CN110975619A - Novel reverse osmosis membrane rinsing system and rinsing method thereof - Google Patents
Novel reverse osmosis membrane rinsing system and rinsing method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention belongs to the technical field of reverse osmosis membranes, and particularly relates to a novel reverse osmosis membrane rinsing system and a rinsing method thereof. The rinsing system sequentially comprises a first rinsing tank, a second rinsing tank and a glycerin tank; an amine washing solution is filled in the first rinsing tank; a washing oil solution is filled in the second rinsing groove; the anti-pollution additive and the glycerin are filled in the glycerin tank. The invention also provides a rinsing method of the reverse osmosis membrane. The novel reverse osmosis membrane rinsing system has excellent rinsing capacity, can keep the membrane low in amine residual quantity, has excellent water flux and salt rejection rate, has good pollution resistance, and is simple in rinsing process and low in price and easy to obtain raw materials.
Description
Technical Field
The invention belongs to the technical field of reverse osmosis membranes, and particularly relates to a novel reverse osmosis membrane rinsing system and a rinsing method thereof.
Background
Water is an indispensable resource in daily life and industrial production process of human beings, is one of the most precious resources on the earth, and is also a non-renewable resource. However, with the annual increase of the world population and the annual intensification of water resource pollution, the number of drinkable water resources is reduced year by year, and particularly in western arid regions and coastal regions, due to drought climate and reverse flow of seawater, the salt content of underground water exceeds the standard and the underground water cannot be drunk directly. According to incomplete statistics, the fresh water resource of the earth only accounts for 2.5 percent of the total water quantity, and about 15 hundred million of people in 80 countries and regions which account for about 40 percent of the total population of the world are insufficient in fresh water.
Therefore, it is necessary to develop efficient water treatment technology and recover and treat polluted water. The reverse osmosis membrane water treatment technology has the advantages of simple operation, low energy consumption, environmental protection, small occupied area, good water quality of produced water and the like, and is widely applied to the fields of sewage treatment, brackish water desalination and high-salinity seawater desalination at present. The reverse osmosis membrane consists of a non-woven fabric layer, a porous polysulfone layer and a surface polyamide desalting layer, wherein the surface polyamide desalting layer determines the water production and the desalting rate of the reverse osmosis membrane, and the polyamide layer is mainly formed by polymerizing polybasic acyl chloride and polybasic amine on the surface of the porous polysulfone layer. Therefore, a large amount of unreacted polyamines and organic oil phase liquid remain in the dried membrane and need to be used after being rinsed. On the one hand, the excessive residual quantity of amine and organic solvent affects the quality of produced water and harms human health. On the other hand, the residual organic amine can be oxidized, yellowed and embrittled in the storage process of the diaphragm, so that the polyamide desalting layer is aged. The amine washing agent commonly used in the industry at present mainly comprises strong acid substances such as sulfuric acid, hydrochloric acid, nitric acid and the like, although the amine washing agent can play a role in reducing the content of amine, strong acid is easy to corrode the surface of a membrane under a high-temperature condition, so that the membrane surface is peeled off and perforated, the desalination rate is greatly reduced, and meanwhile, strong acid substances are easy to corrode a rinsing tank, so that the cost is increased and the quality of a reverse osmosis membrane is reduced.
Accordingly, the invention is particularly directed to.
Disclosure of Invention
In order to solve the defects of high amine and organic oil phase solvent liquid residue, serious rinsing liquid corrosion and low membrane desalination rate of a reverse osmosis membrane rinsing system in the prior art, the invention aims to provide a novel reverse osmosis membrane rinsing system and a rinsing method thereof.
The invention is realized by the following technical scheme:
a novel reverse osmosis membrane rinsing system comprises a first rinsing tank, a second rinsing tank and a glycerin tank in sequence;
an amine washing solution is filled in the first rinsing tank;
a washing oil solution is filled in the second rinsing groove;
the anti-pollution additive and the glycerin are filled in the glycerin tank.
Preferably, the amine washing solution is obtained by dissolving an amine washing agent in water, and the mass concentration of the amine washing agent in the amine washing solution is 2-5%.
Preferably, the amine washing agent is one or more of disodium hydrogen phosphate, sodium citrate, sodium carbonate and sodium nitrite.
Preferably, the oil washing solution is obtained by dissolving an oil washing agent and a hydrophilic additive in water, wherein the mass concentration of the oil washing agent in the oil washing solution is 1-4%, and the mass concentration of the hydrophilic additive in the oil washing solution is 1-4%.
Preferably, the oil washing agent is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium a-alkenyl sulfonate, isooctanol phosphate and isooctanol ether phosphate; the hydrophilic additive is one or more of isopropanol, N-hexanol, N-butanol, ethylene glycol, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone.
Preferably, the mass ratio of the anti-pollution additive to the glycerol in the glycerol tank is (0.2-2): (99.5-98).
Preferably, the anti-pollution additive is one or more of sodium bisulfite, sodium sulfite, polyhexamethylene biguanide, polyhexamethylene guanidine hydrochloride and polyhexamethylene acetate.
The invention also provides a rinsing method using the novel reverse osmosis membrane rinsing system, which comprises the following steps:
(1) placing the reverse osmosis membrane to be rinsed in a first rinsing tank for rinsing for 2-3 min, and then placing the membrane in a first rinsing tank for rinsing for 2-3 min;
(2) rinsing the reverse osmosis membrane washed by the first washing tank in the step (1) in a second rinsing tank for 3-5 min, and then placing the membrane in the second washing tank for 3-5 min;
(3) and (3) rinsing the reverse osmosis membrane washed by the second washing tank in the step (2) in a glycerin tank for 3-5 min, and drying for later use.
Preferably, the temperature in the first rinsing tank in the step (1) is 40-100 ℃.
Preferably, the temperature in the second rinsing tank in the step (2) is 50-80 ℃.
The invention has the beneficial effects that:
(1) compared with the commonly used strong acid amine washing agent in the prior art, the weak base amine washing agent can prevent a polyamide layer on the surface of the reverse osmosis membrane from being corroded and perforated, so that the desalination rate is reduced and the membrane surface becomes brittle; on the other hand, compared with strong acid amine detergents, strong acid amine detergents have the characteristic of being similar to residual amine components in phase dissolution and are weak in oxidizability, so that the phenomenon that the residual amine components on the membrane surface are oxidized and blackened to influence the appearance of the membrane is avoided.
(2) The method comprises the steps of adding a washing oil agent and a hydrophilic additive into a second rinsing tank, wherein the used washing oil agent is an anionic surfactant and has lipophilic and hydrophilic functional groups, and in the rinsing process, the lipophilic end can be fully contacted with the organic alkane oil phase solvent remaining on the membrane surface to reduce the surface tension, so that the remaining oil phase solvent is removed; the added hydrophilic additive is high hydrophilic alcohol, so that the hydrolysis of unreacted acyl chloride functional groups on the surface of polyamide can be promoted in the rinsing process, hydrophilic carboxyl is enriched on the surface of the membrane, and the water flux of the reverse osmosis membrane is increased.
(3) According to the novel reverse osmosis membrane rinsing system, the anti-pollution additive is introduced into the glycerin tank, the glycerin rinsing tank is usually arranged at the tail end of the conventional rinsing system, glycerin is coated on the surface of the rinsed membrane to keep the membrane moist and prevent the membrane from being dried and cracked and shrunk in the long-term storage process, but the surface of the membrane coated with the glycerin is wet, so that bacteria are easily bred in the storage process and mildew occurs to cause irreversible damage to the membrane. According to the invention, the anti-pollution additive with extremely high bactericidal performance is introduced into the glycerin tank, so that the antibacterial performance of the membrane surface is improved while the membrane surface is kept moist, and the storage period of the reverse osmosis membrane is prolonged.
Detailed Description
The present invention will be described in further detail with reference to 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.
Novel reverse osmosis membrane rinsing system and rinsing method thereof
Example 1
A novel reverse osmosis membrane rinsing system comprises a first rinsing tank, a second rinsing tank and a glycerin tank in sequence;
an amine washing solution is filled in the first rinsing tank, and the amine washing solution is a 2% aqueous solution of disodium hydrogen phosphate;
and an oil washing solution is filled in the second rinsing tank, and is obtained by dissolving sodium dodecyl sulfate (an oil washing agent) and isopropanol (a hydrophilic additive) in water, wherein the mass concentration of the sodium dodecyl sulfate in the oil washing solution is 1%, and the mass concentration of the isopropanol in the oil washing solution is 1%.
The glycerol tank is filled with an anti-pollution additive and glycerol, wherein the mass ratio of the anti-pollution additive to the glycerol is 1: 99, the anti-pollution additive is sodium bisulfite.
The rinsing method of the reverse osmosis membrane comprises the following steps:
(1) weighing 20kg of disodium hydrogen phosphate (amine washing agent) and placing the disodium hydrogen phosphate into a first rinsing tank for dissolving, uniformly mixing, diluting to 1000kg with water, heating to 80 ℃, placing the dried reverse osmosis membrane diaphragm into the first rinsing tank for rinsing for 2min, removing redundant water drops on the surface, and placing the reverse osmosis membrane diaphragm into a first washing tank for washing for 2 min;
(2) weighing 10kg of sodium dodecyl sulfate (oil washing agent) and 10kg of isopropanol (hydrophilic additive), dissolving the sodium dodecyl sulfate and the isopropanol in a second rinsing tank, diluting to 1000kg, uniformly mixing, then placing the reverse osmosis membrane washed by the water in the first rinsing tank in the step (1) in the second rinsing tank for rinsing for 4min, removing the redundant solution on the surface, placing the membrane in the second rinsing tank, and washing for 4min at the temperature of 60 ℃;
(3) and (3) weighing 5kg of sodium bisulfite (an anti-pollution additive) and 495kg of glycerin, adding the sodium bisulfite and the glycerin into a glycerin tank, uniformly mixing, then putting the reverse osmosis membrane washed by the water in the second washing tank into the glycerin tank, rinsing for 3-5 min, and drying for later use.
Examples 2 to 12
A novel reverse osmosis membrane rinsing system was substantially the same as in example 1, except as shown in table 1:
TABLE 1
Comparative example 1
The reverse osmosis membrane rinsing system in this comparative example differs from example 8 in that: the amine-washing agent in the first rinsing tank is replaced by a sulfuric acid solution.
The rinsing method comprises the following steps:
(1) weighing 120kg of 30 wt% sulfuric acid solution (amine washing solution) and placing the solution in a first rinsing tank for dissolving, after uniformly mixing, diluting the solution to 1000kg with water, heating to 80 ℃, then placing the dried reverse osmosis membrane diaphragm in the first rinsing tank for rinsing for 2min, removing redundant water drops on the surface, and placing the membrane in a first rinsing tank for rinsing for 2 min;
steps (2) to (3) were the same as in example 8.
Comparative example 2
The reverse osmosis membrane rinsing system in this comparative example differs from example 8 in that: the hydrophilic additive in the second rinse tank is omitted.
The rinsing method comprises the following steps:
(1) the same as in example 8;
(2) the second rinse tank was otherwise identical to example 8 without the addition of hydrophilic additives.
(3) The same as in example 8.
Comparative example 3:
the reverse osmosis membrane rinsing system in this comparative example differs from example 8 in that: the anti-contaminant additive in the glycerin tank was omitted.
The rinsing method comprises the following steps:
the steps (1) to (2) are the same as in example 8;
(3) the same procedure as in example 8 was repeated except that the anti-fouling additive was not added to the glycerin tank.
Secondly, testing the amine residue of the reverse osmosis membrane and testing the performance of the reverse osmosis membrane
1. Amine residual test
The amine residual quantity is tested on an ultraviolet visible spectrophotometer, firstly, a mixed solution of 100mL of ethanol and water is prepared according to the mass ratio of 7:3, then, a reverse osmosis membrane sheet which is rinsed and dried by 10cm x 10cm is cut, the reverse osmosis membrane sheet is cut and placed in the mixed solution, the mixed solution is heated for 4 hours at the temperature of 60 ℃ to dissolve out residual amine, the absorbance of the heated mixed solution is measured at the wavelength of 290nm, and then, the amine residual concentration is calculated according to a standard curve. The residual amine concentrations tested for the rinsed sheets of examples 1-12 and comparative examples 1-3 are shown in Table 2.
TABLE 2
As can be seen from Table 2, the amine-washing agent of weak alkaline salts is introduced into the first rinsing tank, and the composition is optimized, so that the residual amine content of the reverse osmosis membrane after rinsing can be reduced to 35mg/m2The amine residual quantity is far lower than the national wading requirement, so that the preservation period of the membrane can be effectively prolonged.
2. Film Performance testing
The rinsed reverse osmosis membrane membranes of examples 1-12 and comparative examples 1-3 are subjected to membrane flux and desalination tests on a membrane detection table, wherein a test solution is a NaCl aqueous solution with the conductivity of 4000 mu S, the pH of the test solution is adjusted to 7.5 +/-0.5 by using hydrochloric acid or sodium hydroxide, the membranes are firstly put into deionized water for soaking for about 30min before the test, then the membranes are cut to the corresponding size and put into a test membrane pool, the test pressure is adjusted to 250psi, the test temperature is 25 ℃, the membranes are enabled to stably run for 30min under constant temperature and constant pressure, permeate liquid water samples within a certain time after stable running are collected, the conductivity and the volume of the test solution are calculated, the desalination rate and the water flux of the membranes are calculated according to formulas, and the measurement data are shown in Table 3.
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); k is a radical off-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 V volumes of permeate in hours (h).
TABLE 3
As can be seen from Table 3, the hydrophilic additive introduced into the second rinsing tank can effectively improve the water flux of the membrane, and the water flux of the single membrane can be stabilized at 46.1GFD (example 8) by optimizing the proportion, which is far higher than the water flux result of the membrane rinsed in comparative example 2, so that the high water flux can increase the water yield of the membrane element per unit time and reduce the energy consumption required by water production. Meanwhile, the strong acid amine-washing component of comparative example 1 shows that the weak base component used in the invention has little influence on the salt rejection rate of the membrane.
Testing the surface water performance of the membrane:
taking the rinsed reverse osmosis membrane membranes of examples 1-12 and comparative examples 1-3, taking surface river water as a test solution (total organic carbon, TOC is 3.5mg/L), continuously running for 72h under 225psi pressure, washing the surfaces of the membranes with deionized water after running is finished, then taking a NaCl aqueous solution with the conductivity of 4000 mu S as the test solution, testing the water flux and the desalination rate of the membranes under the same conditions, wherein the test pressure is 225psi, the temperature of the test solution is 25 ℃, and the pH of the test solution is 7.0 +/-0.5, collecting produced water after prepressing for 30min, and calculating the water yield and the desalination rate of the membranes, as shown in Table 4.
TABLE 4
Meanwhile, the surface river water test is carried out on the rinsed membrane, the results are shown in table 4, the test shows that the water yield and the desalination rate of the membrane are reduced to a certain degree due to the pollution of the surface river water, compared with the comparative example 3, the anti-pollution component introduced into the glycerin tank has excellent anti-pollution performance, the rinsed membrane can still maintain the water flux of 44.5GFD and the desalination rate of more than 99.7 percent after being rinsed for a long time, and the flux of the comparative example 3 is only about 25GFD after being rinsed and polluted.
In conclusion, the novel reverse osmosis membrane rinsing system disclosed by the invention has excellent rinsing capacity, can keep low amine residual quantity of the membrane, has excellent water flux and salt rejection rate, has good pollution resistance, is simple in rinsing process and cheap and easily available in raw materials, and therefore has great application prospect in industrial production of reverse osmosis 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 (10)
1. A novel reverse osmosis membrane rinsing system is characterized by comprising a first rinsing tank, a second rinsing tank and a glycerin tank in sequence;
an amine washing solution is filled in the first rinsing tank;
a washing oil solution is filled in the second rinsing groove;
the anti-pollution additive and the glycerin are filled in the glycerin tank.
2. The novel rinsing system for reverse osmosis membranes as claimed in claim 1, wherein the amine washing solution is obtained by dissolving an amine washing agent in water, and the mass concentration of the amine washing agent in the amine washing solution is 2-5%.
3. A novel reverse osmosis membrane rinsing system according to claim 2, wherein the amine scrubbing agent is one or more of disodium hydrogen phosphate, sodium citrate, sodium carbonate, and sodium nitrite.
4. The novel rinsing system for reverse osmosis membranes as claimed in claim 1, wherein the oil washing solution is obtained by dissolving an oil washing agent and a hydrophilic additive in water, the mass concentration of the oil washing agent in the oil washing solution is 1-4%, and the mass concentration of the hydrophilic additive in the oil washing solution is 1-4%.
5. A novel reverse osmosis membrane rinsing system according to claim 4, wherein the oil detergent is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium a-alkenyl sulfonate, isooctanol phosphate, isooctanol ether phosphate; the hydrophilic additive is one or more of isopropanol, N-hexanol, N-butanol, ethylene glycol, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone.
6. A novel reverse osmosis membrane rinsing system according to claim 1, wherein the mass ratio of the anti-pollution additive to the glycerol in the glycerol tank is (0.2-2): (99.5-98).
7. A novel reverse osmosis membrane rinsing system according to claim 6 wherein said anti-contaminant additive is one or more of sodium bisulfite, sodium sulfite, polyhexamethylene biguanide, polyhexamethylene guanidine hydrochloride, polyhexamethylene acetate.
8. A rinsing method using the novel reverse osmosis membrane rinsing system according to any one of claims 1 to 7, characterized by comprising the following steps:
(1) placing the reverse osmosis membrane to be rinsed in a first rinsing tank for rinsing for 2-3 min, and then placing the membrane in a first rinsing tank for rinsing for 2-3 min;
(2) rinsing the reverse osmosis membrane washed by the first washing tank in the step (1) in a second rinsing tank for 3-5 min, and then placing the membrane in the second washing tank for 3-5 min;
(3) and (3) rinsing the reverse osmosis membrane washed by the second washing tank in the step (2) in a glycerin tank for 3-5 min, and drying for later use.
9. A rinsing method for a reverse osmosis membrane according to claim 8, wherein the temperature in the first rinsing tank in the step (1) is 40-100 ℃.
10. A rinsing method for a reverse osmosis membrane according to claim 8, wherein the temperature in the second rinsing tank in the step (2) is 50-80 ℃.
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