CN103143260A - Cleaning agent composition and cleaning method for reverse osmosis membrane - Google Patents
Cleaning agent composition and cleaning method for reverse osmosis membrane Download PDFInfo
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- CN103143260A CN103143260A CN2011104028549A CN201110402854A CN103143260A CN 103143260 A CN103143260 A CN 103143260A CN 2011104028549 A CN2011104028549 A CN 2011104028549A CN 201110402854 A CN201110402854 A CN 201110402854A CN 103143260 A CN103143260 A CN 103143260A
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Abstract
The invention relates to a cleaning agent composition, comprising an A agent and a B agent. The A agent and the B agent are stored independently. The A agent comprises citric acid, hydrochloric acid and trisodium nitrilotriacetate; and the B agent contains an anionic surfactant and a dispersing agent, wherein the anionic surfactant is C8-C16 alkylbenzene sulfonate; and the dispersing agent is a (methyl)acrylic homopolymer and/or a (methyl)acrylic acid copolymer. The invention also relates to a method for cleaning a reverse osmosis membrane by using the above cleaning agent composition. A cleaning liquid prepared by the cleaning agent composition can clean the reverse osmosis membrane effectively, makes water yield of a reverse osmosis system restore basically, and can significantly reduce front-and-back pressure difference of the reverse osmosis membrane and reduce conductivity of produced water.
Description
Technical field
The present invention relates to a kind of cleansing composition, and the method for using this cleansing composition that reverse osmosis membrane is cleaned.
Background technology
Along with global water pollutes and water shortage, the equipment-reverse osmosis desalination plant of water treatment (RO) from the end of the fifties U.S. develop rapidly after having made the First high performance membrane.China adopts reverse osmosis desalination plant first the end of the seventies, but until the appearance of the new film of TFC-HR high desalination in 1993 just obtains large development.Counter-infiltration is a kind of function by means of permselectivity membrane, the membrane separation technique take pressure reduction as power, and during greater than the osmotic pressure of solution, hydrone sees through film and enters central tube through producing water flow passage, at one end flows out when institute of system plus-pressure.Enter the influent side that impurity (as ion, colloid, organic matter, bacterium) in water is trapped within film, flow out from dense water water side, thereby reach the purpose of isolation of purified.Reverse osmosis technology is compared with technology such as traditional evaporimeter, electrodialysis, and original characteristics and advantages is arranged, and its total salt clearance is high, the water rate of recovery is high, simple to operate, facility compact, easy to maintenance, can greatly reduce labour intensity, improve operation level and the automaticity of whole water treatment technology, when uniting use with ion-exchange unit, can greatly extend the regeneration period of ion-exchange unit, reduce the discharge capacity of soda acid, be conducive to saving water resource and improve environment.At present, reverse osmosis technology has been contained nearly all industrial department, particularly is widely used in the multiple fields such as concentrating of desalinization, pure water preparation, boiler feedwater, wastewater treatment and drinking-water, beverage and chemical products.
Because counter-infiltration is fully different from traditional filtration, latter's water all passes through filtering layer, rely on the dirt that backwash will be dammed to remove from filtering layer, counter-infiltration is to make a part of water to pass through film with the straight direction of costal fold, this moment, salt and colloidal substance were surperficial concentrated at film, relied on the dense water that the direction parallel with film flows that condensed matter is taken away.Reverse osmosis unit is after operation a period of time, and dense water side can accumulate the materials such as colloid, metal oxide, bacterium, organic matter, incrustation scale on film, causes the problems such as system's salt rejection rate decline, water yield reduction, pressure reduction increase, pollutes thereby can form film.Described film pollutes and refers to that the salt of suspended solid, microorganism and dissolving in water is because being concentrated, its concentration surpasses solubility product and generate unwanted deposit on the film surface, these pollutions can be caused by following reason: the 1) deposition of inorganic matter (fouling), common pollutant such as CaCO
3, CaSO
4, Ca
3(PO
4)
2Deng; 2) absorption of organic molecule; 3) deposition of particle (colloid pollution), common particle such as iron hydroxide, aluminium hydroxide, silicon dioxide colloid etc.; 4) metal oxide deposition, common metal oxide such as iron oxide; 5) adhesion of microorganism and growth (microbial contamination), common microorganism such as bacterium, algae class.
The film pollution of reverse osmosis unit is slowly development, if do not take measures in early days, pollution will damage the performance of membrane component within the relatively short time.In the ordinary course of things, when one of following symptoms appears in counter-infiltration system, show that reverse osmosis membrane is contaminated, should in time clean: under normal pressure, the product water flow compares with normal value the 10-15% that descended; In order to keep normal product water flow, the feed pressure after temperature correction has increased 10-15%; Product water salt transmitance has increased 10-15%.The water flux of reverse-osmosis membrane element is larger, and the rate of recovery is higher, the surperficial more vulnerable to pollution of its film.Under normal running (operation) conditions, all above-mentioned films pollute the aquifer yield that all will make reverse osmosis unit to be reduced, and pressure of supply water increases, and product water quality reduces, and has increased the cleaning frequency of reverse osmosis unit, has increased the product water rate and has used.Therefore, how to prevent or slow down reverse osmosis membrane and pollute, extend the service life of film and improve the membrane washing effect and become one of important subject in current reverse osmosis technology.
In the reverse osmosis unit running, dissimilar pollution usually occurs simultaneously, and influences each other, but at present the interaction between dissimilar pollution is known little about it.The reverse osmosis unit that uses in various fields is no matter how perfect it is, no matter also adopt the membrane component of which kind of type of which kind of manufacturer production, in a single day reverse osmosis unit puts into operation, in case feed liquid contacts with film, film pollutes and namely begins, finally all need to clean, only cleaning frequency length is different.
General reverse osmosis unit removal of pollutants can rinse with two kinds of methods of Chemical cleaning by physics and realize.Usually, if reducing has just appearred in the water permeability of film, enabled production water rinsed 20-40 minute the film surface under the low pressure high flow rate according to physical method, made the water permeability of film get to a certain extent recovery; And be heavily polluted at reverse osmosis membrane, and in the situation of the DeGrain that cleans with physical method, usually adopt chemical method to clean.Need to carry out chemical analysis to pollutant when adopting chemical method to clean, distinguish the kind of pollutant, and select corresponding chemicals and formula according to different pollutants.
The surface of reverse osmosis membrane is easy to be subjected to the pollution of foreign substance and produces dirt, and these foreign substances are present in the RO water inlet with various forms.Because the various places source quality is different, the preprocess method that adopts is not quite similar, so the pollutant of reverse osmosis membrane is also different.Surface water is affected by environment, complicated component is changeable, suspension, colloid, organic matter, microorganism are very many, and added again many inorganic, organic flocculants, flocculation aid, bactericide, reducing agent etc. in preprocessing process, so former hydromining is easy to contaminated with the reverse osmosis membrane of surface water and pollutant is complicated and changeable.
Usually mainly contain following several pollution modes with surface water as the counter-infiltration system at water source: (1) is because the deposition of dissolved organic matter causes the film surface contamination; (2) absorption due to various colloids causes the film surface contamination; (3) because the bacteria flora breeding causes to aquaporin and film surface obstruction; (4) solid particle in the feedwater stops up to aquaporin.
Experimental study shows, the contamination phenomenon that various different pollutants cause is different: various colloids, its symptom are that salt rejection rate slightly has reduction, and system pressure drop rises gradually, and system's aquifer yield reduces gradually; Various organic sediments, its symptom are that salt rejection rate may reduce, and system pressure drop raises gradually, and system's aquifer yield reduces gradually; Germ contamination, its symptom are that salt rejection rate may reduce, and system pressure drop obviously increases, and system's aquifer yield obviously reduces.
Many chemical reagent are all effective to removing dirt and other deposits.Chemical cleaning is in fact make selected chemical agent and deposit, dirt, corrosion product and affect flux rates and produce other pollutant reactions of water water quality, impels its disengaging film surperficial.Product four classes that these chemical reagent can be divided into acid, alkali, chelating agent and make by formula.The pollutant that film pollutes is different, and the cleaning agent of selecting is different.Select a kind of suitable cleaning agent, can play a multiplier effect.
US4976876 discloses the cleaning program that a kind of method by regular backwash is cleaned counter-infiltration system, but not mentioned Chemical cleaning part also wherein.US5499197 discloses a kind of automatic control scheme of counter-infiltration system, this cover counter-infiltration system is for the production of drinking water, monitor the various indexs of producing water by automatic control system, when the product water index that monitors is defective, the prompting counter-infiltration system that can automatically give the alarm needs to clean, and can not stop voluntarily the running of counter-infiltration system in the situation that get effective washing, but not mentioned concrete cleaning program also wherein.
Summary of the invention
The purpose of this invention is to provide a kind of cleansing composition that reverse osmosis membrane is cleaned of being applicable to, and adopt this cleansing composition to clean the method for reverse osmosis membrane.
The invention provides a kind of cleansing composition, wherein, said composition comprises A agent and B agent, and A agent and B agent independently preservation separately, and the A agent contains citric acid, hydrochloric acid and nitrilotriacetic acid trisodium salt; The B agent contains anion surfactant and dispersant, and described anion surfactant is the C8-C16 alkylbenzenesulfonate, and described dispersant is (methyl) acrylate homopolymer and/or (methyl) acrylic copolymer.
The present invention also provides a kind of method of using above-mentioned cleansing composition that reverse osmosis membrane is cleaned, and the method comprises the following steps:
(1) described A agent is mixed with the pH value and is the cleaning fluid L1 of 2.5-3.5;
(2) described B agent is mixed with the pH value and is the cleaning fluid L2 of 10.5-11.5;
(3) in turn reverse osmosis membrane is cleaned with described cleaning fluid L1 and described cleaning fluid L2.
In described cleansing composition of the present invention, the mixed acid that hydrochloric acid and citric acid form has good dissolving removal effect to dirty class and metal oxide-type deposit, citric acid easily with iron ion formation complex compound, compare with other acid solution and have stronger de-iron ability.Nitrilotriacetic acid trisodium salt is the chelating agent of excellent performance, there is more bonding position can form with calcium, magnesium, iron, barium plasma the complex compound of solubility, help to remove and stable reverse osmosis membrane on the dirt that washes down, and the dissolubility of nitrilotriacetic acid trisodium salt and chelating ability all are better than EDTA class chelating agent commonly used, and fully biodegradable, safety and environmental protection.
In the present invention, the cleaning fluid by the B agent that contains described anion surfactant and described dispersant (polymer class dirt dispersion agent) is mixed with has good dissolubility to silica isocolloid class material; Described polymer class dirt dispersion agent can effectively prevent easily to become the ion of dirt (as Ca
2+, PO
4 3-Deng) in the deposition on reverse osmosis membrane surface, thus stable, disperse the pollutant that washes down from reverse osmosis membrane, make cleaning more thorough, and prevent the generation of secondary pollution; Described anion surfactant can improve the wettability of cleaning agent, strengthen washing performance, increase the contact between chemical and dirt, especially can strengthen cleaning fluid to floatingization, the dispersion effect of organic matter, biological substance, reduce consumption and the washing time of flushing water.
In addition, compare with some nonionic surface active agent with cationic surfactant, anion surfactant can not be adsorbed onto on the reverse osmosis membrane surface, thereby can not affect the flux of reverse osmosis membrane.
Therefore, the cleaning fluid that is mixed with by described cleansing composition of the present invention can clean reverse osmosis membrane effectively, particularly can solve the metal oxide and the incrustation scale class that occur on reverse osmosis membrane pollutes, and the colloid that slowly occurs on reverse osmosis membrane, organic matter and microbiology class pollute, the aquifer yield of counter-infiltration system is recovered substantially, can significantly reduce the front and back pressure differential of reverse osmosis membrane, and reduce and produce electrical conductivity of water.
Description of drawings
Fig. 1 is the water treatment process figure of two-stage two-segment counter-infiltration system.
The specific embodiment
The invention provides a kind of cleansing composition, wherein, said composition comprises A agent and B agent, and A agent and B agent independently preservation separately,
The A agent contains citric acid, hydrochloric acid and nitrilotriacetic acid trisodium salt;
The B agent contains anion surfactant and dispersant, and described anion surfactant is the C8-C16 alkylbenzenesulfonate, and described dispersant is (methyl) acrylate homopolymer and/or (methyl) acrylic copolymer.
Composition according to the present invention, in described A agent, the total amount of citric acid and hydrochloric acid and the weight ratio of nitrilotriacetic acid trisodium salt can be 1-150: 6, be preferably 6-30: 6; The weight ratio of citric acid and hydrochloric acid can be 0.5-2: 1, be preferably 0.8-1.2: 1.
Composition according to the present invention, in described B agent, the weight ratio of described anion surfactant and described dispersant can be 100-4500: 3, be preferably 375-1500: 3.
Composition according to the present invention, for making described cleansing composition show better cleaning performance in the process that reverse osmosis membrane is cleaned, described anion surfactant is preferably the C12-C16 alkylbenzenesulfonate, more preferably be selected from least a in neopelex, myristyl benzene sulfonic acid sodium salt and cetyl benzene sulfonic acid sodium salt, most preferably be neopelex.In the present invention, described alkylbenzenesulfonate can be conventionally used as for this area the commercially available prod of anion surfactant.
Composition according to the present invention, for described dispersant, the number-average molecular weight of described (methyl) acrylate homopolymer and (methyl) acrylic copolymer can be 300-10000 separately, is preferably 300-6000.Further preferably, in order to reduce secondary pollution as far as possible, and guarantee that cleaning performance preferably, described dispersant select (methyl) acrylic copolymer.Described (methyl) acrylic copolymer can be conventionally used as for this area the various acrylic copolymers of dirt dispersion agent, for example, described (methyl) acrylic copolymer can be bipolymer and/or the terpolymer between (methyl) acrylic acid, (methyl) hydroxypropyl acrylate and 2-acrylamide-2-methyl-propyl sulfonic acid.Preferably, described dispersant is at least a in (methyl) acrylic acid/(methyl) hydroxypropyl acrylate copolymer, (methyl) acrylic acid/2-acrylamide-2-methyl-propyl sulfonic acid copolymer and (methyl) acrylic acid/(methyl) hydroxypropyl acrylate/2-acrylamide-2-methyl-propyl sulfonic acid copolymer.Most preferably, described dispersant is (methyl) acrylic acid/(methyl) hydroxypropyl acrylate/2-acrylamide-2-methyl-propyl sulfonic acid copolymer.
In embodiment more preferably, described anion surfactant is neopelex, and described dispersant is (methyl) acrylic acid/(methyl) hydroxypropyl acrylate/2-acrylamide-2-methyl-propyl sulfonic acid copolymer.In this preferred embodiment, described anion surfactant and described dispersant can improve cleaning performance synergistically.
Composition according to the present invention can also contain deionized water in described A agent and B agent separately, they are diluted to respectively the concentration that is fit to storage or uses arbitrarily.
The present invention also provides a kind of method of using above-mentioned cleansing composition that reverse osmosis membrane is cleaned, and the method comprises the following steps:
(1) described A agent is mixed with the pH value and is the cleaning fluid L1 of 2.5-3.5;
(2) described B agent is mixed with the pH value and is the cleaning fluid L2 of 10.5-11.5;
(3) in turn reverse osmosis membrane is cleaned with described cleaning fluid L1 and described cleaning fluid L2.
Method according to the present invention, described A agent and described B agent are respectively with above-described identical.
The cleaning method of reverse osmosis membrane according to the present invention, its main improvements are to have used the cleaning fluid that is mixed with by cleansing composition of the present invention, and the method for operating of concrete cleaning process and operating condition can be same or similar with the reverse osmosis membrane cleaning method of routine.
Method according to the present invention, because the acid-resistant corrosion of reverse osmosis membrane requires pH 〉=2.0 usually, alkali corrosion resistance requirement pH≤12, therefore, pH value with described cleaning fluid L1 in the present invention is controlled to be 2.5-3.5, and the pH value of described cleaning fluid L2 is controlled to be 10.5-11.5.
In order to guarantee that described method of the present invention has cleaning performance preferably, in described cleaning fluid L1, the concentration of nitrilotriacetic acid trisodium salt can be the 0.2-3 % by weight, is preferably the 0.5-1.5 % by weight.In this case, the total concentration of citric acid and hydrochloric acid can be the 0.5-5 % by weight, is preferably the 1.5-2.5 % by weight.In above-mentioned concentration range, need to add alkali in cleaning fluid in the process of the pH value of regulating cleaning fluid L1, described alkali for example can be NaOH and/or potassium hydroxide.
Method according to the present invention, described dispersant only need add on a small quantity can stablize, disperse the pollutant that washes down from reverse osmosis membrane, makes cleaning more thorough.Under preferable case, have cleaning performance preferably in order to guarantee described method of the present invention, in described cleaning fluid L2, the concentration of described anion surfactant can be the 0.2-3 % by weight, is preferably the 0.5-1.5 % by weight.In this case, the concentration of described dispersant can be 20-60mg/L, is preferably 30-40mg/L.In above-mentioned concentration range, need to add alkali in cleaning fluid in the process of the pH value of regulating cleaning fluid L2, described alkali for example can be NaOH and/or potassium hydroxide.
Method according to the present invention in order to improve cleaning performance, in step (3), is preferably first cleaned described reverse osmosis membrane with described cleaning fluid L1, then with described cleaning fluid L2, described reverse osmosis membrane is cleaned.More preferably, first with described cleaning fluid L1, described reverse osmosis membrane was cleaned 1-10 hour, then with described cleaning fluid L2, described reverse osmosis membrane was cleaned 1-10 hour.
In the present invention, described cleaning process is preferably carried out under lower operating pressure (as 0.4-0.6MPa) and larger dense water flux.Lower operating pressure can balance out the pressure drop from feedwater to dense water, and essentially no infiltration water produces, and can reduce so the again precipitation of booty on film; Larger dense water flux can ensure more cleaning fluid and wash away the reverse osmosis membrane surface, and the lip-deep pollutant of reverse osmosis membrane is helpful for removing.
Usually, for reverse osmosis water treatment system, 1 ℃ of the every raising of water temperature, the permeability rate of reverse osmosis membrane can increase approximately 3%.In the process that reverse osmosis membrane is cleaned, after cleaning fluid is heated to certain temperature, can when improving the reverse osmosis membrane water permeability, significantly improve cleaning fluid to the cleaning performance of reverse osmosis membrane; Yet due to the consideration of reverse osmosis membrane material and the scope of application, the temperature of cleaning fluid should not be over 50 ℃.
As shown in Figure 1, take the water treatment procedure of two-stage two-segment counter-infiltration system as example, the reverse osmosis water processing procedure can comprise usually: Jiang Yuanshui carries out pretreatment, to inject the first-stage reverse osmosis membrane treatment appts by high-pressure pump through pretreated water processes, the injection flush box of purifying waste water that will obtain after processing through the first-stage reverse osmosis film, then injecting the two-pass reverse osmosis membrane treatment appts by high-pressure pump carries out after-treatment, the pure water that obtains after collection and treatment.Preferably, former water is carried out pretreated method can adopt conventional method to implement, for example, preprocess method can be included in and add flocculant (as aluminium polychloride) in former water, to be adjusted to 6-7 through the pH value of the clear water that obtains after flocculation, and then add clorox to carry out sterilization, and then the water that obtains be sent into the filtration with manganese sand device and filter, filter through more medium filter and active carbon filter again, add afterwards sodium hydrogensulfite to regulate the water body oxidation-reduction potential to neutral.More preferably, before will injecting the first-stage reverse osmosis membrane treatment appts by high-pressure pump through pretreated water, adding antisludging agent (as the Flocon135 antisludging agent available from U.S. Biglake chemical Corp) through in pretreated water.
In the present invention, the cleaning method of described reverse osmosis membrane is applicable to the reverse osmosis membrane to various routines, particularly is applicable to PA membrane is cleaned.When described reverse osmosis membrane was PA membrane, cleaning method according to the present invention can obtain excellent cleaning performance.
In the present invention, the cleaning process of described reverse osmosis membrane preferably includes washing, cleaning fluid is washed (comprising cleaning fluid L1 and cleaning fluid L2) and three steps of washing.Concrete operating process as:
(1) water rinses reverse osmosis membrane, preferably rinses 10-15 minute;
(2) above-mentioned cleaning fluid L1 is added in the reverse osmosis membrane processing device, wash cycles was preferably cleaned 1-2 hour;
(3) cleaning fluid is rested in the reverse osmosis membrane processing device, reverse osmosis membrane is soaked, preferably soaked 3-6 hour; Perhaps every immersion is 20-30 minute, and wash cycles 10-30 minute, and make and soak and the temporal summation of wash cycles is 1-6 hour;
(4) discharge cleaning fluid, then water rinses reverse osmosis membrane, preferably rinses 10-40 minute;
(5) above-mentioned cleaning fluid L2 is added in the reverse osmosis membrane processing device, wash cycles was preferably cleaned 1-2 hour;
(6) cleaning fluid is rested in the reverse osmosis membrane processing device, reverse osmosis membrane is soaked, preferably soaked 3-6 hour; Perhaps every immersion is 20-30 minute, and wash cycles 10-30 minute, and make and soak and the temporal summation of wash cycles is 1-6 hour;
(7) discharge cleaning fluid, then water rinses reverse osmosis membrane, preferably rinses 10-40 minute.
The invention will be further described by the following examples.
Embodiment 1
The present embodiment is used for illustrating the cleaning method of described cleansing composition of the present invention and reverse osmosis membrane.
Take nitrilotriacetic acid trisodium salt 1kg, citric acid/mixed in hydrochloric acid acid 2kg, wherein the part by weight of citric acid and hydrochloric acid is 1: 1, add the 70kg deionized water, stirring is fully dissolved it, and adding deionized water to solution weight is 100kg, and be 3.0 with NaOH adjusting pH value, obtain cleaning fluid L1-1.
Take neopelex (reviving as chemical industry Co., Ltd available from Nanjing) 1kg, acrylic acid/hydroxypropyl acrylate/2-acrylamide-2-methyl-propyl sulfonic acid copolymer is (available from Shandong Taihe Water Treatment Co., Ltd., trade mark TH-613) 3.5g, add the 70kg deionized water, stirring is fully dissolved it, adding deionized water to solution weight is 100kg, and is 11.0 with NaOH adjusting pH value, obtains cleaning fluid L2-1.
According to process shown in Figure 1, adopt the two-stage two-segment counter-infiltration system that water quality parameter former water as shown in table 1 is processed, the water treatment amount is 200L/h, until the front and back pressure differential of first-stage reverse osmosis film increase 20% or pure water output stop when reducing 20%.Then, the reverse osmosis membrane in the two-stage two-segment counter-infiltration system (PA membrane, available from Hydranautics Water Management Equipment Ltd., trade mark RE4021-TL) is cleaned according to following process according to following:
(1) pressure with the first-stage reverse osmosis film is adjusted to 0.4MPa, and the dense aquatic products amount of regulating the first-stage reverse osmosis membrane treatment appts is 160L/h, and primary reverse osmosis water output is 40L/h, closes the two-pass reverse osmosis membrane treatment appts.Rinse the first-stage reverse osmosis film with counter-infiltration product water, rinsed 12 minutes;
(2) described cleaning fluid L1-1 is added the first-stage reverse osmosis membrane treatment appts, until till displacing original liquid, make described first-stage reverse osmosis membrane treatment appts circular flow 2 hours, then soaked 4 hours;
(3) discharge cleaning fluid;
(4) rinsed the first-stage reverse osmosis film 15 minutes with counter-infiltration product water;
(5) described cleaning fluid L2-1 is added the first-stage reverse osmosis membrane treatment appts, until till displacing original liquid, make described first-stage reverse osmosis membrane treatment appts circular flow 2 hours, then soaked 4 hours;
(6) discharge cleaning fluid;
(7) rinsed the first-stage reverse osmosis film 15 minutes with counter-infiltration product water;
(8) close the first-stage reverse osmosis membrane treatment appts.The pressure of two-pass reverse osmosis film is adjusted to 0.4MPa, and the dense aquatic products amount of regulating the two-pass reverse osmosis membrane treatment appts is 160L/h, and two-pass reverse osmosis aquatic products amount is 40L/h, rinses the two-pass reverse osmosis film 12 minutes with counter-infiltration product water;
(9) described cleaning fluid L1-1 is added the two-pass reverse osmosis membrane treatment appts, until till displacing original liquid, make described two-pass reverse osmosis membrane treatment appts circular flow 1.5 hours, then soaked 2 hours;
(10) discharge cleaning fluid;
(11) rinsed the two-pass reverse osmosis film 15 minutes with counter-infiltration product water;
(12) described cleaning fluid L2-1 is added the two-pass reverse osmosis membrane treatment appts, until till displacing original liquid, make described two-pass reverse osmosis membrane treatment appts circular flow 1.5 hours, then soaked 2 hours;
(13) discharge cleaning fluid;
(14) rinsed the two-pass reverse osmosis film 15 minutes with counter-infiltration product water;
(15) first-stage reverse osmosis membrane treatment appts and two-pass reverse osmosis membrane treatment appts are opened simultaneously, the pressure 0.4MPa that keeps the first-stage reverse osmosis film, the pressure of two-pass reverse osmosis film is 0.6MPa, cleans counter-infiltration system with counter-infiltration product water circulation and discharges after 20 minutes.
Table 1
| Project | Calcium ion | Total alkalinity | Total hardness | pH | Chlorion |
| Numerical value | 170.4 | 189.5 | 260.3 | 7.82 | 35.7 |
| Project | Dissolved oxygen | Positive phosphorus | Total iron | Sulfate | COD |
| Numerical value | 9.9 | 0.72 | 0.08 | 46.9 | 13 |
| Project | Electrical conductivity | Potassium ion | Suspension | Soluble solids | Ammonia nitrogen |
| Numerical value | 571 | 2.2 | 4.2 | 327 | 1.973 |
Annotate: the unit of electrical conductivity is μ s/cm, and the unit of all the other parameters is mg/L.
Embodiment 2
Take nitrilotriacetic acid trisodium salt 2.8kg, citric acid/mixed in hydrochloric acid acid 4.8kg, wherein the part by weight of citric acid and hydrochloric acid is 1.1: 1, add the 70kg deionized water, stirring is fully dissolved it, adding deionized water to solution weight is 100kg, and is 3.1 with KOH adjusting pH value, obtains cleaning fluid L1-2.
Take neopelex (reviving as chemical industry Co., Ltd available from Nanjing) 2.8kg, acrylic acid/hydroxypropyl acrylate/2-acrylamide-2-methyl-propyl sulfonic acid copolymer is (available from Shandong Taihe Water Treatment Co., Ltd., trade mark TH-613) 5.9g, add the 70kg deionized water, stirring is fully dissolved it, adding deionized water to solution weight is 100kg, and is 11.1 with KOH adjusting pH value, obtains cleaning fluid L2-2.
According to the method for embodiment 1, the reverse osmosis membrane in the two-stage two-segment counter-infiltration system is cleaned, difference is to replace respectively cleaning fluid L1-1 and the cleaning fluid L2-1 of use in embodiment 1 with cleaning fluid L1-2 and cleaning fluid L2-2.
Comparative Examples 1
According to the method for embodiment 1, the reverse osmosis membrane in the two-stage two-segment counter-infiltration system is cleaned, difference is to replace respectively the cleaning fluid L1-1 and the cleaning fluid L2-1 that use in embodiment 1 with cleaning fluid L2-2.
Comparative Examples 2
According to the method for embodiment 1, the reverse osmosis membrane in the two-stage two-segment counter-infiltration system is cleaned, difference is to replace respectively the cleaning fluid L1-1 and the cleaning fluid L2-1 that use in embodiment 1 with cleaning fluid L1-2.
Embodiment 3
Take nitrilotriacetic acid trisodium salt 1.4kg, citric acid/mixed in hydrochloric acid acid 2.4kg, wherein the part by weight of citric acid and hydrochloric acid is 0.9: 1, add the 70kg deionized water, stirring is fully dissolved it, adding deionized water to solution weight is 100kg, and is 3.2 with NaOH adjusting pH value, obtains cleaning fluid L1-3.
Take neopelex (reviving as chemical industry Co., Ltd available from Nanjing) 1.4kg, acrylic acid/hydroxypropyl acrylate/2-acrylamide-2-methyl-propyl sulfonic acid copolymer is (available from Shandong Taihe Water Treatment Co., Ltd., trade mark TH-613) 3.9g, add the 70kg deionized water, stirring is fully dissolved it, adding deionized water to solution weight is 100kg, and is 11.2 with NaOH adjusting pH value, obtains cleaning fluid L2-3.
According to the method for embodiment 1, the reverse osmosis membrane in the two-stage two-segment counter-infiltration system is cleaned, difference is to replace respectively cleaning fluid L1-1 and the cleaning fluid L2-1 of use in embodiment 1 with cleaning fluid L1-3 and cleaning fluid L2-3.
Embodiment 4
Take nitrilotriacetic acid trisodium salt 0.6kg, citric acid/mixed in hydrochloric acid acid 1.6kg, wherein the part by weight of citric acid and hydrochloric acid is 0.8: 1, add the 70kg deionized water, stirring is fully dissolved it, adding deionized water to solution weight is 100kg, and is 3.3 with KOH adjusting pH value, obtains cleaning fluid L1-4.
Take neopelex (reviving as chemical industry Co., Ltd available from Nanjing) 0.6kg, acrylic acid/hydroxypropyl acrylate/2-acrylamide-2-methyl-propyl sulfonic acid copolymer is (available from Shandong Taihe Water Treatment Co., Ltd., trade mark TH-613) 3.0g, add the 70kg deionized water, stirring is fully dissolved it, adding deionized water to solution weight is 100kg, and is 11.3 with KOH adjusting pH value, obtains cleaning fluid L2-4.
According to the method for embodiment 1, the reverse osmosis membrane in the two-stage two-segment counter-infiltration system is cleaned, difference is to replace respectively cleaning fluid L1-1 and the cleaning fluid L2-1 of use in embodiment 1 with cleaning fluid L1-4 and cleaning fluid L2-4.
Embodiment 5
Take nitrilotriacetic acid trisodium salt 0.3kg, citric acid/mixed in hydrochloric acid acid 0.6kg, wherein the part by weight of citric acid and hydrochloric acid is 1.2: 1, add the 70kg deionized water, stirring is fully dissolved it, adding deionized water to solution weight is 100kg, and is 3.4 with NaOH adjusting pH value, obtains cleaning fluid L1-5.
Take neopelex (reviving as chemical industry Co., Ltd available from Nanjing) 0.3kg, acrylic acid/hydroxypropyl acrylate/2-acrylamide-2-methyl-propyl sulfonic acid copolymer is (available from Shandong Taihe Water Treatment Co., Ltd., trade mark TH-613) 2.1g, add the 70kg deionized water, stirring is fully dissolved it, adding deionized water to solution weight is 100kg, and is 11.4 with NaOH adjusting pH value, obtains cleaning fluid L1-5.
According to the method for embodiment 1, the reverse osmosis membrane in the two-stage two-segment counter-infiltration system is cleaned, difference is to replace respectively cleaning fluid L1-1 and the cleaning fluid L2-1 of use in embodiment 1 with cleaning fluid L1-5 and cleaning fluid L2-5.
Embodiment 6
Take nitrilotriacetic acid trisodium salt 1.1kg, citric acid/mixed in hydrochloric acid acid 1.9kg, wherein the part by weight of citric acid and hydrochloric acid is 1: 1, add the 70kg deionized water, stirring is fully dissolved it, and adding deionized water to solution weight is 100kg, and be 2.9 with KOH adjusting pH value, obtain cleaning fluid L1-6.
Take myristyl benzene sulfonic acid sodium salt (reviving as chemical industry Co., Ltd available from Nanjing) 1.1kg, acrylic acid/hydroxypropyl acrylate copolymer is (available from Shandong Taihe Water Treatment Co., Ltd., trade mark T225) 3.4g, add the 70kg deionized water, stirring is fully dissolved it, adding deionized water to solution weight is 100kg, and is 10.9 with KOH adjusting pH value, obtains cleaning fluid L1-6.
According to the method for embodiment 1, the reverse osmosis membrane in the two-stage two-segment counter-infiltration system is cleaned, difference is to replace respectively cleaning fluid L1-1 and the cleaning fluid L2-1 of use in embodiment 1 with cleaning fluid L1-6 and cleaning fluid L2-6.
Embodiment 7
Take nitrilotriacetic acid trisodium salt 1.2kg, citric acid/mixed in hydrochloric acid acid 1.8kg, wherein the part by weight of citric acid and hydrochloric acid is 1: 1, add the 70kg deionized water, stirring is fully dissolved it, adding deionized water to solution weight is 100kg, and is 2.8 with NaOH adjusting pH value, obtains cleaning fluid L1-7.
Take cetyl benzene sulfonic acid sodium salt (reviving as chemical industry Co., Ltd available from Nanjing) 0.9kg, acrylic acid/2-acrylamide-2-methyl-propyl sulfonic acid copolymer is (available from Shandong Taihe Water Treatment Co., Ltd., trade mark AA-AMPS) 3.6g, add the 70kg deionized water, stirring is fully dissolved it, adding deionized water to solution weight is 100kg, and is 10.8 with NaOH adjusting pH value, obtains cleaning fluid L1-7.
According to the method for embodiment 1, the reverse osmosis membrane in the two-stage two-segment counter-infiltration system is cleaned, difference is to replace respectively cleaning fluid L1-1 and the cleaning fluid L2-1 of use in embodiment 1 with cleaning fluid L1-7 and cleaning fluid L2-7.
Embodiment 8
Take nitrilotriacetic acid trisodium salt 0.9kg, citric acid/mixed in hydrochloric acid acid 2.1kg, wherein the part by weight of citric acid and hydrochloric acid is 1: 1, add the 70kg deionized water, stirring is fully dissolved it, and adding deionized water to solution weight is 100kg, and be 2.7 with KOH adjusting pH value, obtain cleaning fluid L1-8.
Take ten sodium alkyl benzene sulfonates (reviving as chemical industry Co., Ltd available from Nanjing) 1.2kg, acrylic acid/hydroxypropyl acrylate copolymer is (available from Shandong Taihe Water Treatment Co., Ltd., trade mark T225) 3.3g, add the 70kg deionized water, stirring is fully dissolved it, adding deionized water to solution weight is 100kg, and is 10.7 with KOH adjusting pH value, obtains cleaning fluid L1-8.
According to the method for embodiment 1, the reverse osmosis membrane in the two-stage two-segment counter-infiltration system is cleaned, difference is to replace respectively cleaning fluid L1-1 and the cleaning fluid L2-1 of use in embodiment 1 with cleaning fluid L1-8 and cleaning fluid L2-8.
Embodiment 9
Take nitrilotriacetic acid trisodium salt 0.8kg, citric acid/mixed in hydrochloric acid acid 2.2kg, wherein the part by weight of citric acid and hydrochloric acid is 1: 1, add the 70kg deionized water, stirring is fully dissolved it, adding deionized water to solution weight is 100kg, and is 2.6 with NaOH adjusting pH value, obtains cleaning fluid L1-9.
Take eight sodium alkyl benzene sulfonates (reviving as chemical industry Co., Ltd available from Nanjing) 0.8kg, polyacrylic acid is (available from Shandong Taihe Water Treatment Co., Ltd., trade mark PAA) 3.7g, add the 70kg deionized water, stirring is fully dissolved it, adding deionized water to solution weight is 100kg, and is 10.6 with NaOH adjusting pH value, obtains cleaning fluid L1-9.
According to the method for embodiment 1, the reverse osmosis membrane in the two-stage two-segment counter-infiltration system is cleaned, difference is to replace respectively cleaning fluid L1-1 and the cleaning fluid L2-1 of use in embodiment 1 with cleaning fluid L1-9 and cleaning fluid L2-9.
Test case
,, according to process shown in Figure 1 the former water that water quality parameter is as shown in table 1 is processed again through after cleaning at above-mentioned two-stage two-segment counter-infiltration system, the water treatment amount is 200L/h.When again processing, the performance indications of first-stage reverse osmosis film and two-pass reverse osmosis film are as shown in table 2 below.
Table 2
Annotate: the unit of pure water flow, concentrated stream amount is L/h, and pressure drop unit is MPa, and electrical conductivity unit is μ s/cm.
As can be seen from Table 2, the cleaning fluid that is mixed with by described cleansing composition of the present invention can clean reverse osmosis membrane effectively, the aquifer yield of counter-infiltration system is recovered substantially, can significantly be reduced the front and back pressure differential of reverse osmosis membrane, and reduce and produce electrical conductivity of water.
Claims (10)
1. a cleansing composition, is characterized in that, said composition comprises A agent and B agent, and A agent and B agent independently preservation separately,
The A agent contains citric acid, hydrochloric acid and nitrilotriacetic acid trisodium salt;
The B agent contains anion surfactant and dispersant, and described anion surfactant is the C8-C16 alkylbenzenesulfonate, and described dispersant is (methyl) acrylate homopolymer and/or (methyl) acrylic copolymer.
2. composition according to claim 1, wherein, in described A agent, the total amount of citric acid and hydrochloric acid and the weight ratio of nitrilotriacetic acid trisodium salt are 1-150: 6, be preferably 6-30: 6; The weight ratio of citric acid and hydrochloric acid is 0.5-2: 1, be preferably 0.8-1.2: 1.
3. composition according to claim 1, wherein, in described B agent, the weight ratio of described anion surfactant and described dispersant is 100-4500: 3, be preferably 375-1500: 3.
4. according to claim 1 or 3 described compositions, wherein, described anion surfactant is to be selected from least a in neopelex, myristyl benzene sulfonic acid sodium salt and cetyl benzene sulfonic acid sodium salt.
5. according to claim 1 or 3 described compositions, wherein, described dispersant is (methyl) acrylic copolymer, and described (methyl) acrylic copolymer is bipolymer and/or the terpolymer between (methyl) acrylic acid, (methyl) hydroxypropyl acrylate and 2-acrylamide-2-methyl-propyl sulfonic acid.
6. composition according to claim 5, wherein, described dispersant is at least a in (methyl) acrylic acid/(methyl) hydroxypropyl acrylate copolymer, (methyl) acrylic acid/2-acrylamide-2-methyl-propyl sulfonic acid copolymer and (methyl) acrylic acid/(methyl) hydroxypropyl acrylate/2-acrylamide-2-methyl-propyl sulfonic acid copolymer.
7. a right to use requires the method that in 1-6, the described cleansing composition of any one cleans reverse osmosis membrane, and the method comprises the following steps:
(1) described A agent is mixed with the pH value and is the cleaning fluid L1 of 2.5-3.5;
(2) described B agent is mixed with the pH value and is the cleaning fluid L2 of 10.5-11.5;
(3) in turn reverse osmosis membrane is cleaned with described cleaning fluid L1 and described cleaning fluid L2.
8. method according to claim 7, wherein, in step (3), first clean described reverse osmosis membrane with described cleaning fluid L1, then with described cleaning fluid L2, described reverse osmosis membrane cleaned.
9. according to claim 7 or 8 described methods, wherein, in described cleaning fluid L1, the concentration of nitrilotriacetic acid trisodium salt is the 0.2-3 % by weight, is preferably the 0.5-1.5 % by weight.
10. according to claim 7 or 8 described methods, wherein, in described cleaning fluid L2, the concentration of described anion surfactant is the 0.2-3 % by weight, is preferably the 0.5-1.5 % by weight.
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