CN110960987B - High-performance nano hybrid reverse osmosis membrane and preparation method thereof - Google Patents
High-performance nano hybrid reverse osmosis membrane and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of reverse osmosis membranes, and particularly relates to a high-performance nano hybrid reverse osmosis membrane and a preparation method thereof. The preparation method comprises the following steps: (1) uniformly mixing camphorsulfonic acid and triethylamine to be used as a catalyst, then adding m-phenylenediamine, a water phase modifier and a cross-linking agent, adding deionized water, and uniformly mixing to form a m-phenylenediamine water phase solution; (2) dissolving trimesoyl chloride in an organic solvent, adding a nano precursor, uniformly mixing, and then adjusting the pH of the solution to 4-5 to obtain a modified trimesoyl chloride oil phase solution; (3) and soaking the porous support layer in the m-phenylenediamine aqueous phase solution for 0.5-1min, then soaking in the modified trimesoyl chloride oil phase solution for reaction for 0.5-1min, and drying to obtain the high-performance nano hybrid reverse osmosis membrane. According to the invention, the nano material is introduced in situ, so that nano particles in a desalting layer on the surface of the nano hybrid reverse osmosis membrane are uniformly dispersed, and the water flux and the desalting rate of the nano hybrid reverse osmosis membrane are improved.
Description
Technical Field
The invention belongs to the technical field of reverse osmosis membranes, and particularly relates to a high-performance-resistant nano hybrid reverse osmosis membrane and a preparation method thereof.
Background
At present, with the rise of the industries such as printing and dyeing, chemical industry, electronics, medicine and the like all over the world, water resource pollution is aggravated year by year, the quantity of polluted water bodies is increased day by day, and in addition, the salt content of underground water is too high, the water quality is bitter and astringent, the water cannot be directly drunk in a large-scale arid area of China, and the shortage of fresh water resources becomes the current global environmental problem. The means of water purification, seawater and brackish water desalination and the like are one of effective means for solving the problem of the lack of drinking water resources at present. The membrane method water treatment technology has the advantages of good separation effect, low energy consumption, small occupied area, stable operation and the like, is widely applied to various fields of municipal reclaimed water reuse, printing and dyeing, power plant wastewater treatment, brackish water desalination, island seawater desalination and the like at present, and obtains excellent water production effect.
The reverse osmosis membrane produced industrially at present is composed of a non-woven fabric layer, a porous polysulfone layer, a desalting layer and other multilayer structures. The non-woven fabric layer has enough structural strength, the membrane can be stably operated under high pressure, the porous polysulfone layer has rich pore channels, a water flow channel can be provided, a polymerization place is provided for the desalting layer, the desalting layer is an ultrathin polyamide layer formed by polymerizing polyamine and polyacyl chloride components on the surface of the porous polysulfone layer, and the function layer of the reverse osmosis membrane has a separation effect. In current research, in order to further improve the water flux of a reverse osmosis membrane and reduce the energy consumption of water production, a hydrophilic nano material is generally introduced into a desalination layer, so as to improve the porosity and the hydrophilicity of the desalination layer. But the following problems generally arise: 1. the surface of the nano material has high hydrophilic functional groups, and the nano material can be agglomerated in both organic oil phase solution and aqueous phase solution, so that a desalting layer is easy to break, and a conveying pump is easy to block in industrial production. 2. The introduced nano material has poor stability in a desalting layer, is easy to fall off in a long-time scouring process, damages the desalting layer and reduces the desalting rate of the composite membrane.
The present invention has been made in view of the above problems.
Disclosure of Invention
In order to overcome the defects of nano material agglomeration and easy falling-off in the later period in the process of introducing the nano material into the reverse osmosis membrane in the prior art, the invention provides the high-performance nano hybrid reverse osmosis membrane and the preparation method thereof, which avoid the agglomeration and precipitation phenomenon caused by directly adding the nano material into a water phase solution or an oil phase solution, improve the industrial preparation efficiency of the reverse osmosis membrane and have higher water flux and desalination rate.
The invention provides a preparation method of a high-performance nano hybrid reverse osmosis membrane, which comprises the following steps:
(1) uniformly mixing camphorsulfonic acid and triethylamine to be used as a catalyst, then adding m-phenylenediamine, a water phase modifier and a cross-linking agent, adding deionized water, and uniformly mixing to form a m-phenylenediamine water phase solution;
(2) dissolving trimesoyl chloride in an organic solvent, adding a nano precursor, uniformly mixing, and then adjusting the pH of the solution to 4-5 to obtain a modified trimesoyl chloride oil phase solution;
(3) and (3) soaking the porous support layer in the m-phenylenediamine aqueous phase solution obtained in the step (1) for 0.5-1min, then soaking in the modified trimesoyl chloride oil phase solution obtained in the step (2) for reaction for 0.5-1min, and drying to obtain the high-performance nano hybrid reverse osmosis membrane.
Preferably, the mass ratio of the camphorsulfonic acid to the triethylamine in the catalyst in the step (1) is 2-3: 1.
Preferably, the aqueous phase modifier in step (1) is one or more of dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, dimethyl p-phenylenediamine, isopropanol, N-butanol, N-hexanol, ethylene glycol methyl ether, ethylene glycol butyl ether, ethylene glycol ethyl ether and diethylene glycol butyl ether.
Preferably, the cross-linking agent in step (1) is one or more of chitosan, dopamine and polyvinyl alcohol.
Preferably, in the step (1), the mass concentration of the catalyst in the m-phenylenediamine aqueous phase solution is 7.5-10%, the mass concentration of the aqueous phase modifier is 1-2%, the mass concentration of the cross-linking agent is 1-2%, and the mass concentration of the m-phenylenediamine is 1-3%.
Preferably, the nano precursor in the step (2) is one or more of ethyl orthosilicate, titanium isopropoxide and tetrabutyl titanate; the organic solvent is one or more of n-hexane, cyclohexane and petroleum hydrocarbon.
Preferably, the glacial acetic acid is added in the step (2) in an amount such that the pH of the modified trimesoyl chloride oil-phase solution is 4-5.
Preferably, the mass concentration of the trimesoyl chloride in the modified trimesoyl chloride oil phase solution is 0.08-0.2%, and the mass concentration of the nano precursor is 0.01-0.09%.
Preferably, the drying temperature in the step (3) is 60-100 ℃, and the drying time is 5-10 min.
The invention also provides a high-performance nano hybrid reverse osmosis membrane prepared by the method, which comprises a porous supporting layer and a polyamide desalting layer, wherein the polyamide desalting layer comprises a silicon-containing or/and titanium-containing nano material.
The invention has the beneficial effects that:
(1) the invention aims to overcome the defects of nano material agglomeration and easy shedding in the process of introducing nano materials in the prior art, and particularly provides an innovative method for introducing nano materials in situ, which comprises the following steps: the nano precursor which is easily dissolved in an organic solvent is introduced into the trimesoyl chloride oil phase solution, so that the nano precursor is uniformly dispersed in the trimesoyl chloride oil phase solution, can be synchronously hydrolyzed when contacting the m-phenylenediamine water phase solution, and forms nano particles in a desalting layer, thereby avoiding the agglomeration caused by directly introducing the nano particles.
(2) The common ester and isopropanol nanometer precursor is easy to absorb moisture and hydrolyze in the air to form hydroxide flocculate, and the hydrolysis is serious especially under neutral or alkaline conditions. According to the invention, glacial acetic acid is synchronously introduced into the trimesoyl chloride oil phase solution to adjust the pH value of the solution to be weakly acidic (pH is 4-5), so that the hydrolysis of the nano precursor in the air can be effectively reduced, the storage period of the modified trimesoyl chloride oil phase solution is prolonged, and the industrialization efficiency is improved.
(3) According to the invention, a water phase modifier and a cross-linking agent are introduced into m-phenylenediamine water phase liquid, and the addition of the water phase modifier can improve the hydrolysis rate of a nano precursor in the polymerization process, so that the generated nano material is uniformly dispersed in a desalting layer; the cross-linking agent is a high-molecular-weight polymer, can form a film-shaped structure in the polymerization process, has hydrophilic functional groups on the surface, and can adsorb the nano material generated by hydrolysis on the surface, so that the nano material is firmly connected in a desalting layer, and the falling of the nano material in the using process is reduced, thereby increasing the service cycle of the reverse osmosis membrane.
(4) The camphorsulfonic acid is used as an organic weak acid, so that the surface tension of an aqueous phase solution can be reduced in the dip-coating process of the aqueous phase solution, the adsorption and diffusion of m-phenylenediamine on the surface of the porous supporting layer are accelerated, the amine concentration on the surface of the porous supporting layer is promoted to be more uniform, and a polyamide desalting layer formed by polymerization is more uniform; meanwhile, triethylamine is used as an organic weak base and forms a catalyst together with camphorsulfonic acid, and can quickly form an alkaline buffer system with the camphorsulfonic acid to counteract hydrochloric acid generated in the polymerization process, so that the reaction is carried out in the forward direction. Compared with potassium hydroxide inorganic strong base, the composite material is more stable, is less influenced by the environment, has more stable pH value, is difficult to control the alkalinity of the inorganic strong base, and is easy to corrode the membrane surface to cause membrane surface damage.
Drawings
FIG. 1 is an SEM image of a high performance nano-hybrid reverse osmosis membrane prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and specific embodiments, but the invention is not limited thereto, and any modification or replacement within the basic spirit of the embodiments of the present invention will still fall within the scope of the present invention.
Preparation of high-performance nano hybrid reverse osmosis membrane
Example 1
The preparation method of the high-performance nano hybrid reverse osmosis membrane comprises the following specific implementation steps:
(1) uniformly mixing 40g of camphorsulfonic acid and 25g of triethylamine to serve as a catalyst, sequentially adding 20g of m-phenylenediamine, 15g of dimethylformamide (a water phase modifier) and 15g of chitosan (a cross-linking agent), diluting to 1000g, and uniformly mixing to obtain a m-phenylenediamine water phase solution;
(2) dissolving 2g of trimesoyl chloride in n-hexane (organic solvent), then adding 0.1g of tetraethoxysilane (nano precursor) to mix uniformly, and simultaneously adding a small amount of glacial acetic acid to adjust the pH value of the solution to 5 to obtain a modified trimesoyl chloride oil phase solution;
(3) and (2) firstly, placing the porous polysulfone support layer in the m-phenylenediamine aqueous phase solution obtained in the step (1) to be soaked for 0.5min, then soaking in the modified trimesoyl chloride oil phase solution obtained in the step (2) for 0.5min, and drying at 80 ℃ for 5-10 min to obtain the high-performance nano hybrid reverse osmosis membrane.
Fig. 1 is an SEM image of the high performance nano hybrid reverse osmosis membrane prepared in example 1, and it can be seen that the surface of the reverse osmosis membrane has a distinct convex structure, and the surface of the convex nano structure is coated with a film structure. The nano precursor is added into the trimesoyl chloride oil phase solution, and in the process of contacting with the m-phenylenediamine water phase solution to carry out interfacial polymerization reaction, the nano precursor is hydrolyzed to obtain silicon-containing nano particles, and the silicon-containing nano particles are compounded into the polyamide desalting layer, so that the convex structure is more favorable for water molecule diffusion in the water treatment process, and the water yield of reverse osmosis is greatly increased. Meanwhile, the crosslinking agent is added, so that the nano particles are tightly attached to the surface of the membrane, the nano particles can be prevented from being washed away and lost in the long-time use process, the service cycle of the reverse osmosis membrane is prolonged, and the energy consumption of water production is reduced.
Examples 2 to 9
The preparation method of the high-performance nano hybrid reverse osmosis membrane in the embodiments 2 to 9 is basically the same as that in the embodiment 1, and the difference is only that: the types and the addition amounts of the aqueous phase modifier and the cross-linking agent added in the step (1) and the nano precursor added in the step (2) are different, and are specifically shown in table 1:
TABLE 1
Comparative example 1
The preparation method of the high-performance nano hybrid reverse osmosis membrane in the comparative example is different from that of the example 1 in that: the ethyl orthosilicate (nano precursor) in the step (2) of the embodiment 1 is omitted, and the specific implementation method is as follows:
(1) same as example 1, step (1);
(2) dissolving 2g of trimesoyl chloride in n-hexane (organic solvent), uniformly mixing, and simultaneously adding a small amount of glacial acetic acid to adjust the pH value of the solution to 5 to obtain a modified trimesoyl chloride oil phase solution;
(3) same as example 1, step (3).
Comparative example 2
The preparation method of the high-performance nano hybrid reverse osmosis membrane in the comparative example is different from that of the example 1 in that: dimethyl formamide (aqueous phase modifier) in step (1) of example 1 is omitted, and the specific implementation method is as follows:
(1) uniformly mixing 40g of camphorsulfonic acid and 25g of triethylamine to serve as a catalyst, sequentially adding 20g of m-phenylenediamine and 15g of chitosan (a cross-linking agent), diluting to 1000g, and uniformly mixing to obtain a m-phenylenediamine aqueous phase solution;
steps (2) to (3) were the same as in example 1.
Comparative example 3
The preparation method of the high-performance nano hybrid reverse osmosis membrane in the comparative example is different from that of the example 1 in that: the chitosan (cross-linking agent) in step (1) of example 1 is omitted, and the specific implementation method is as follows:
(1) uniformly mixing 40g of camphorsulfonic acid and 25g of triethylamine to serve as a catalyst, sequentially adding 20g of m-phenylenediamine and 15g of dimethylformamide (aqueous phase modifier), diluting to 1000g, and uniformly mixing to obtain a m-phenylenediamine aqueous phase solution;
steps (2) to (3) were the same as in example 1.
Second, performance test of reverse osmosis membrane
1. Flux desalination test
According to the test method, referring to a GB/T32373-2015 reverse osmosis membrane detection method, a NaCl aqueous solution with the concentration of 2000ppm is prepared in advance, the pH value is adjusted to 7.0 +/-0.5 by using dilute sulfuric acid or dilute sodium hydroxide solution, reverse osmosis membrane membranes to be tested (reverse osmosis membranes obtained in examples 1-9 and comparative examples 1-3) are cut to the corresponding size and placed into a membrane pool, the test pressure is adjusted to 225psi, the raw water flow is 1GPM, the raw water temperature is controlled to be 25 +/-0.5 ℃, water samples of produced water in a certain time are collected after stable operation is carried out for 30min, the conductivity and the weight of the produced water are tested, the water flux and the desalination rate of the test membranes are calculated according to the following formulas, and the test results are shown in Table 2.
The calculation formula of the reverse osmosis membrane desalination rate is as follows:
in the formula:
r-salt rejection rate;
kp-permeant conductivity in microsiemens per centimeter (μ S/cm);
kf-measuring the conductivity of the fluid in microsiemens per centimeter (. mu.S/cm).
The water flux calculation formula of the reverse osmosis membrane is as follows:
in the formula:
f-water flux in liters per square meter hour [ L/(m)2.h)]；
The volume of permeate collected over time V-t, in liters (L);
a-effective membrane area in square meters (m)2)；
t-the time taken to collect a volume of V permeate in hours (h).
TABLE 2
| Examples | Water flux (GFD) | Salt rejection (%) |
| Example 1 | 38.12 | 99.72 |
| Example 2 | 39.23 | 99.71 |
| Example 3 | 40.15 | 99.66 |
| Example 4 | 43.58 | 99.71 |
| Example 5 | 43.77 | 99.51 |
| Example 6 | 36.11 | 99.79 |
| Example 7 | 43.31 | 99.37 |
| Example 8 | 39.13 | 99.74 |
| Example 9 | 37.79 | 99.83 |
| Comparative example 1 | 34.19 | 99.78 |
| Comparative example 2 | 36.28 | 99.69 |
| Comparative example 3 | 38.35 | 99.77 |
As can be seen from Table 2, the nano precursor is introduced into the trimesoyl chloride oil phase solution, the water phase modifier and the cross-linking agent are introduced into the m-phenylenediamine water phase solution, the nano precursor is hydrolyzed in the desalting layer, and the addition amount is optimized, so that the prepared high-performance nano hybrid reverse osmosis membrane can obtain the water flux of 42.32GFD and the desalting rate of 99.69% under the condition of 225psi, and the water yield of the reverse osmosis membrane is greatly improved.
2. Reverse osmosis membrane surface water performance test
Taking the reverse osmosis membranes prepared in the examples 1 to 9 and the comparative examples 1 to 3 as test membranes, taking surface river water as a test solution (total organic carbon, TOC is 3.5mg/L), continuously running for 72 hours under the pressure of 225psi, testing the anti-pollution performance of the membranes, after the running is finished, washing the membranes with deionized water, then continuously taking a NaCl aqueous solution with the conductivity of 4000 mu S as the test solution, collecting water under the conditions that the test pressure is 225psi, the test solution temperature is 25 ℃ and the test solution pH is 7.0 +/-0.5, and calculating the water yield and the desalination rate of the test membranes, wherein the results are shown in table 3:
TABLE 3
| Examples | Water flux (GFD) | Salt rejection (%) |
| Example 1 | 36.11 | 99.68 |
| Example 2 | 37.25 | 99.69 |
| Example 3 | 38.03 | 99.61 |
| Example 4 | 42.32 | 99.69 |
| Example 5 | 42.17 | 99.46 |
| Example 6 | 33.01 | 99.57 |
| Example 7 | 41.31 | 99.41 |
| Example 8 | 37.53 | 99.61 |
| Example 9 | 37.79 | 99.68 |
| Comparative example 1 | 32.01 | 99.58 |
| Comparative example 2 | 34.10 | 99.65 |
| Comparative example 3 | 45.51 | 98.51 |
As can be seen from Table 3, after a long-time surface river water test, the water flux of the reverse osmosis membrane without the cross-linking agent in the comparative example 3 is obviously increased, but the salt rejection rate is greatly reduced, so that the addition of the cross-linking agent in the aqueous phase solution can effectively improve the adhesion between the nano material and the polyamide desalting layer, the nano material is firmly connected in the desalting layer, the falling of the nano material in a long-time scouring process is reduced, and the service cycle of the reverse osmosis membrane is prolonged.
Compared with the traditional method for directly introducing the nano material into the water phase or oil phase solution, the method can effectively avoid the agglomeration of the nano material in the feed liquid and improve the industrial film coating efficiency, thereby having great application prospect in the fields of industrial reverse osmosis membranes and nanofiltration membranes.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A preparation method of a high-performance nano hybrid reverse osmosis membrane is characterized by comprising the following steps:
(1) uniformly mixing camphorsulfonic acid and triethylamine to be used as a catalyst, then adding m-phenylenediamine, a water phase modifier and a cross-linking agent, adding deionized water, and uniformly mixing to form a m-phenylenediamine water phase solution;
(2) dissolving trimesoyl chloride in an organic solvent, adding a nano precursor, uniformly mixing, and then adjusting the pH of the solution to 4-5 to obtain a modified trimesoyl chloride oil phase solution;
(3) soaking the porous support layer in the m-phenylenediamine aqueous phase solution obtained in the step (1) for 0.5-1min, then soaking in the modified trimesoyl chloride oil phase solution obtained in the step (2) for reaction for 0.5-1min, and drying to obtain the high-performance nano hybrid reverse osmosis membrane;
the water phase modifier in the step (1) is one or more of dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, dimethyl p-phenylenediamine, isopropanol, N-butanol, N-hexanol, ethylene glycol methyl ether, ethylene glycol butyl ether, ethylene glycol ethyl ether and diethylene glycol butyl ether;
the cross-linking agent in the step (1) is one or more of chitosan, dopamine and polyvinyl alcohol;
the nano precursor in the step (2) is titanium isopropoxide and/or tetrabutyl titanate; the organic solvent is one or more of n-hexane, cyclohexane and petroleum hydrocarbon.
2. The preparation method of the high-performance nano hybrid reverse osmosis membrane according to claim 1, wherein the mass ratio of the camphorsulfonic acid to the triethylamine in the catalyst in the step (1) is 2-3: 1.
3. The preparation method of the high-performance nano hybrid reverse osmosis membrane according to any one of claims 1-2, wherein the mass concentration of the catalyst in the m-phenylenediamine aqueous phase solution is 7.5% -10%, the mass concentration of the aqueous phase modifier is 1% -2%, the mass concentration of the cross-linking agent is 1% -2%, and the mass concentration of the m-phenylenediamine is 1% -3%.
4. The preparation method of the high-performance nano hybrid reverse osmosis membrane according to claim 1, wherein the mass concentration of trimesoyl chloride in the modified trimesoyl chloride oil phase solution is 0.08% -0.2%, and the mass concentration of the nano precursor is 0.01% -0.09%.
5. The preparation method of the high-performance nano hybrid reverse osmosis membrane according to claim 1, wherein the drying temperature in the step (3) is 60-100 ℃, and the drying time is 5-10 min.
6. A high performance nanohybrid reverse osmosis membrane prepared according to the method of any one of claims 1-5, comprising a porous support layer and a polyamide desalination layer comprising silicon-containing or/and titanium-containing nanomaterials.
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| CN107158978A (en) * | 2017-05-10 | 2017-09-15 | 浙江工业大学 | The preparation method of polyamine self-assembly NF membrane |
| CN107413207A (en) * | 2017-06-28 | 2017-12-01 | 宁波日新恒力科技有限公司 | A kind of preparation method of polyamide reverse osmose membrane |
| CN109985531A (en) * | 2019-04-08 | 2019-07-09 | 天津大学 | A method of reverse osmosis membrane is prepared using silester as oily phase cosolvent |
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