it will be distributed to by modified molecular sieve of Nano zeolite
In polynary amine aqueous solution and/or polynary solution of acid chloride, solution A and and/B are obtained；Finally, it is solution A and B progress interfacial polymerizations is anti-
The reverse osmosis composite membrane containing modified nano-zeolite molecular sieve should be made.United States Patent (USP) US8177978B2 by contain m-phenylene diamine (MPD)
Aqueous phase solution and pyromellitic trimethylsilyl chloride organic phase solution interfacial polymerization, wherein at least one aqueous phase solution and organic phase solution
Comprising nano-particle, Thief zone RO films are prepared.The flux of polyamide composite film has lifting made from report described above, but
Combination property is undesirable.Therefore, from suitable porous nanometer material, its multi-pore channel structure is combined with reverse osmosis composite membrane
The reverse osmosis composite membrane for preparing excellent combination property just seems particularly significant.
In addition to above-mentioned porous nano particle, attapulgite is also the nano-particle of loose structure, and its main component is slope thread
Stone (attapulgite), is a kind of clay mineral of magnesium silicate containing Shuifu County for having chain layer structure.Its skeleton structure is in 3 D stereo
Shape, is formed by octahedra be connected with each other by sharing summit of silicon-oxy tetrahedron and magnalium, with it is numerous parallel to rod it is brilliant (needle-like,
Micro- bar-shaped or fibrous monocrystal) direction arrangement tubular nanometer level duct, duct run through total, from section Shang Kan ducts
It is cellular in (about 0.38nm × 0.63nm) equal in magnitude, thus the effect of tool molecular sieve.
Attapulgite is big because of specific surface area, and hydroxyl of the surface containing polarized, it is difficult to scattered independent rhabdolith shape
State is present, but forms the crystal aggregates of certain forms, and this just constitutes the microstructure of attapulgite powder.Its micro- knot
Structure has brilliant rod, brilliant beam, three different levels of aggregation.Rod crystalline substance is the basic structural unit of attapulgite, a diameter of 0.01 μ
The m orders of magnitude, length is up to 0.1~1 μm；Brilliant beam is formed by the brilliant close parallel aggregation of rod；Aggregation is by brilliant beam (including rod is brilliant)
Between mutually aggregation pile up and formed, particle diameter is usually 0.01~0.1mm orders of magnitude.In actual applications, the rod of attapulgite is brilliant
If being agglomerated into brilliant beam or aggregation, the nanostructured advantage of itself cannot be played.Therefore, in actual applications, especially use
It must be carried out when organic polymer organically-modified.
The organically-modified method of attapulgite has a variety of, wherein quaternary ammonium salt ion-exchange be it is a kind of by through frequently with side
Method.Quaternary ammonium salt cationic is mainly had an effect by ion exchange absorption with attapulgite, and generation attapulgite-organic surface is lived
Property agent complex, macromolecule organic group instead of original inorganic cation；Attapulgite particle surface is also because of various work
The presence at property center and adsorb a part of organic matter；Partially crystallizable water and absorption water simultaneously inside and outside lattice is replaced by organic matter,
So as to improve the hydrophobicity of attapulgite, its affinity with organic matter is also enhanced.Attapulgite with very big because comparing table
Area, it is widely paid attention to as the application study of adsorbent, but not yet finds to be applied to the preparation neck of film at present
Domain.
The content of the invention
To solve produced problem in the prior art, the invention provides a kind of reverse osmosis containing organically-modified attapulgite
Saturating composite membrane and preparation method thereof.The present invention in interfacial polymerization process by introducing purified and organically-modified concave convex rod
Soil, so as to improve the separating property of reverse osmosis composite membrane.
An object of the present invention is to provide a kind of reverse osmosis composite membrane containing organically-modified attapulgite.
In described reverse osmosis composite membrane containing draw ratio be less than or equal to 20 attapulgite, attapulgite have needle-like,
Bar-shaped or filamentary structure, and with hollow nanoscale duct, the brilliant a diameter of 10nm~20nm of attapulgite rod, attapulgite
By organically-modified, preferably it can be dispersed in organic phase solution.
The present invention is introduced in reverse osmosis composite membrane through organically-modified attapulgite nano-particle, by through organically-modified
Attapulgite is directly added into organic phase solution, only ultrasonically treated can need to preferably be divided in organic phase solution through the short period
Dissipate.Attapulgite is present in the top layer of reverse osmosis composite membrane functional layer, it is easier to given play to its nano effect, prepared reverse osmosis
Saturating composite membrane salt-stopping rate is with being not introduced into the suitable of attapulgite, and water flux is improved significantly.
The second object of the present invention is to provide a kind of preparation side of the reverse osmosis composite membrane containing organically-modified attapulgite
Method.
Comprise the following steps：
(1) porous support layer is contacted with the aqueous phase solution containing two or more reactive amino compounds；
(2) aqueous phase solution of the porous support layer excess surface after aqueous phase infiltrates is removed；
(3) porous support layer after step (2) processing and the acyl chlorides chemical combination containing two or more acid chloride groups
Composite membrane is made in thing and process purification, the organic phase solution contact of organically-modified attapulgite；
(4) reverse osmosis composite membrane is made after dry, heat treatment；
Described porous support layer is polysulfone porous supporting layer, polyether sulfone porous support layer, sulfonated polyether sulfone open support
One kind in layer, polypropylene porous support layer；
Two or more reactive amino compounds in the aqueous phase solution are aromatic series, aliphatic, alicyclic
Polyfunctional amine, the one or more in polyhydric alcohol amine；
Preferably：
The aromatic series polyfunctional amine is m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine, 1,3,5- triaminobenzenes, 1,2,4-
Triaminobenzene, 3,5- diaminobenzoic acids, 2,4 di amino toluene, 2,4- diamino anisoles, amidol, xylylene diamine
At least one of；The aliphatic polyfunctional amine be ethylenediamine, propane diamine, butanediamine, pentanediamine, three (2- aminoethyls) amine,
At least one of diethylenetriamine；The alicyclic polyfunctional amine be 1,2- diaminocyclohexanes, 1,4- diaminocyclohexanes,
At least one of piperazine, 1,3- bipiperidine bases propane, 4- aminomethylpiperazines；The polyhydric alcohol amine is monoethanolamine, diethanol
At least one of amine, hexylene glycol amine, diglycolamine.
The chloride compounds of two or more acid chloride groups in the organic phase solution are aromatic series, aliphatic, fat
The one or more of the multifunctional chloride compounds of ring race；
Preferably：
The multifunctional chloride compounds of aromatic series are paraphthaloyl chloride, m-phthaloyl chloride, o-phthaloyl chloride, connection
At least one of phthalyl chloride, benzene-disulfo-chloride, pyromellitic trimethylsilyl chloride；The multifunctional chloride compounds of aliphatic are fourth
Three acyl chlorides, succinyl chloride, penta 3 acyl chlorides, glutaryl chlorine.In oneself three acyl chlorides, Adipoyl Chloride, sebacoyl chloride, the acyl chlorides of the last of the ten Heavenly stems three at least
It is a kind of；The alicyclic multifunctional chloride compounds are the acyl chlorides of cyclopropane three, cyclobutane diacid chloride, the acyl chlorides of cyclobutane four, ring penta
Alkane diacid chloride, the acyl chlorides of pentamethylene three, the acyl chlorides of pentamethylene four, hexamethylene diacid chloride, the acyl chlorides of hexamethylene three, the acyl chlorides of hexamethylene four, four
At least one of hydrogen furans diacid chloride, the acyl chlorides of tetrahydrofuran four.
The organic solvent of the organic phase solution is n-hexane, hexamethylene, trifluorotrichloroethane, normal heptane, normal octane, first
One or more of mixtures in benzene, ethylbenzene, ISOPAR solvent naphthas；
The concentration of two or more reactive amino compounds in the aqueous phase solution is 1~60g/L；
In described aqueous phase solution can also the surfactant containing 0~5g/L and 0~10g/L acid absorbent；Table
Face activating agent and acid absorbent can be used in general surfactant and acid absorbent in the art, the present invention, preferably：
Described surfactant is lauryl sodium sulfate, neopelex, trimethyl bromination
At least one of ammonium, bay disulfonate acid, Qula logical -100,1-METHYLPYRROLIDONE；Acid absorbent is triethylamine, carbonic acid
At least one of sodium, sodium acid carbonate, dibastic sodium phosphate, sodium phosphate, sodium hydroxide, potassium hydroxide.
The concentration of the chloride compounds of two or more acid chloride groups in the organic phase solution is 0.5~5g/L；
The content of attapulgite is 0.01~0.4g/L in the organic phase solution.
Time of contact in above method step is preferably 5~300 seconds, and heat treatment temperature is preferably 30~120 DEG C, heat
Processing time is preferably 1~10 minute.
Attapulgite passes through the organically-modified dispersiveness for improving it in organic solution.Its it is organically-modified including purification and
Organically-modified two steps.Purification is with organically-modified using general purification and organically-modified method in the prior art.
In the present invention, the purification of attapulgite is preferably according to the following steps：
(1) a certain amount of attapulgite is put into Muffle furnace, be calcined 30 minutes at 400 DEG C；
(2) above-mentioned roasting attapulgite is put into ball mill, at 500 rpm ball milling 3h；
(3) a certain amount of attapulgite is weighed, adding makes attapulgite mass concentration be 10% after distilled water, then add one
Quantitative sodium hexametaphosphate dispersant, mechanical agitation 30 minutes；
(4) ultrasonication 30 minutes；
(5) and then by centrifuge 12000r/min centrifugal treating is carried out；
(6) upper liquid is discarded, is dried in 80 DEG C of baking ovens；
(7) attapulgite purified by more than, which is placed in drier, stores standby with modification.
In the present invention, attapulgite it is organically-modified preferably quaternary ammonium salt-modified, but be not limited to this, can also be with other
Inorganic filler equally carries out organically-modified processing using the coupling agent modified method commonly used in plastic processing.
The organically-modified method of attapulgite is preferably carried out according to the following steps：
(1) a certain amount of purified attapulgite is weighed, adding distilled water makes its mass concentration reach 10%, adds one
The cetyl trimethylammonium bromide of quantitative (quality is the 20% of attapulgite quality)；
(2) at 70 DEG C, magnetic agitation is reacted 2 hours；
(3) above-mentioned reaction solution is handled after certain time by centrifuging (12000r/min), discards supernatant liquor；
(4) modified attapulgite is put into 80 DEG C of oven for drying, standby with mortar grinder after cooling.
The present invention can be achieved through the following technical solutions using polysulfone supporting layer：
(1) first, by porous polysulfone supporting layer and the aqueous phase containing two or more reactive amino compounds
Solution is contacted, and time of contact is 5~300 seconds；
(2) the polysulfone porous supporting layer with rubber rollers roll-in after aqueous phase infiltrates, removes the aqueous phase solution of excess surface；
(3) and then by the polysulfone porous supporting layer after aqueous phase solution infiltrates with containing two or more acid chloride groups
Chloride compounds and by organically-modified attapulgite organic phase solution contact 5~300 seconds, it is anti-by interfacial polymerization
Should, in one layer of functional layer containing attapulgite of porous support layer Surface Creation, composite membrane is made；
(4) after finally above-mentioned film is spontaneously dried in atmosphere, it is put into 30~120 DEG C of baking ovens and is heat-treated 1~10 minute,
Reverse osmosis composite membrane is made after washing.Containing polymer and by organically-modified in the functional layer of reverse osmosis composite membrane
Attapulgite.
Compared with prior art, the present invention is taken the contact of porous support layer liquid compatible with water, then again with containing organic
The organic phase solution contact of modified attapulgite, is answered organically-modified attapulgite loaded to counter-infiltration by interfacial polymerization
Close in film functional layer.The experimentation for preparing the reverse osmosis composite membrane containing organically-modified attapulgite is simple, reaction condition
Gently, meanwhile, the peculiar property in the nanometer porous road of attapulgite can lift the separating property of composite membrane again so that reverse osmosis
Saturating composite membrane salt-stopping rate keeps suitable, and flux is improved significantly, and the application of reverse osmosis composite membrane greatly reduces
Operating cost.
Embodiment
With reference to embodiment, the present invention is further illustrated.
Reverse osmosis membrane separation performance evaluation：
Salt rejection rate R is defined as：Under the conditions of certain operating pressure, feeding liquid salinity (Cf) with penetrating fluid in salinity
(Cp) difference, then divided by feeding liquid salinity.
Water flux is defined as：Under certain operating conditions, the volume of the water of per membrane area is passed through in the unit interval, its
Unit is L/ (m2·h)。
The operating condition that reverse osmosis membrane separation performance is used in the present invention for：Feed liquor is 2000ppm sodium-chloride water solution,
Operating pressure is 224psi, and operation temperature is 25 DEG C, and pH value of water solution is 6.8.
In embodiment it is raw materials used be it is commercially available, the draw ratio of attapulgite used is less than or equal to 20, diameter in embodiment
Between 10~20nm.
Attapulgite it is organically-modified including purification and organically-modified two steps：
(1) purification step of attapulgite：A certain amount of attapulgite is put into Muffle furnace, 30 are calcined at 400 DEG C
Minute；Above-mentioned roasting attapulgite is put into ball mill, at 500 rpm ball milling 3h；It is 10% to be made into mass concentration
The attapulgite aqueous solution, it is 30 points of mechanical agitation after 10% sodium hexametaphosphate dispersant of attapulgite quality to add quality
Clock, ultrasonication 30 minutes, centrifugal treating is carried out by centrifuge 12000r/min；Upper liquid is discarded, in 80 DEG C of baking ovens
Dry.
(2) the step of Organic Surface Modification of Attapulgite：It is made into mass concentration water-soluble for 10% attapulgite by purification
Liquid, adds 20% cetyl trimethylammonium bromide (CTAB) that quality is attapulgite quality；At 70 DEG C, magnetic agitation
Reaction 2 hours；Above-mentioned reaction solution is handled after certain time by centrifuging (12000r/min), discards supernatant liquor；Modified
Attapulgite is put into 80 DEG C of oven for drying, standby with mortar grinder after cooling.
Embodiment 1
Polysulfone porous supporting layer contacts about 60 seconds, wherein m-phenylene diamine (MPD) with concentration for 20g/L m-phenylene diamine (MPD) aqueous phase solution
Triethylamine (TEA), 2g/L dodecyl sodium sulfate (SBS) of the aqueous phase solution also containing 10g/L, are removed through isophthalic with rubber rollers
Polysulfones support membrane excess surface solution after the infiltration of diamines aqueous phase solution.Then by this support membrane and equal benzene three of the concentration for 1g/L
The ISOPAR E solution of formyl chloride is contacted 60 seconds, wherein also containing the organic of 0.01g/L in pyromellitic trimethylsilyl chloride organic phase solution
Modified attapulgite；Then the aramid layer of formation is dried in atmosphere, 3min is handled in the baking oven for being placed on 70 DEG C, then
Rinsed in 25 DEG C of deionized water and the polyamide reverse osmosis composite film containing attapulgite, the reverse osmosis composite membrane prepared is made
Preserve in deionized water.The separating property of composite membrane is carried out by the method for testing of the separating property of foregoing reverse osmosis composite membrane
Test, the test result of gained is listed in table 1.
Embodiment 2
In addition to the content of attapulgite organically-modified in pyromellitic trimethylsilyl chloride organic phase solution is adjusted into 0.05g/L,
Other processing steps are same as Example 1 with test condition, the separating property test result of prepared reverse osmosis composite membrane
It is listed in table 1.
Embodiment 3
In addition to the content of attapulgite organically-modified in pyromellitic trimethylsilyl chloride organic phase solution is adjusted into 0.1g/L, its
Its processing step is same as Example 1 with test condition, and the separating property test result of prepared reverse osmosis composite membrane is arranged
In table 1.
Embodiment 4
In addition to the content of attapulgite organically-modified in pyromellitic trimethylsilyl chloride organic phase solution is adjusted into 0.2g/L, its
Its processing step is same as Example 1 with test condition, and the separating property test result of prepared reverse osmosis composite membrane is arranged
In table 1.
Embodiment 5
In addition to the content of attapulgite organically-modified in pyromellitic trimethylsilyl chloride organic phase solution is adjusted into 0.4g/L, its
Its processing step is same as Example 1 with test condition, and the separating property test result of prepared reverse osmosis composite membrane is arranged
In table 1.
Comparative example 1
In addition to the content of attapulgite organically-modified in pyromellitic trimethylsilyl chloride organic phase solution is adjusted into 0.8g/L, its
Its processing step is same as Example 1 with test condition, and the separating property test result of prepared reverse osmosis composite membrane is arranged
In table 1.
Comparative example 2
Except the attapulgite in pyromellitic trimethylsilyl chloride organic phase solution is adjusted into only purification and non-modified concave convex rod
Soil, and attapulgite concentration is that other processing steps are same as Example 1 with test condition, and prepared is anti-outside 0.1g/L
The separating property test result of osmosis composite membrane is listed in table 1.
Comparative example 3
In addition to organically-modified attapulgite is free of in pyromellitic trimethylsilyl chloride organic phase solution, other processing steps and test
Condition is same as Example 1, and the separating property test result of prepared reverse osmosis composite membrane is listed in table 1.
Embodiment 6
Polyether sulfone porous support layer contacts about 5 seconds, wherein o-phenylenediamine with concentration for 60g/L o-phenylenediamine aqueous phase solution
The aqueous phase solution also sodium carbonate containing 10g/L, 5g/L neopelex, are removed through o-phenylenediamine aqueous phase with rubber rollers
Polyether sulfone support membrane excess surface solution after solution impregnation.Then by this support membrane and m-phthaloyl chloride of the concentration for 5g/L
ISOPAR G solution contact 300 seconds, wherein also containing the organically-modified of 0.05g/L in m-phthaloyl chloride organic phase solution
Attapulgite；Then the aramid layer of formation is dried in atmosphere, 1min is handled in the baking oven for being placed on 120 DEG C, finally 25
DEG C deionized water in rinse the polyamide reverse osmosis composite film containing attapulgite be made, the reverse osmosis composite membrane for preparing is preserved
In deionized water.The separating property of composite membrane is surveyed by the method for testing of the separating property of foregoing reverse osmosis composite membrane
Examination, the test result of gained is listed in table 1.
Comparative example 4
In addition to organically-modified attapulgite is free of in m-phthaloyl chloride organic phase solution, other processing steps and test
Condition is same as Example 6, and the separating property test result of prepared reverse osmosis composite membrane is listed in table 1.
Embodiment 7
Polysulfone porous supporting layer is contacted about 300 seconds with concentration for 1g/L m-phenylene diamine (MPD) aqueous phase solution, is removed with rubber rollers
Polysulfones support membrane excess surface solution after being infiltrated through m-phenylene diamine (MPD) aqueous phase solution.Then it is 0.5g/L by this support membrane and concentration
Pyromellitic trimethylsilyl chloride hexane solution contact 5 seconds, wherein also containing 0.2g/L's in pyromellitic trimethylsilyl chloride organic phase solution
Organically-modified attapulgite；Then the aramid layer of formation is dried in atmosphere, is placed in 30 DEG C of baking oven and handles
10min, then rinses in 25 DEG C of deionized water and the polyamide reverse osmosis composite film containing attapulgite is made, what is prepared is anti-
Osmosis composite membrane is preserved in deionized water.By foregoing reverse osmosis composite membrane separating property method of testing to the property of composite membrane
It can be tested, the test result of gained is listed in table 1.
Comparative example 5
In addition to organically-modified attapulgite is free of in pyromellitic trimethylsilyl chloride organic phase solution, other processing steps and test
Condition is same as Example 7, and the test result of prepared reverse osmosis composite membrane is listed in table 1.
Table 1
When can be seen that interfacial polymerization from the test result of table 1 and preparing reverse osmosis composite membrane, added into organic phase solution
Through organically-modified attapulgite, the salt-stopping rate of reverse osmosis composite membrane is suitable, and flux is increased substantially.Because by having
The attapulgite that machine is modified can be dispersed in organic phase solution, so as to disperse in the separating. functional layer of reverse osmosis composite membrane
Also uniform, the composite membrane of preparation will not produce defect, in addition, attapulgite has unique pore passage structure.But attapulgite
Excessive concentration (comparative example 1), although water flux increases, but salt-stopping rate have dropped, so, through organically-modified concave convex rod
The concentration of soil need to be controlled in the range of 0.01-0.4g/L.
Claims (8)
1. a kind of polyamide reverse osmosis composite film containing organically-modified attapulgite, it is characterised in that：
It is less than or equal to containing draw ratio 20 attapulgite in described reverse osmosis composite membrane, attapulgite has needle-like, bar-shaped
Or filamentary structure, and with hollow nanoscale duct, the brilliant a diameter of 10nm~20nm of rod of attapulgite, attapulgite warp
Cross organically-modified.
2. contain the polyamide reverse osmosis composite film of organically-modified attapulgite as claimed in claim 1, it is characterised in that：Institute
Stating reverse osmosis composite membrane is prepared by the method comprised the following steps：
(1) porous support layer is contacted with the aqueous phase solution containing two or more reactive amino compounds；
(2) aqueous phase solution of the porous support layer excess surface after aqueous phase infiltrates is removed；
(3) porous support layer and the chloride compounds containing two or more acid chloride groups after step (2) processing and
Composite membrane is made by the organic phase solution contact of purification, organically-modified attapulgite；
(4) reverse osmosis composite membrane is made after dry, heat treatment；
Described porous support layer is polysulfone porous supporting layer, polyether sulfone porous support layer, sulfonated polyether sulfone porous support layer, poly-
One kind in propylene porous support layer；
Two or more reactive amino compounds in the aqueous phase solution are aromatic series, aliphatic, alicyclic many
One or more in functional amine, polyhydric alcohol amine；
The chloride compounds of two or more acid chloride groups in the organic phase solution are aromatic series, aliphatic, alicyclic
Multifunctional chloride compounds one or more；
The organic solvent of the organic phase solution be n-hexane, hexamethylene, trifluorotrichloroethane, normal heptane, normal octane, toluene,
One or more in ethylbenzene, ISOPAR solvent naphthas；
The concentration of two or more reactive amino compounds in the aqueous phase solution is 1~60g/L；
The concentration of the chloride compounds of two or more acid chloride groups in the organic phase solution is 0.5~5g/L；
The content of attapulgite is 0.01~0.4g/L in the organic phase solution.
3. a kind of preparation of the polyamide reverse osmosis composite film containing organically-modified attapulgite as claimed in claim 1 or 2
Method, it is characterised in that methods described includes：
(1) porous support layer is contacted with the aqueous phase solution containing two or more reactive amino compounds；
(2) porous support layer after aqueous phase infiltrates removes unnecessary aqueous phase solution；
(3) porous support layer and the chloride compounds containing two or more acid chloride groups after step (2) processing and
Composite membrane is made by the organic phase solution contact of purification, organically-modified attapulgite；
(4) reverse osmosis composite membrane is made after dry, heat treatment；
Described porous support layer is polysulfone porous supporting layer, polyether sulfone porous support layer, sulfonated polyether sulfone porous support layer, poly-
One kind in propylene porous support layer；
Two or more reactive amino compounds in the aqueous phase solution are aromatic series, aliphatic, alicyclic many
One or more in functional amine, polyhydric alcohol amine；
The chloride compounds of two or more acid chloride groups in the organic phase solution are aromatic series, aliphatic, alicyclic
Multifunctional chloride compounds one or more；
The organic solvent of the organic phase solution be n-hexane, hexamethylene, trifluorotrichloroethane, normal heptane, normal octane, toluene,
One or more of mixtures in ethylbenzene, ISOPAR solvent naphthas；
The concentration of two or more reactive amino compounds in the aqueous phase solution is 1~60g/L；
The concentration of the chloride compounds of two or more acid chloride groups in the organic phase solution is 0.5~5g/L；
The content of attapulgite is 0.01~0.4g/L in the organic phase solution.
4. preparation method as claimed in claim 3, it is characterised in that：
The time of contact is 5~300 seconds；
Described heat treatment temperature is 30~120 DEG C, and heat treatment time is 1~10 minute.
5. preparation method as claimed in claim 3, it is characterised in that:
The aromatic series polyfunctional amine is m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine, 1,3,5- triaminobenzenes, the ammonia of 1,2,4- tri-
In base benzene, 3,5- diaminobenzoic acids, 2,4 di amino toluene, 2,4- diamino anisoles, amidol, xylylene diamine
It is at least one；
The aliphatic polyfunctional amine is ethylenediamine, propane diamine, butanediamine, pentanediamine, three (2- aminoethyls) amine, diethylenetriamine
At least one of；
The alicyclic polyfunctional amine is 1,2- diaminocyclohexanes, 1,4- diaminocyclohexanes, piperazine, 1,3- bipiperidines base third
At least one of alkane, 4- aminomethylpiperazines；
The polyhydric alcohol amine is at least one of monoethanolamine, diethanol amine, hexylene glycol amine, diglycolamine.
6. preparation method as claimed in claim 3, it is characterised in that：
The multifunctional chloride compounds of aromatic series are paraphthaloyl chloride, m-phthaloyl chloride, o-phthaloyl chloride, biphenyl two
At least one of formyl chloride, benzene-disulfo-chloride, pyromellitic trimethylsilyl chloride；
The multifunctional chloride compounds of aliphatic be the acyl chlorides of fourth three, succinyl chloride, penta 3 acyl chlorides, glutaryl chlorine, oneself three acyl chlorides,
At least one of Adipoyl Chloride, sebacoyl chloride, the acyl chlorides of the last of the ten Heavenly stems three；
The alicyclic multifunctional chloride compounds are the acyl chlorides of cyclopropane three, cyclobutane diacid chloride, the acyl chlorides of cyclobutane four, pentamethylene
Diacid chloride, the acyl chlorides of pentamethylene three, the acyl chlorides of pentamethylene four, hexamethylene diacid chloride, the acyl chlorides of hexamethylene three, the acyl chlorides of hexamethylene four, tetrahydrochysene
At least one of furans diacid chloride, the acyl chlorides of tetrahydrofuran four.
7. preparation method as claimed in claim 3, it is characterised in that:
Surfactant containing 0~5g/L and 0~10g/L acid absorbent in described aqueous phase solution；
Described surfactant is lauryl sodium sulfate, neopelex, DTAB, the moon
At least one of cinnamic acid sodium sulfonate, Qula logical -100,1-METHYLPYRROLIDONE；
Acid absorbent be triethylamine, sodium carbonate, sodium acid carbonate, phosphoric acid hydrogen that, in sodium phosphate, sodium hydroxide, potassium hydroxide extremely
Few one kind.
8. preparation method as claimed in claim 3, it is characterised in that：
It is organically-modified to be quaternary ammonium salt-modified in step (3).
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| CN109012241A (en) * | 2018-09-13 | 2018-12-18 | 中煤能源研究院有限责任公司 | A kind of compound forward osmosis membrane and preparation method thereof with separation function |
| CN109908758A (en) * | 2019-04-24 | 2019-06-21 | 山东大学 | A kind of preparation method of Thief zone, anti-fouling type doped attapulgite-argentum nano composite material reverse osmosis membrane |
| CN112237842A (en) * | 2020-11-12 | 2021-01-19 | 山东建筑大学 | Reverse osmosis membrane and preparation method thereof |
| CN112516799A (en) * | 2020-12-18 | 2021-03-19 | 山东建筑大学 | Reverse osmosis membrane and preparation method thereof |
| CN113856498B (en) * | 2021-10-26 | 2023-04-18 | 宁波日新恒力科技有限公司 | Polyamide reverse osmosis membrane doped with polyamide modification layer coated molecular sieve |
| CN116272418B (en) * | 2023-05-26 | 2023-08-01 | 湖南沁森高科新材料有限公司 | Reverse osmosis composite membrane and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5501798A (en) * | 1994-04-06 | 1996-03-26 | Zenon Environmental, Inc. | Microfiltration enhanced reverse osmosis for water treatment |
| CN102089068A (en) * | 2008-04-15 | 2011-06-08 | 纳米水公司 | Hybrid nanoparticle TFC membranes |
| CN102500244A (en) * | 2011-11-30 | 2012-06-20 | 杭州水处理技术研究开发中心有限公司 | Preparation method of reverse osmosis composite membrane for sea water desalinization |
| CN103143271A (en) * | 2013-03-20 | 2013-06-12 | 中国科学院长春应用化学研究所 | Reverse osmosis complex membrane and preparation method thereof |
-
2014
- 2014-04-24 CN CN201410168500.6A patent/CN105080358B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5501798A (en) * | 1994-04-06 | 1996-03-26 | Zenon Environmental, Inc. | Microfiltration enhanced reverse osmosis for water treatment |
| CN102089068A (en) * | 2008-04-15 | 2011-06-08 | 纳米水公司 | Hybrid nanoparticle TFC membranes |
| CN102500244A (en) * | 2011-11-30 | 2012-06-20 | 杭州水处理技术研究开发中心有限公司 | Preparation method of reverse osmosis composite membrane for sea water desalinization |
| CN103143271A (en) * | 2013-03-20 | 2013-06-12 | 中国科学院长春应用化学研究所 | Reverse osmosis complex membrane and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Effect of modified attapulgite addition on the performance of a PVDF ultrafiltration membrane;Yalei Zhang et al;《Desalination》;20140402;第344卷;第71页"摘要"，第74页第3.1节"改性凹凸棒土的表征"和图1 * |
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