CN109133433A - A kind of organic dirty blocking control method of reverse osmosis membrane - Google Patents
A kind of organic dirty blocking control method of reverse osmosis membrane Download PDFInfo
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- CN109133433A CN109133433A CN201811210475.8A CN201811210475A CN109133433A CN 109133433 A CN109133433 A CN 109133433A CN 201811210475 A CN201811210475 A CN 201811210475A CN 109133433 A CN109133433 A CN 109133433A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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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
- B01D65/08—Prevention of membrane fouling or of concentration polarisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/16—Use of chemical agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/21—Dissolved organic carbon [DOC]
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
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Abstract
The invention discloses a kind of organic dirty blocking control methods of reverse osmosis membrane to primarily determine that active carbon and iron chloride add ratio by the molecular weight of organic matter and its measurement result of three-dimensional fluorescence spectrum figure in water inlet water sample；Concentration ranges are added according to what the concentration of DOC determined active carbon and iron chloride, and corresponding DOC removal rate is obtained respectively, determine that optimum activity charcoal adds concentration A and optimal chlorination iron adds concentration B by minimizing agent magnitude needed for steady removal DOC, the active carbon of A concentration is added into feed water by reverse osmosis, after absorption 0.5-1 hours, the iron chloride of B concentration is added again, and coagulation removes active carbon and residual organic substances.The present invention has the characteristics that low cost, low energy consumption, easy to operate, by the organic pollutant in removal RO system water inlet, reach stable RO system influent quality, slows down RO system dirt and block up rate, increase RO system run all right and runing time, to reduce the purpose of RO system operation cost.
Description
Technical field
The present invention relates to organic dirty stifled controls of recycled water reverse osmosis deaslination technical field more particularly to a kind of reverse osmosis membrane
Method.
Background technique
China's water resource critical shortage, reuse of wastewater are the effective ways for solving the problems, such as this, and be in full swing regeneration
The utilization of water has a very important significance to China's shortage of water resources is alleviated.Reverse osmosis process (Reverse Osmosis,
RO) since producing water water quality is good, stable, it is gradually applied to regeneration effluent field, but the organic matter in sewage will cause sternly
The RO film dirt of weight is stifled, causes RO system to produce water water and deteriorating water quality, operation energy consumption and increased costs, limits pushing away for RO technique
Extensively.
Most cities sanitary sewage regenerates water factory before RO system body technique, will increase some column pretreating process,
The organic pollutant in the water inlet of RO system can be removed by these pretreatment modes, reaches stable RO system influent quality, subtracts
Rate is blocked up in slow RO system dirt, increases RO system run all right and runing time, to reduce the purpose of RO system operation cost.
Common pretreating process includes: coagulating sedimentation, active carbon filtering, micro-filtration/ultrafiltration etc., wherein coagulating sedimentation and work
Property charcoal technique is easy to operate and be widely used because cost is relatively low for it, but these pretreating process are usually all single use,
There is no the precedent of combined use, different pretreatments process combination uses the research to the component removal situation into Organic substance in water
It is extremely short of, is also not bound with the specific method used, how to design a kind of combination pretreating process further to slow down RO system
The dirty stifled rate of system is of great significance in terms of control RO film is organic dirty.
Summary of the invention
To solve the above-mentioned problems, the object of the present invention is to before counter-infiltration system main process, one kind is provided and is based on
Iron chloride coagulating sedimentation combines pretreated organic dirty blocking control method with granular activated carbon, for controlling the organic of reverse osmosis membrane
Dirt is stifled.
The present invention is achieved by the following technical solutions: a kind of organic dirty blocking control method of reverse osmosis membrane, including with
Lower step:
(1) two kinds of water treatment agents of iron chloride stock solution and clean active carbon are prepared；
(2) from reverse osmosis membrane target water inlet in take out water inlet water sample, water sample is divided into several pieces, add respectively active carbon and
Iron chloride show that the solubility in the case where the difference of active carbon and iron chloride adds concentration in corresponding water sample has to various concentration
Machine carbon (DOC) removal rate, according to concentration and DOC removal rate is added, determine active carbon most preferably adds concentration A, iron chloride most
Good to add concentration B, the concentration that adds is the concentration after water treatment agent is added to water sample in water sample；
(3) concentration is most preferably added according to the active carbon and iron chloride determined in (2), adds active carbon into target water inlet
Make its concentration A in target water inlet, after absorption 0.5-1 hours, then adding iron chloride into target water inlet makes it in target
Concentration in water inlet is B, and coagulation removes active carbon and residual organic substances.
Since DOC is a major class index in organic matter of sewage, and the fundamental characteristics of water inlet, according to DOC removal rate
The stifled characteristic of dirt to judge reverse osmosis membrane is representative, and the present invention is obtained by adding active carbon and iron chloride in water sample
The two corresponding DOC removal rate in the case where difference adds concentration out, according to the removal rate of DOC, determine the two most preferably adds concentration,
Then sequentially adding active carbon and iron chloride into target water inlet again keeps concentration of the two in target water inlet best
Add concentration；Determine that the purpose for most preferably adding concentration is the minimizing agent that water treatment agent is selected while guaranteeing steady removal DOC
Amount, can not only make the removal efficiency highest of organic matter, moreover it is possible to increase economic efficiency, it is excessive or too small to add concentration, DOC removal rate
Cannot be in a higher stable state, satisfactory water quality cannot be reached, and add concentration it is excessive when, water process
The additive capacity of agent is higher, and maximization is not achieved in economic benefit；Active carbon as adsorbent can first in absorption effluent one
Partial organic substances, after absorption 0.5-1 hours, absorption property is gradually decreased, then adds the iron chloride as coagulant, surplus in removal
While remaining organic matter can also coagulation remove extra active carbon, reduce the processing step to active carbon.
The present invention combines pretreated mode with granular activated carbon using iron chloride coagulating sedimentation, compared to iron chloride coagulation
When precipitating is individually pre-processed with granular activated carbon, the removal rate of organic matter increases, and with runing time
Extend, situation when again smaller than two kinds pretreatment modes of decrease speed of production water speed rate are used alone further improves reverse osmosis
The service life of permeable membrane, and improve producing water water quality.
The present invention has the characteristics that low cost, low energy consumption, easy to operate, passes through the organic contamination in removal RO system water inlet
Object reaches stable RO system influent quality, slows down RO system dirt and blocks up rate, increases RO system run all right and runing time,
To reduce the purpose of RO system operation cost.
Preferably, in step (1), the preparation and storage method of iron chloride stock solution are as follows: iron chloride is stored in airtight bottle
In, the iron chloride stock solution that configuration concentration is 1g/L at room temperature is protected from light after configuration is good and is sealed as coagulant.
Since iron chloride is added with the concentration in water sample in the next steps, the concentration of 1g/L is selected, just
Dilution when subsequent add；The moisture in air impacts iron chloride stock solution in order to prevent, is protected by the way of sealing
It deposits, light impacts the temperature of ferric chloride solution in order to prevent, further results in iron chloride and goes bad, by the way of being protected from light
It saves.
Preferably, in step (1), the preparation and storage method of active carbon are as follows: living using the coconut husk particle of partial size 1-2mm
Property charcoal, active carbon is using preceding needing to be cleaned repeatedly with water, until wash rear active carbon water outlet dissolved organic carbon (DOC) lower than 0.5mg/L,
I.e. it is believed that preparing clean active carbon；Clean active carbon is placed in 70 DEG C of drying in oven, is subsequently placed in beaker and keeps away
Light is sealed.
In step (2), initial DOC concentration value is a in measurement water inlet water sample0Mg/L is measured and is added in water inlet water sample
Water treatment agent and its add concentration be biCorresponding DOC concentration value is a when mg/LiMg/L, then the concentration that adds of water treatment agent be
biWhen mg/L, corresponding DOC removal rate ciAre as follows: (ai-a0)/a0。
Preferably, in step (2), the measuring method of DOC concentration are as follows: take water sample 5ml to be measured, cross benefit after 0.45 μm of filter membrane
The DOC concentration in water sample is measured with TOC analyzer.
Preferably, in step (2), the method for most preferably adding concentration is determined are as follows: select the increment rate of opposite DOC removal rate
When adding the ratio between increment rate of concentration with opposite water treatment agent closest to 1 corresponding water treatment agent add concentration be most preferably add it is dense
Degree；Assuming that two adjacent concentration that add of same water treatment agent are respectively bi-1、bi(bi>bi-1), corresponding DOC removal rate difference
For ci-1、ci, then it is b that water treatment agent, which adds concentration,iWhen, the increment rate of opposite DOC removal rate is (ci-ci-1)/ci-1, opposite water
The increment rate that inorganic agent adds concentration is (bi-bi-1)/bi-1。
It is further preferred that in step (2), first determine active carbon and iron chloride adds concentration ranges, then is adding
It is determined in concentration ranges and most preferably adds concentration；
Add the determination method of concentration ranges are as follows: initial DOC concentration value is a in measurement water inlet water sample0Mg/L, then it is active
The concentration ranges that add of charcoal and iron chloride are respectively (3-9) * a0Mg/L and (1-9) * a0mg/L.Here concentration ranges are DOC's
Best removal section, DOC removal rate at this time can achieve highest.
It is further preferred that the concentration that adds of active carbon is 3a in step (2)0mg/L、4.5a0mg/L、6a0mg/L、
7.5a0mg/L、9a0mg/L.It is further preferred that first determining that active carbon and the best of iron chloride add concentration in step (2)
Ratio, further according to most preferably add concentration ratio and active carbon add that concentration determines iron chloride add concentration；
Preferably, the determination method of concentration ratio is most preferably added are as follows: the molecule of organic matter in measurement feed water by reverse osmosis water sample
Amount measures and obtains the three-dimensional fluorescence spectrum figure of reverse osmosis membrane water inlet water sample, judges whether water sample has (1) molecular weight 102-
103Have in obvious absorption peaks and IVth area (2) three-dimensional fluorescence spectrum Zhong and VIth area within the scope of Da have obvious fluorescence response both
Water sample feature；If above two water sample feature is provided with, it is determined that active carbon and iron chloride most preferably adding in water inlet water sample
Concentration ratio is 1:1；If only having above-mentioned a certain water sample feature, it is determined that it is 2:1 that the two, which most preferably adds concentration ratio,；On if
It states two kinds of water sample features not have, it is determined that it is 3:1 that the two, which most preferably adds concentration ratio,.
Preferably, in step (2), determine that most preferably adding concentration A and most preferably adding another method of concentration B includes such as
Lower step:
(21) according to the organic molecule measure feature and three-dimensional fluorescence spectrum figure feature of water inlet water sample, active carbon and chlorine are determined
Change iron and most preferably add concentration ratio in water inlet water sample:
Preferably, for having (1) molecular weight 102-103There are obvious absorption peaks and (2) three-dimensional fluorescence spectrum within the scope of Da
There is the water sample of both water sample features of obvious fluorescence response in IVth area Zhong and VIth area, determines that the two is best in water inlet water sample
Adding concentration ratio is 1:1；If only meeting above-mentioned a certain water sample feature, it is determined that it is 2:1 that the two, which most preferably adds concentration ratio,；
If not having features described above, determining that the two most preferably adds concentration ratio is 3:1；
(22) the initial DOC concentration value of measurement water inlet water sample is a0Mg/L determines that active carbon is dense in adding for water inlet water sample
Spending section is respectively (3-9) * a0Mg/L, and obtain and add the removal rate of DOC in water sample under concentration in different activities charcoal；
(23) according to determine in (21) most preferably add active carbon in concentration ratio and (22) add concentration ranges, from
And determine that iron chloride adds concentration ranges in water inlet water sample, and obtain and add under concentration DOC in water sample in different iron chloride
Removal rate；
(24) the DOC removal rate under concentration is added in difference according to Water condition agent in (22) and (23), selection is opposite
The increment rate of DOC removal rate when adding the ratio between increment rate of concentration with opposite water treatment agent closest to 1 corresponding water treatment agent throw
Adding concentration is that the best of the water treatment agent adds concentration.
In step (3), the three-dimensional fluorescence spectrum figure is intake according to regeneration of urban sewage system reverse osmosis process
The corresponding relationship of middle Representative fluorescence substance (amino acid, protein, polysaccharide and class humic acid substance etc.), by three-dimensional fluorescence fingerprint image
6 big regions are divided into, each region corresponds to different substances, is respectively: I-class tyrosine, tryptophan；II-class tyrosine, color
Propylhomoserin albumen；III-polysaccharide；IV-class polycarboxylic acid humic acid substance；V-class multiring aromatic hydrocarbon humic acid substance；VI-class
Fulvic acid class material.
Detailed description of the invention
Fig. 1 is the flow chart of organic dirty blocking control method of reverse osmosis membrane provided by the invention；
Fig. 2 is the graph of molecular weight distribution of water inlet water sample 1；
Fig. 3 is the three-dimensional fluorescence spectrum figure of water inlet water sample 1；
Fig. 4 is the production water speed rate variation diagram that water inlet water sample 1 passes through reverse osmosis membrane after different preprocess methods；
Fig. 5 is the graph of molecular weight distribution of water inlet water sample 2；
Fig. 6 is the three-dimensional fluorescence spectrum figure of water inlet water sample 2；
Fig. 7 is the production water speed rate variation diagram that water inlet water sample 2 passes through reverse osmosis membrane after different preprocess methods；
Fig. 8 is the graph of molecular weight distribution of water inlet water sample 3；
Fig. 9 is the three-dimensional fluorescence spectrum figure of water inlet water sample 3；
Figure 10 is the production water speed rate variation diagram that water inlet water sample 3 passes through reverse osmosis membrane after different preprocess methods；
Figure 11 is the graph of molecular weight distribution of water inlet water sample 3；
Figure 12 is the three-dimensional fluorescence spectrum figure of water inlet water sample 3；
Figure 13 is the production water speed rate variation diagram that water inlet water sample 3 passes through reverse osmosis membrane after different preprocess methods.
Specific embodiment
Following further describes the present invention with reference to the drawings.
Organic dirty blocking control method of reverse osmosis membrane provided by the invention, step is as shown in Figure 1, especially by following reality
It applies example to be specifically described, also, it is identical with the method for cleaning action charcoal to prepare iron chloride stock solution in different embodiments.
Prepare iron chloride stock solution and storage method are as follows: iron chloride is stored in airtight bottle, configuration concentration is at room temperature
The iron chloride stock solution of 1g/L is protected from light after configuration is good and is sealed as coagulant.
The preparation and storage method of cleaning action charcoal are as follows: using the coconut husk granular activated carbon of partial size 1-2mm, active carbon is used
Before need to be cleaned repeatedly with water, until washing rear active carbon water outlet dissolved organic carbon (DOC) lower than 0.5mg/L, i.e., it is believed that preparing
Clean active carbon；Clean active carbon is placed in 70 DEG C of drying in oven, is subsequently placed in be protected from light in beaker and is sealed.
The present invention passes through the molecular weight of organic matter and its measurement result of three-dimensional fluorescence spectrum figure in measurement water sample first, just
It walks and determines that active carbon and iron chloride add ratio；The concentration ranges that add of active carbon and iron chloride are determined according to the concentration of DOC, and
Corresponding DOC removal rate is obtained respectively, determines that optimum activity charcoal adds concentration by minimizing agent magnitude needed for steady removal DOC
A and optimal chlorination iron add concentration B, and active carbon is added into feed water by reverse osmosis makes it add concentration A, then add chlorination again
Iron makes it add concentration B, and coagulation removes active carbon and residual organic substances.
The present invention determine most preferably add concentration when, can first determine and corresponding when DOC removal rate is higher add concentration area
Between, it then adds at this and is determined in concentration ranges and most preferably add concentration, reduce selection number, improve test efficiency；Due to adding
Point value in concentration ranges is more, and obtaining value method is varied, so the present invention provides a kind of method of uniform intervals value,
Concentration is added for active carbon, it can be according to the initial concentration value a of DOC in water sample0Mg/L, limit active carbon adds concentration
For 3a0mg/L、4.5a0mg/L、6a0mg/L、7.5a0mg/L、9a0Mg/L, this obtaining value method for adding concentration not only facilitate fast
Victory, and the DOC removal rate at the point value is also higher.
Efficiency when in order to improve active carbon and iron chloride combined treatment, and the additive amount of the two is made to be in lower as far as possible
It is horizontal, it may be predetermined that active carbon and the best of iron chloride add concentration ratio, add concentration ratio and work according to best
Property charcoal add concentration i.e. and can determine iron chloride add concentration；The present invention is when determination most preferably adds concentration ratio, selection
(1) molecular weight is 102-103Having in obvious absorption peaks and IVth area (2) three-dimensional fluorescence spectrum Zhong and VIth area within the scope of Da has obviously
Both water sample features of fluorescence response, both water sample features are simply easily surveyed, and wherein molecular size range embodies Organic substance in water
Bulk of molecule, fluorescence spectral characteristic then reflect the molecular structure (chemical functional group) of Organic substance in water.According to different target
The water sample feature of water inlet, select it is different most preferably add concentration ratio, the standardization for making target intake produces water speed rate and is in higher
Level, for same water sample, standardization when selection most preferably adds concentration ratio produces water speed rate enhancing rate compared to other ratios
Enhancing rate under example is higher by about 15%-30%, and the stifled control effect of dirt is more preferable.
Embodiment 1
Target water inlet 1 is used in the present embodiment, the determination of organic dirty blocking control method is as follows in reverse osmosis membrane water inlet 1:
(1) two kinds of water treatment agents of iron chloride stock solution and clean active carbon are prepared；
(2) determine active carbon most preferably add concentration A, iron chloride most preferably add concentration B:
(21) water inlet water sample 1 is taken out from reverse osmosis membrane target water inlet 1, measures feed water by reverse osmosis water using liquid chromatograph
The molecular weight of organic matter in sample 1, graph of molecular weight distribution is as shown in Fig. 2, using fluorescent spectrophotometer assay and obtain reverse osmosis
The three-dimensional fluorescence spectrum figure of permeable membrane water inlet water sample 1, as shown in Figure 3；As shown in Figure 2, water inlet water sample 1 is 102-103Have within the scope of Da
The water sample of obvious absorption peaks determines live as a result, from the figure 3, it may be seen that water inlet water sample 1 has obvious fluorescence response in IVth area and VIth area
Property charcoal and iron chloride water inlet water sample 1 in most preferably add concentration ratio be 1:1；
(22) water sample 5ml to be measured is taken, the DOC concentration for crossing measurement water inlet water sample 1 after 0.45 μm of filter membrane is 4mg/L, determines and lives
Property charcoal add concentration be 12mg/L, 18mg/L, 24mg/L, 30mg/L, 36mg/L, it is above-mentioned add concentration refer to active carbon into
Water inlet water sample is divided into several pieces, adds active carbon respectively to above-mentioned and add concentration, and obtain above-mentioned by the concentration of water water sample 1
Active carbon adds the removal rate of DOC in water sample 1 under concentration, as shown in table 1:
1 different activities charcoal of table adds under concentration to the removal rate of DOC in water inlet water sample 1
(23) adding for active carbon in concentration ratio and (22) is most preferably added according to active carbon in (21) and iron chloride
Concentration, determine iron chloride add concentration (i.e. iron chloride water inlet water sample 1 in concentration) for 12mg/L, 18mg/L, 24mg/L,
Water inlet water sample is divided into several pieces, adds iron chloride respectively to above-mentioned and add concentration, and obtain above-mentioned by 30mg/L, 36mg/L
Iron chloride adds the DOC removal rate under concentration in water sample 1, as shown in table 2:
The different iron chloride of table 2 add under concentration to the removal rate of DOC in water inlet water sample 1
(24) the DOC removal rate under concentration is added according to different activities charcoal in (22), selects opposite DOC removal rate increment rate
When adding the ratio between concentration increment rate closest to 1 with relative activity charcoal corresponding active carbon add concentration 24mg/L be active carbon most
It is good to add concentration A；
The DOC removal rate under concentration is added according to iron chloride different in (23), selects opposite DOC removal rate increment rate and phase
Corresponding iron chloride adds the best throwing that concentration 18mg/L is iron chloride when adding the ratio between concentration increment rate closest to 1 to iron chloride
Add concentration B；
(3) concentration is most preferably added according to the active carbon and iron chloride determined in (24), adds activity into target water inlet 1
Charcoal makes its concentration 24mg/L in target water inlet 1, and after absorption 0.5 hour, then adding iron chloride makes it in target water inlet 1
Concentration be 18mg/L, coagulation removes active carbon and residual organic substances.
Target water inlet 1 is pre-processed by the combination of 24mg/L active carbon and 18mg/L iron chloride, merely through 24mg/L activity
Pass through the standardization of reverse osmosis membrane after charcoal pretreatment, when pre-processing merely through 18mg/L iron chloride and do not carry out any pretreatment
It is as shown in Figure 4 to produce the variation of water speed rate；As shown in Figure 4, in reverse osmosis membrane system operational process, combined pretreated production water speed
Rate is above other three kinds of modes, and with the extension of time, the combined pretreated decrease speed for producing water speed rate is less than
Other three kinds of modes, thus illustrate, combine pretreated mode for controlling the stifled effect of dirt more effectively and stablizing persistently.
Under above-mentioned 4 kinds of modes run 30h when each group standardization produce water speed rate and standardization produce water speed rate enhancing rate (with
Production water speed rate when untreated is compared) as shown in table 3 below:
Each group when the water inlet water sample 1 of table 3 runs 30h under each pretreatment mode
Standardization produces water speed rate and standardization produces water speed rate enhancing rate
As shown in Table 3, in the case where combining pretreatment mode, standardization produces water speed rate and pre-processes higher than other two when running 30h
Standardization when mode is used alone produces water speed rate, and standardizes and produce water speed rate enhancing rate compared to active carbon and iron chloride list
Solely 19.66% and 14.5% are not improved using the time-division.
In above-mentioned steps, step (21) and the sequence of step (22) can be exchanged.
Embodiment 2
In the present embodiment choose target water inlet 2, it is organic dirt blocking control method with embodiment 1, the difference is that:
Organic matter molecular mass distribution map in (I) water inlet water sample 2 is as shown in figure 5, its three-dimensional fluorescence spectra is as shown in Figure 6；
As shown in Figure 5, water inlet water sample 2 is 103-104There is the water sample of obvious absorption peaks within the scope of Da, and 102-103Do not have within the scope of Da
The water sample of obvious absorption peaks determines live as a result, it will be appreciated from fig. 6 that water inlet water sample 2 has obvious fluorescence response in IVth area and VIth area
Property charcoal and iron chloride water inlet water sample 2 in most preferably add concentration ratio be 2:1；
(II) takes water sample 5ml to be measured, and the DOC concentration of measurement water inlet water sample 2 is 4mg/L after 0.45 μm of filter membrane excessively, according to DOC
Measurement result, determining that active carbon adds concentration is 12mg/L, 18mg/L, 24mg/L, 30mg/L, 36mg/L, and is obtained upper
The removal rate that active carbon adds DOC in water sample 2 under concentration is stated, as shown in table 4:
4 different activities charcoal of table adds under concentration to the removal rate of DOC in water inlet water sample 2
Concentration and active carbon are added according to active carbon and the best of iron chloride adds concentration ratio, determine that iron chloride adds
Concentration is 6mg/L, 9mg/L, 12mg/L, 15mg/L, 18mg/L, and obtains and add under concentration in water sample 2 in above-mentioned iron chloride
DOC removal rate, as shown in table 5:
The different iron chloride of table 5 add under concentration to the removal rate of DOC in water inlet water sample 2
The DOC removal rate under concentration is added according to different activities charcoal in table 4, selects opposite DOC removal rate increment rate and phase
It is most preferably to add concentration A that corresponding active carbon, which adds concentration 18mg/L, when adding the ratio between concentration increment rate closest to 1 to active carbon；
The DOC removal rate under concentration is added according to iron chloride different in table 5, selects opposite DOC removal rate increment rate and opposite iron chloride
It is most preferably to add concentration B that corresponding iron chloride, which adds concentration 12mg/L, when adding the ratio between concentration increment rate closest to 1；
(III) most preferably adds concentration according to determining active carbon and iron chloride, and adding active carbon into target water inlet 2 makes
Its target water inlet 2 in concentration be 18mg/L, absorption 1 hour after, then add iron chloride make its target water inlet 2 in concentration
For 12mg/L, coagulation removes active carbon and residual organic substances.
Target water inlet 2 is pre-processed by the combination of 18mg/L active carbon and 12mg/L iron chloride, merely through 18mg/L activity
Pass through the standardization of reverse osmosis membrane after charcoal pretreatment, when pre-processing merely through 12mg/L iron chloride and do not carry out any pretreatment
It is as shown in Figure 7 to produce the variation of water speed rate.
Each group standardization produces water speed rate when running 30h under above-mentioned 4 kinds of modes and standardization produces water speed rate enhancing rate such as
Shown in the following table 6:
Each group standardization produces water speed rate when the water inlet water sample 2 of table 6 runs 30h under each pretreatment mode and standardization produces water
Rate enhancing rate
As shown in Table 6, in the case where combining pretreatment mode, standardization produces water speed rate and pre-processes higher than other two when running 30h
Production water speed rate when mode is used alone, and it produces water speed rate enhancing rate and the time-division is used alone compared to active carbon and iron chloride
24.48% and 17.28% are not improved.
Embodiment 3
In the present embodiment using target water inlet 3, it is organic dirt blocking control method with embodiment 1, the difference is that:
Organic matter molecular mass distribution map in (I) water inlet water sample 3 is as shown in figure 8, its three-dimensional fluorescence spectra is as shown in Figure 9；
As shown in Figure 8, water inlet water sample 3 is 102-103There is the water sample of obvious absorption peaks within the scope of Da, as shown in Figure 9, water sample 3 of intaking is in I
There is an obvious fluorescence response in area and the area II, without obvious fluorescence response in IVth area Er and VIth area, determine active carbon and chlorination as a result,
Most preferably add concentration ratio of the iron in water inlet water sample 3 is 2:1；
(II) takes water sample 5ml to be measured, and the DOC concentration of measurement water inlet water sample 3 is 6mg/L after 0.45 μm of filter membrane excessively, according to DOC
Measurement result, determining that active carbon adds concentration is 18mg/L, 27mg/L, 36mg/L, 45mg/L, 54mg/L, and is obtained upper
The removal rate that active carbon adds DOC in water sample under concentration is stated, as shown in table 7:
7 different activities charcoal of table adds under concentration to the removal rate of DOC in water inlet water sample 3
According to active carbon add concentration and active carbon and iron chloride most preferably add concentration ratio, determine that iron chloride is thrown
Adding concentration is 9mg/L, 13.5mg/L, 18mg/L, 22.5mg/L, 27mg/L, and show that adding concentration in above-mentioned iron chloride is lauched
DOC removal rate in sample, as shown in table 8:
The different iron chloride of table 8 add under concentration to the removal rate of DOC in water inlet water sample 3
The DOC removal rate under concentration is added according to different activities charcoal in table 7, selects opposite DOC removal rate increment rate and phase
It is most preferably to add concentration A that corresponding active carbon, which adds concentration 27mg/L, when adding the ratio between concentration increment rate closest to 1 to active carbon；
The DOC removal rate under concentration is added according to iron chloride different in table 8, selects opposite DOC removal rate increment rate and opposite iron chloride
It is most preferably to add concentration B that corresponding iron chloride, which adds concentration 13.5mg/L, when adding the ratio between concentration increment rate closest to 1；
(III) most preferably adds concentration according to determining active carbon and iron chloride, and adding active carbon into target water inlet 3 makes
Its concentration in target water inlet 3 is 27mg/L, and after absorption 0.75 hour, then adding iron chloride makes it in target water inlet 3
Concentration is 13.5mg/L, and coagulation removes active carbon and residual organic substances.
Target water inlet 3 is lived by the combination pretreatment of 27mg/L active carbon and 13.5mg/L iron chloride, merely through 27mg/L
Property charcoal pretreatment after, pass through the mark of reverse osmosis membrane when pre-processing merely through 13.5mg/L iron chloride and do not carry out any pretreatment
It is as shown in Figure 10 that standardization produces the variation of water speed rate.
Each group standardization produces water speed rate when running 30h under above-mentioned 4 kinds of modes and standardization produces water speed rate enhancing rate such as
Shown in the following table 9:
Each group standardization produces water speed rate when the water inlet water sample 3 of table 9 runs 30h under each pretreatment mode and standardization produces water
Rate enhancing rate
As shown in Table 9, in the case where combining pretreatment mode, standardization produces water speed rate and pre-processes higher than other two when running 30h
Production water speed rate when mode is used alone, and it produces water speed rate enhancing rate and the time-division is used alone compared to active carbon and iron chloride
16.18% and 20.51% are not improved.
Embodiment 4
In the present embodiment using target water inlet 4, it is organic dirt blocking control method with embodiment 1, the difference is that:
Organic matter molecular mass distribution map is as shown in figure 11 in (I) water inlet water sample 4, three-dimensional fluorescence spectra such as Figure 12 institute
Show；As shown in Figure 11, water inlet water sample 4 is 103-104There is the water sample of obvious absorption peaks within the scope of Da, and 102-103Within the scope of Da
There is no the water sample of obvious absorption peaks, as shown in Figure 12, water sample 4 of intaking has obvious fluorescence response, IVth area Er and VIth area in Vth area
In without obvious fluorescence response, determine that the concentration ratio that most preferably adds of active carbon and iron chloride in water inlet water sample 4 is 3 as a result:
1；
(II) takes water sample 5ml to be measured, and the DOC concentration of measurement water inlet water sample 4 is 5mg/L after 0.45 μm of filter membrane excessively, according to DOC
Measurement result, determine active carbon adds concentration be 15mg/L, 22.5mg/L, 30mg/L, 37.5mg/L, 45mg/L, and
The removal rate of DOC in water sample under concentration is added in above-mentioned active carbon out, as shown in table 10:
10 different activities charcoal of table adds under concentration to the removal rate of DOC in water inlet water sample 4
According to active carbon add concentration and active carbon and iron chloride most preferably add concentration ratio, determine that iron chloride is thrown
Adding concentration ranges is 5mg/L, 7.5mg/L, 10mg/L, 12.5mg/L, 15mg/L, and obtains and add under concentration in above-mentioned iron chloride
DOC removal rate in water sample, as shown in table 11:
The different iron chloride of table 11 add under concentration to the removal rate of DOC in water inlet water sample 4
The DOC removal rate under concentration is added according to different activities charcoal in table 10, selects opposite DOC removal rate increment rate and phase
It is most preferably to add concentration that corresponding active carbon, which adds concentration 22.5mg/L, when adding the ratio between concentration increment rate closest to 1 to active carbon
A；The DOC removal rate under concentration is added according to iron chloride different in table 11, selects opposite DOC removal rate increment rate and opposite chlorination
Corresponding iron chloride adds concentration 10mg/L to iron when adding the ratio between concentration increment rate closest to 1 is most preferably to add concentration B；
(III) most preferably adds concentration according to determining active carbon and iron chloride, and adding active carbon into target water inlet 4 makes
Its concentration in target water inlet 4 is 22.5mg/L, and after absorption 0.8 hour, then adding iron chloride makes it in target water inlet 4
Concentration is 10mg/L, and coagulation removes active carbon and residual organic substances.
Target water inlet 4 pre-processes, by the combination of 22.5mg/L active carbon and 10mg/L iron chloride merely through 22.5mg/L
Pass through the mark of reverse osmosis membrane after Activated Carbon Pretreatment, when pre-processing merely through 10mg/L iron chloride and do not carry out any pretreatment
It is as shown in figure 13 that standardization produces the variation of water speed rate.
Each group standardization produces water speed rate when running 30h under above-mentioned 4 kinds of modes and standardization produces water speed rate enhancing rate such as
Shown in the following table 12:
Each group when the water inlet water sample 4 of table 12 runs 30h under each pretreatment mode
Standardization produces water speed rate and standardization produces water speed rate enhancing rate
As shown in Table 12, in the case where combining pretreatment mode, standardization produces water speed rate and pre-processes higher than other two when running 30h
Production water speed rate when mode is used alone, and it produces water speed rate enhancing rate and the time-division is used alone compared to active carbon and iron chloride
34.15% and 52.88% are not improved.
By Fig. 4, Fig. 7, Figure 10, Figure 13 in above-described embodiment it is found that after increasing pretreatment, the water speed rate decline of production slows down, and says
Organic matter is partially removed in bright water sample, stifled to reverse osmosis membrane dirt to mitigate, wherein progress is applied in combination in active carbon and iron chloride
The organic matter in water inlet can be further removed when pretreatment, the production water speed rate of system is above production water speed when exclusive use
Rate, and the production water speed rate decline for combining pretreatment mode is the slowest, reaches stable RO system influent quality.Thus illustrate, group
Pretreated mode is closed for controlling dirty stifled effect more effectively and stablizing and persistently slow down the dirt of RO system and block up rate, is had
Effect mitigates reverse osmosis membrane dirt and blocks up situation, increases the stability and runing time of the operation of RO system, to extend making for reverse osmosis membrane
With the service life, and reduce the operating cost of RO system, control RO film it is organic dirty in terms of be of great significance.
In above-mentioned 4 embodiments, if the determination method for most preferably adding concentration is replaced are as follows: selection DOC removal rate is maximum
The concentration that adds for being worth corresponding water treatment agent is most preferably to add concentration, and when running 30h under combining pretreatment mode, standardization is produced
Water speed rate enhancing rate does not improve about 16%-34% and 14%-53% compared to active carbon and iron chloride exclusive use time-division, and
And with the extension of time, the pretreated decrease speed for producing water speed rate of combination is greater than most preferably adding for above-described embodiment use
Density determination method, it is therefore preferable that is used in above-described embodiment most preferably adds density determination method.
The invention has the following advantages:
(1) invention creates a kind of organic dirty blocking control method of simple and easy reverse osmosis membrane, previous research is compensated for
In defect that preprocess method removal effect is still not clear；
(2) removal of present invention dissolved organic matter suitable for reverse osmosis membrane water inlet, can pointedly mitigate RO film has
Machine dirt is stifled；
(3) the present invention is based on the preprocessing process of iron chloride coagulation and activated carbon adsorption, raw material is easy to get, is low in cost；
(4) present invention according to the characteristics of water inlet water sample adjust iron chloride and active carbon add ratio and concentration, method letter
It is single easy.
Embodiment described above only expresses numerous embodiments of the invention, and the description thereof is more specific and detailed, but
It cannot be construed as a limitation to the scope of the present invention.It should be pointed out that for the ordinary skill people of this field
For member, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to of the invention
Protection scope.
Claims (10)
1. a kind of organic dirty blocking control method of reverse osmosis membrane, which comprises the following steps:
(1) two kinds of water treatment agents of iron chloride stock solution and clean active carbon are prepared；
(2) water inlet water sample is taken out from the water inlet of reverse osmosis membrane target, and water sample is divided into several pieces, adds active carbon and chlorination respectively
Iron obtains the dissolved organic carbon in the case where the difference of active carbon and iron chloride adds concentration in corresponding water sample to various concentration
(DOC) removal rate determines the best throwing for most preferably adding concentration A, iron chloride of active carbon according to concentration and DOC removal rate is added
Add concentration B, the concentration that adds is the concentration after water treatment agent is added to water sample in water sample；
(3) concentration is most preferably added according to the active carbon and iron chloride determined in (2), adding active carbon into target water inlet makes it
Concentration in target water inlet is A, and after absorption 0.5-1 hours, then adding iron chloride into target water inlet makes it intake in target
In concentration be B, coagulation removes active carbon and residual organic substances.
2. organic dirty blocking control method of reverse osmosis membrane according to claim 1, which is characterized in that in step (1), chlorine
Change the preparation and storage method of Blood lipids liquid are as follows: iron chloride is stored in airtight bottle, configuration concentration is the chlorine of 1g/L at room temperature
Change Blood lipids liquid as coagulant, is protected from light and is sealed after configuration is good.
3. organic dirty blocking control method of reverse osmosis membrane according to claim 1, which is characterized in that living in step (1)
The preparation and storage method of property charcoal are as follows: using the coconut husk granular activated carbon of partial size 1-2mm, active carbon is repeatedly clear with water using preceding needing
It washes, until washing rear active carbon water outlet dissolved organic carbon lower than 0.5mg/L, i.e., it is believed that preparing clean active carbon；It is clean
Active carbon is placed in 70 DEG C of drying in oven, is subsequently placed in be protected from light in beaker and is sealed.
4. organic dirty blocking control method of reverse osmosis membrane according to claim 1, which is characterized in that in step (2), survey
Surely DOC concentration value initial in water inlet water sample is a0Mg/L, measurement water inlet water sample in add water treatment agent and its add concentration be bi
Corresponding DOC concentration value is a when mg/LiMg/L, then the concentration that adds of water treatment agent is biWhen mg/L, corresponding DOC removal
Rate ciAre as follows: (ai-a0)/a0。
5. organic dirty blocking control method of reverse osmosis membrane according to claim 4, which is characterized in that in step (2),
The measuring method of DOC concentration are as follows: take water sample 5ml to be measured, measured in water sample after crossing 0.45 μm of filter membrane using TOC analyzer
DOC concentration.
6. organic dirty blocking control method of reverse osmosis membrane according to claim 1, which is characterized in that in step (2), really
The fixed method for most preferably adding concentration are as follows: the increment rate of opposite DOC removal rate and opposite water treatment agent is selected to add the increase of concentration
It is most preferably to add concentration that corresponding water treatment agent, which adds concentration, when the ratio between rate is closest to 1；Assuming that two phases of same water treatment agent
It is respectively b that neighbour, which adds concentration,i-1、bi(bi>bi-1), corresponding DOC removal rate is respectively ci-1、ci, then water treatment agent adds concentration
For biWhen, the increment rate of opposite DOC removal rate is (ci-ci-1)/ci-1, the increment rate that opposite water treatment agent adds concentration is
(bi-bi-1)/bi-1。
7. organic dirty blocking control method of reverse osmosis membrane according to claim 1, which is characterized in that in step (2), first
It determines the concentration ranges that add of active carbon and iron chloride, then is determined in concentration ranges adding and most preferably add concentration；
Add the determination method of concentration ranges are as follows: initial DOC concentration value is a in measurement water inlet water sample0Mg/L, then active carbon and
The concentration ranges that add of iron chloride are respectively (3-9) * a0Mg/L and (1-9) * a0mg/L。
8. organic dirty blocking control method of reverse osmosis membrane according to claim 7, which is characterized in that living in step (2)
Property charcoal add concentration be 3a0mg/L、4.5a0mg/L、6a0mg/L、7.5a0mg/L、9a0mg/L。
9. organic dirty blocking control method of reverse osmosis membrane according to claim 1, which is characterized in that in step (2), first
Determine active carbon and iron chloride most preferably adds concentration ratio, and further according to most preferably adding, adding for concentration ratio and active carbon is dense
That spends determining iron chloride adds concentration；
Most preferably add the determination method of concentration ratio are as follows: the molecular weight of organic matter in measurement feed water by reverse osmosis water sample is measured and obtained
To the three-dimensional fluorescence spectrum figure of reverse osmosis membrane water inlet water sample, judge whether water sample has (1) molecular weight 102-103Within the scope of Da
Having in obvious absorption peaks and IVth area (2) three-dimensional fluorescence spectrum Zhong and VIth area has both water sample features of obvious fluorescence response；If
Above two water sample feature is provided with, it is determined that the concentration ratio that most preferably adds of active carbon and iron chloride in water inlet water sample is 1:
1；If only having above-mentioned a certain water sample feature, it is determined that it is 2:1 that the two, which most preferably adds concentration ratio,；If above two water sample is special
Sign does not have, it is determined that it is 3:1 that the two, which most preferably adds concentration ratio,.
10. organic dirty blocking control method of reverse osmosis membrane described in -9 according to claim 1, which is characterized in that in step (2)
In, determine that the method for most preferably adding concentration A and most preferably adding concentration B includes the following steps:
(21) according to the organic molecule measure feature and three-dimensional fluorescence spectrum figure feature of water inlet water sample, active carbon and iron chloride are determined
Concentration ratio is most preferably added in water inlet water sample；
(22) the initial DOC concentration value of measurement water inlet water sample is a0Mg/L determines that active carbon adds concentration ranges in water inlet water sample
Respectively (3-9) * a0Mg/L, and obtain and add the removal rate of DOC in water sample under concentration in different activities charcoal；
(23) according to determine in (21) most preferably add active carbon in concentration ratio and (22) add concentration ranges, thus really
Determine iron chloride and add concentration ranges in water inlet water sample, and obtains and add the removal of DOC in water sample under concentration in different iron chloride
Rate；
(24) the DOC removal rate under concentration is added in difference according to Water condition agent in (22) and (23), opposite DOC is selected to go
Corresponding water treatment agent adds concentration when adding the ratio between increment rate of concentration closest to 1 except increment rate and the opposite water treatment agent of rate
Concentration is most preferably added for the water treatment agent.
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