CN102049198B - Method for flushing reverse osmosis membrane - Google Patents
Method for flushing reverse osmosis membrane Download PDFInfo
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- CN102049198B CN102049198B CN 200910236766 CN200910236766A CN102049198B CN 102049198 B CN102049198 B CN 102049198B CN 200910236766 CN200910236766 CN 200910236766 CN 200910236766 A CN200910236766 A CN 200910236766A CN 102049198 B CN102049198 B CN 102049198B
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Abstract
The invention provides a method for flushing a reverse osmosis (RS) membrane, which aims at the problems of filtration surface contamination and first-section contamination of a reverse osmosis system membrane caused by high salt, organic colloidal silica, high molecular organic contaminants and microbiological remains during reverse osmosis treatment of olefin production process water, circulating cooling water and sewerage. In the method, positive flushing and concentrated water side reverse flushing are adopted, and agents such as an organic solvent and the like are matched, so hydraulic flushing is formed on the RO membrane filtration surface, blocking contaminants on the membrane surface which cannot be chemically removed are obviously removed, the problem of the first-section contamination of a membrane system is solved, and stable running period of the RO system is prolonged.
Description
Technical field
The present invention relates to a kind of purging method of reverse osmosis membrane, relate in particular to the purging method of the counter-infiltration system film surface contamination that is caused by inorganic salts, organosilicon colloid, macromolecule organic pollution and bacterium algae remains in the advanced treatment of wastewater reuse of a kind of petroleum chemical enterprise.
Background technology
Reverse osmosis process (being called for short RO) is one of main method of advanced treatment of wastewater reuse at present.Due to petrochemical wastewater, particularly chemical industry olefin production plant fresh water (FW), recirculated cooling water sewer, exist water quality inferiority, water quality complexity, colloid and cation, bacterium algae content high, easily counter-infiltration system caused dirty stifled.
At present, for the stifled Chemical cleaning of usually taking routine of the dirt of counter-infiltration system, main cleaning agent has NaOH, sodium polyphosphate, neopelex, hydrochloric acid, citric acid, oxalic acid, acetone, EDTA, fosthiazate ketone etc., and common cleaning way is the mode of circulation, immersion, recirculation.
For general inorganic scale pollutant or simple organic contamination, usually can well be removed by above method, clean the caudacoria system and can return to the initial launch value.But chemical industry olefin production plant fresh water (FW) and recirculated cooling water sewer, characteristics with high salinity, high content of organics, high biology and high colloidal content, the counter-infiltration system film that causes for this class organosilicon colloid, macromolecule organic pollution and bacterium algae remains pollutes, and conventional method is difficult to the removal effect that reaches satisfied usually.When the relatively poor sewage of above-mentioned water quality is carried out the embrane method advanced treating, often face the difficult problems such as stable operation cycle is short, Chemical cleaning is not thorough.
Summary of the invention
Counter-infiltration system is caused dirty stifled when carrying out the embrane method advanced treating for petroleum chemical enterprise's olefin production plant fresh water (FW), recirculated cooling water sewer, adopt the problem of the cleaning performance that conventional chemical cleaning method is difficult to reach satisfied, the invention provides a kind of effective counter-infiltration system purging method, counter-infiltration system membrane filtration surface and first section pollution problem that solution is caused by organosilicon colloid, macromolecule organic pollution and bacterium algae remains extend the counter-infiltration system stable operation cycle to reach, remove the difficult purpose of removing pollutant of Chemical cleaning.
This technique for process spent water and the recirculated cooling water sewer of petroleum chemical enterprise's olefin production plant, this sewage carries out advanced treatment process through finally entering counter-infiltration system after corresponding pre-treatment step.Its main water quality characteristics sees the following form 1.
Table 1
| Analysis project | Unit | Indication range |
| pH | 6～9 | |
| Total phosphorus | mg/L | 0～8 |
| Sulfate radical | mg/L | 0～1000 |
| Total iron | mg/L | 5 |
| Turbidity | NTU | ＜20 |
| Total silicon | mg/L | 5～30, even higher |
| COD | mg/L | 50～100 |
| Oil content | mg/L | ＜10 |
| Heterotroph | Individual/ml | 10 5, even higher |
In addition, also contain a large amount of high molecular polymers and olefin hydrocarbon apparatus in this sewage and reveal the multiple indefinite organic pollutions such as raw material, and these pollutants all are insoluble to acid, alkali and other organic solvents usually together with the microbial contamination shown in upper table, siliceous organic matter, phosphorus-containing matter etc., so can't remove by conventional Chemical cleaning.
Reverse osmosis thick water treatment method of the present invention is achieved in that
A kind of purging method of reverse osmosis membrane, carrying out embrane method when processing for olefin production plant fresh water (FW), recirculated cooling water sewer, the dirt on the reverse osmosis membrane surface of being caused by organosilicon colloid, macromolecule organic pollution and bacterium algae remains is stifled, and the purging method of described reverse osmosis membrane comprises the following steps successively:
(1) the influent side forward rinses, from the water inlet end water inlet of RO system, and the draining of concentrated water discharge end, to reverse osmosis membrane surface formation hydraulic blow, the dirt of removing on reverse osmosis membrane is stifled by sluicing;
When described forward rinses, the flushing flow rate of single film be 2～10t/h, washing time be 20s～5min, rinse 4～35 ℃ of temperature, pressure is 0.01～0.5MPa;
(2) dense water side backwash, from the concentrated water discharge end water inlet of RO system, the water inlet end draining, to reverse osmosis membrane surface formation hydraulic blow, the dirt of removing on reverse osmosis membrane is stifled by sluicing;
When described backwash, the flushing flow rate of single film is that 2～10t/h, washing time are that 20s～5min, flushing temperature are 4～35 ℃, pressure≤0.1MPa;
Add neopelex, acetone or alcohol in the flushing water of described influent side forward flushing and the backwash of described dense water side.
In the specific implementation, described influent side forward rinses and the flushing water of described dense water side backwash is selected from: RO system product water, industrial fresh water or desalted water.Described influent side forward rinses and the mode of described dense water side backwash adopts pulse to rinse, and the flushing cycle that described pulse is rinsed is 0.5～10s.
For petroleum chemical enterprise's olefin process waste water and recirculated cooling water sewer, in order to guarantee the long-period stable operation of counter-infiltration system, carrying out the influent side forward in the film running rinses and the back flush of dense water side, stopping pregnancy water in namely after counter-infiltration system operation one-period, carry out respectively forward and back flush, enter the next film cycle of operation after flushing is completed.
Contain a large amount of macromolecule organics, colloid, microorgranic contaminant in petroleum chemical enterprise and related industries technique waste water, recirculated cooling water sewer, restriction due to the filtering accuracy of RO pretreatment system, residual pollutant can pollute the RO system, main manifestations is that the pollution to RO system influent side filtering surface, especially system filter first section pressure reduction and obviously increase.This kind pollute to be difficult to uses chemical cleaning method effectively to remove, and due to the restriction of filtration path after RO membrane filtration passage and film series winding, is difficult to these pollutants are cleared out of system by the normal developing method.Due to pollutant in the RO system with dense water homonymy, and pollutant mainly is present in the water inlet end on membrane filtration surface, coordinate the mode of dense water side backwash to rinse so adopt the influent side forward to rinse, dense water side in traditional RO system increases pipeline, by-pass valve control and feed pump, reaches the non-rigid and conventional chemical of effective removal and cleans the difficult purpose of removing pollutant.
The frequency of rinsing generally judges by first section TMP of RO system operation, observes about first section TMP rising 0.01MPa and can open cleaning procedure; Also can according to the understanding of on-the-spot ruuning situation is selected reasonably to rinse frequency, utilize automatic control of PLC system's realization.
Carrying out forward when rinsing, RO system water intaking valve is closed, and rinses water intaking valve and opens, dense valve standard-sized sheet; Utilize high-pressure pump or booster pump directly to supply water, to RO membrane filtration surface formation hydrodynamic cleaning, reach the purpose of slowing down concentration polarization phenomenon in service and pollutant accumulation.
The forward flushing flow rate is decided according to on-the-spot reverse osmosis membrane system scale and withstand voltage degree, and the range of flow that common single film bears is 2～10t/h.The setting of washing time relates to developing result and operating cost, generally can set washing time 20s～5min.
The inflow temperature that forward rinses temperature and RO system coincide, for the more serious system of organic contamination, can be in the short time in flushing process suitable rising flushing water temperature, still can not exceed the ceiling temperature of the restriction of concrete film system.
The medicament that adds in the forward flushing water mainly contains: acid, alkali, bactericide and organic solvent.Add chemical agent for on-the-spot water quality in forward flushing water inlet, can play the effect of further removal RO membrane filtration surface contaminant.For the former water with fouling tendency, usually add HCl, citric acid etc. not to be provided as the acid of dirty anion, general control pH value is greater than 2.Higher for content of organics, and without the former water of fouling tendency, usually add NaOH or select to dodge into other possible bases of dirt for water quality, general control pH value is less than 12; In order to improve developing result, can add appropriate surfactant in flushing water, usually select to contain nonionic or anionic surfactant; For the organic matter that may cause in former water that RO is dirty stifled, can allocate certain density organic solvent in rinsing water inlet, when selecting organic solvent, guarantee that solvent is free from side effects to the RO film.
The pulse flushing is controlled flushing current frequency by pulse pump and is reached enhancing waterpower turbulent flow and to the surperficial impulse force effect of RO membrane filtration, can coordinate forward flushing and the backwash of dense water side to carry out.
When carrying out backwash, RO system water intaking valve is closed, and dense water side water inlet valve is opened, and influent side drain valve standard-sized sheet, dense water side blow are washed intake pump and opened, and RO membrane filtration surface is formed hydrodynamic cleaning.
The flushing flow rate of dense water side backwash is subject to the restriction of developing result and hydraulic pressure equally, and range of flow is 2～10t/h usually.The washing time setting range also can be at 20s～5min.Rinsing the control method of temperature and flushing pressure rinses identical with forward.
The backwash of dense water side mainly for be the pollutant that is insoluble to conventional RO Chemical cleaning medicament that dirt gets lodged in RO system water inlet end, so must not add conventional acid, alkalization to learn medicament in this technique.If former water also has obvious fouling tendency or other Organic Pollution tendency when containing Chemical cleaning pollutant in distress, the organic solvent and the surfactant that add in dense water side backwashing water, be conducive to the disengaging of the difficult Chemical cleaning pollutant in membrane filtration surface, strengthen the effect of dense water side backwash.
Purging method of the present invention, can effectively slow down counter-infiltration system membrane filtration surface concentration polarization phenomenon, alleviate the pollution problem that the conventional chemical medicament difficulties such as reverse osmosis membrane head end organic colloid, macromolecule pollutant, biology clear the pollution off, improve the stability of reverse osmosis membrane system operation, to extending the film system stable operation cycle, strengthen the Chemical cleaning effect, improving film and have very large effect service life.
Description of drawings
The process flow diagram of reverse osmosis membrane purging method of the present invention.
The specific embodiment
Be described in further detail technical scheme of the present invention below in conjunction with embodiment, protection scope of the present invention is not limited to the following specific embodiment.
Embodiment 1
Certain petroleum chemical enterprise's olefin production plant fresh water (FW), recirculated cooling water sewer embrane method advanced treatment apparatus.
(1) sewage quality:
The sewage quality that reverse osmosis unit is processed sees Table 2.
Table 2
| Analysis project | Unit | Mean value | Peak | Minimum |
| pH | 8.4 | 8.5 | 8.2 | |
| Total phosphorus | mg/L | 4.3 | 6.3 | 0.7 |
| Total hard | Mg/L is with CaCO 3Meter | 875 | 1056 | 511 |
| Calcium is hard | Mg/L is with CaCO 3Meter | 440 | 528 | 390 |
| Chlorion | mg/L | 242 | 283 | 131 |
| Sulfate radical | mg/L | 544 | 734 | 235 |
| Total iron | mg/L | 1.43 | 4.16 | 0.77 |
| Turbidity | NTU | 6.8 | 12.0 | 2.9 |
| Chlorine residue | mg/L | 0.04 | 6.60 | 0.01 |
| Total silicon | mg/L | 8.33 | 15.70 | 2.20 |
| COD | mg/L | 52 | 64 | 33 |
| Oil content | mg/L | N.D. | N.D. | N.D. |
| Heterotroph | Individual/ml | - | 6×10 3 | 0 |
As can be seen from the above table, it is higher that technique is processed COD in sewage, total silicon and biological content, and wherein total silicon occurs mainly with organosilyl form, and main source is water quality stabilizer.
(2) dirt of reverse osmosis membrane is stifled
Under above-mentioned waste water quality condition, the RO system is that first section dirt occurs very soon is stifled.It shows as: operating pressure totally rises not obvious, but intersegmental pressure reduction (TMP) obviously rises.RO cycle chemistry wash result shows, the dirt that waste water causes is stifled adopts conventional chemical cleaning formula and cleaning method not to reach cleaning performance, and after Chemical cleaning, pressure reduction can not return to the index before operation.The dirty stifled material of film is white cotton-shaped solid in water, is brown after oven dry.Infrared and EDAX results shows, its main component is unazotized organosilicon material.
(3) flushing of reverse osmosis membrane
Increase forward and rinse and dense water side backwash step in the reverse-osmosis treated process of normal operation, the normal operation of recovery film system after rinsing step is completed.
1. reverse osmosis membrane system normal operating phase
The normal cycle of operation of reverse osmosis membrane system is 8h.
2. the influent side forward rinses
Carry out the influent side forward when rinsing, RO system water intaking valve is closed, and rinses water intaking valve and opens, dense valve standard-sized sheet; Utilize high-pressure pump or booster pump directly to supply water, to RO membrane filtration surface formation hydrodynamic cleaning.The operating condition that the influent side forward rinses is:
The flushing flow rate of single film is 3t/h; Washing time 2min; Pressure 0.2MPa; Rinsing the water source is that on-the-spot ultrafiltration system produces water; Rinsing temperature is 25 ℃.
3. dense water side backwash
When carrying out backwash, RO system water intaking valve is closed, and dense water side water inlet valve is opened, influent side drain valve standard-sized sheet.Dense water side blow is washed intake pump and is opened, to RO membrane filtration surface formation hydrodynamic cleaning.The operating condition of dense water side backwash is:
The flushing flow rate of single film is 3t/h; Washing time 2min; Pressure≤0.1MPa; Rinsing the water source is that on-the-spot ultrafiltration system produces water; Rinsing temperature is 25 ℃; Allocate neopelex in flushing water into, concentration is 0.1 ‰; The pulse flushing cycle is 10s.
(4) operational effect
Rinse and dense water side backwash step through the influent side forward, to alleviating colloid, organic matter and bacterium algae residue, obvious effect has been played in the pollution of RO system, improved the stability that the RO system moves, first section pressure reduction of RO system obviously tends towards stability.The performance of TMP value is steady, and the TMP value is at 0.015-0.026MPa.
(5) Chemical cleaning effect and cycle
When reaching cleaning condition, adopt following condition to carry out Chemical cleaning to counter-infiltration system, the control index in Chemical cleaning reagent combination and cleaning process sees Table 3.
Table 3
After Chemical cleaning, the TMP of system and first section film intake pressure standardized value return to initial runtime value fully, and system's product water desalination rate is identical with film operation initial value.It is mainly to cause owing to cleaning the solubility pollutant that can remove by conventional chemical that the film that the illustrative system operation causes pollutes.In system, soluble pollutant is removed substantially by back flush technique.
After adopting this kind developing technique, can effectively extend the cycle of operation of film, cleaning frequency was reached about 2 months, the rising (mainly being caused by inorganic salts fouling and solubility organic pollution) of the dirty stifled situation main manifestations overall operation pressure of system before Chemical cleaning, and first section TMP of nonsystematic rises.
Comparative Examples 1
Under the identical condition of counter-infiltration system operation source quality, operation process, operational factor, do not adopt reverse osmosis membrane rinsing step of the present invention, only adopt a conventional timing forward to rinse, cleaning parameter is as follows: the flushing flow rate of single film is 3t/h; Washing time 2min; Pressure 0.2MPa; Rinsing the water source is that on-the-spot ultrafiltration system produces water; Rinsing temperature is 25 ℃.Carry out the Chemical cleaning identical with embodiment 1.
After cleaning, it is only 0.01MPa that the film system pressure difference reduces amplitude, can not make one section pressure reduction of RO film system return to initial value.When taking this technique, the Chemical cleaning cycle of system is only 7～14 days, and before Chemical cleaning, TMP rises 16%.
Compare with Comparative Examples 1, embodiment 1 adopts the purging method of reverse osmosis membrane of the present invention, alleviated the pollution to the RO system of colloid, organic matter and bacterium algae residue, particularly clean the stifled material of the dirt that to remove for the film surface chemistry and played obvious removal effect, effectively alleviate first section pollution of film system, reached the difficult effect of removing pollutant, prolongation counter-infiltration system stable operation cycle, strengthening the Chemical cleaning effect of Chemical cleaning of removing.
Claims (2)
1. the purging method of a reverse osmosis membrane, carrying out embrane method when processing for olefin production plant fresh water (FW), recirculated cooling water sewer, the dirt on the reverse osmosis membrane surface of being caused by organosilicon colloid, macromolecule organic pollution and bacterium algae remains is stifled, and the purging method of described reverse osmosis membrane comprises the following steps successively:
(1) the influent side forward rinses, from the water inlet end water inlet of RO system, and the draining of concentrated water discharge end, to reverse osmosis membrane surface formation hydraulic blow, the dirt of removing on reverse osmosis membrane is stifled by sluicing;
When described forward rinses, the flushing flow rate of single film be 2 ~ 10t/h, washing time be 20s ~ 5min, rinse 4 ~ 35 ℃ of temperature, pressure is 0.01 ~ 0.5MPa;
(2) dense water side backwash, from the concentrated water discharge end water inlet of RO system, the water inlet end draining, to reverse osmosis membrane surface formation hydraulic blow, the dirt of removing on reverse osmosis membrane is stifled by sluicing;
When described backwash, the flushing flow rate of single film is that 2 ~ 10t/h, washing time are that 20s ~ 5min, flushing temperature are 4 ~ 35 ℃, pressure≤0.1MPa;
Described influent side forward rinses and the mode of described dense water side backwash adopts pulse to rinse, and the flushing cycle that described pulse is rinsed is 0.5 ~ 10s;
Add neopelex, acetone or alcohol in the flushing water of described influent side forward flushing and the backwash of described dense water side.
2. processing method according to claim 1 is characterized in that:
Described influent side forward rinses and the flushing water of described dense water side backwash is selected from: RO system product water, industrial fresh water or desalted water.
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