CN103143260B - 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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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 using this cleansing composition to clean reverse osmosis membrane.
Background technology
Along with global water pollutions and water shortage, the equipment-reverse osmosis desalination plant (RO) of water treatment from the end of the fifties U.S. develop rapidly after having made 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, take pressure reduction as the membrane separation technique of power, and when system institute plus-pressure is greater than the osmotic pressure of solution, hydrone enters central tube through film through producing water flow passage, at one end flows out.The impurity (as ion, colloid, organic matter, bacterium) entered in water is trapped within the influent side of film, flows out, thus reach the object of isolation of purified from dense water water side.Reverse osmosis technology is compared with the technology such as traditional evaporimeter, electrodialysis, and have original characteristics and advantages, its total salt clearance is high, Water Sproading rate is high, simple to operate, facility compact, easy to maintenance, greatly can reduce labour intensity, improve operation level and the automaticity of whole water treatment technology, when with ion-exchange unit conbined usage, greatly can extend the regeneration period of ion-exchange unit, reduce the discharge capacity of soda acid, be conducive to saving water resource and environmental protect.At present, reverse osmosis technology has covered nearly all industrial department, is particularly widely used in the multiple fields such as concentrated of desalinization, pure water preparation, boiler feedwater, wastewater treatment and drinking-water, beverage and chemical products.
Because counter-infiltration is completely different from traditional filtration, the latter's water all passes through filtering layer, backwash is relied on to be removed from filtering layer by the dirt dammed, counter-infiltration is then make a part of water pass through film with the direction straight with costal fold, now salt and colloidal substance concentrate on film surface, rely on the dense water of the direction flowing parallel with film to be taken away by condensed matter.Reverse osmosis unit is after operation a period of time, and on film, dense water side can accumulate the materials such as colloid, metal oxide, bacterium, organic matter, incrustation scale, causes the problems such as the decline of system salt rejection rate, water yield reduction, pressure reduction increase, thus can form fouling membrane.Described fouling membrane refer to suspended solid in water, microorganism and dissolving salt because being concentrated, its concentration exceedes solubility product and generates unwanted deposit on the surface of the film, these pollutions can be caused by following reason: the 1) deposition (fouling) of inorganic matter, common pollutant is as CaCO
3, CaSO
4, Ca
3(PO
4)
2deng; 2) absorption of organic molecule; 3) deposition (colloid pollution) of particle, common particle is as iron hydroxide, aluminium hydroxide, silicon dioxide colloid etc.; 4) metal oxide deposition, common metal oxide is as iron oxide; 5) adhesion of microorganism and growth (microbial contamination), common microorganism is as bacterium, algae class.
The fouling membrane of reverse osmosis unit is slowly development, if do not taken measures in early days, pollutes the performance will damaging membrane component within the relatively short time.In the ordinary course of things, when counter-infiltration system occurs that following symptoms for the moment, show that reverse osmosis membrane is contaminated, should clean in time: under normal pressure, product water flow have dropped 10-15% compared with normal value; In order to maintain normal product water flow, the feed pressure after temperature correction adds 10-15%; Product water salt transmitance adds 10-15%.The water flux of reverse-osmosis membrane element is larger, and the rate of recovery is higher, then its film surface more vulnerable to pollution.Under normal operating conditions, all above-mentioned fouling membrane all will make the aquifer yield of reverse osmosis unit reduce, and pressure of supply water increases, and product water quality reduces, and adds the cleaning frequency of reverse osmosis unit, add and produce water rate use.Therefore, how to prevent or slow down reverse osmosis membrane and pollute, extend service life of film and the cleaning performance improving film has become one of important subject in current reverse osmosis technology.
In reverse osmosis unit running, dissimilar pollution usually occurs simultaneously, and influences each other, but knows little about it to the interaction between dissimilar pollution at present.The reverse osmosis unit used in various field, no matter how perfect it is, no matter also adopt the membrane component of which kind of type of which kind of manufacturer production, reverse osmosis unit is once put into operation, once feed liquid contacts with film, namely fouling membrane starts, final all needs cleans, and only cleaning frequency length is different.
The removal of general reverse osmosis unit pollutant is rinsed by physics and Chemical cleaning two kinds of methods realize.Usually, if reducing just has appearred in the water permeability of film, enabled production water, has carried out flushing 20-40 minute to film surface according to physical method under low pressure high flow rate, makes the water permeability of film obtain recovery to a certain extent; And be heavily polluted at reverse osmosis membrane, and when DeGrain with physical method cleaning, chemical method is usually adopted to clean.Needing to carry out chemical analysis to pollutant when adopting chemical method to clean, distinguishing the kind of pollutant, and selecting corresponding chemicals and formula according to different pollutants.
The surface of reverse osmosis membrane is easy to the pollution by foreign substance and produces dirt, and these foreign substances are present in RO water inlet in a variety of manners.Because various places source quality is different, the preprocess method adopted 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 the reverse osmosis membrane of former hydromining surface water is easy to contaminated and pollutant is complicated and changeable.
Usually following several pollution modes is mainly contained using surface water as the counter-infiltration system at water source: (1) causes film surface contamination due to the deposition of dissolved organic matter; (2) film surface contamination is caused due to the absorption of various colloid; (3) because bacteria flora breeding causes to aquaporin and the blocking of film surface; (4) solid particle in feedwater blocks to aquaporin.
Experimental study shows, the contamination phenomenon that various different pollutant causes is different: various colloid, and its symptom is that salt rejection rate is in a slight decrease, and system pressure drop rises gradually, and system aquifer yield reduces gradually; Various organic sediment, its symptom is that salt rejection rate may reduce, and system pressure drop raises gradually, and system aquifer yield reduces gradually; Germ contamination, its symptom is that salt rejection rate may reduce, and system pressure drop obviously increases, and system aquifer yield obviously reduces.
Many chemical reagent to removal dirt and other deposits all effective.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 it to depart from film surface.Product four class that these chemical reagent can be divided into acid, alkali, chelating agent and manufacture by formula.The pollutant of fouling membrane is different, then the cleaning agent selected is different.Select a kind of suitable cleaning agent, can play a multiplier effect.
US4976876 discloses the cleaning program of a kind of method by regular backwash cleaning counter-infiltration system, but wherein and not mentioned Chemical cleaning part.US5499197 discloses a kind of automatic control scheme of counter-infiltration system, this cover counter-infiltration system is for the production of drinking water, the various indexs of water are produced by automatic control system monitoring, when the product water index monitored is defective, the prompting counter-infiltration system that can automatically give the alarm needs cleaning, and the running of counter-infiltration system can be stopped voluntarily when not getting effective washing, but wherein and not mentioned concrete cleaning program.
Summary of the invention
The object of this invention is to provide a kind of cleansing composition being applicable to that reverse osmosis membrane is cleaned, 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 are independently preserved separately, and A agent contains citric acid, hydrochloric acid and nitrilotriacetic acid trisodium salt; B agent contains anion surfactant and dispersant, and described anion surfactant is C8-C16 alkylbenzenesulfonate, and described dispersant is (methyl) acrylate homopolymer and/or (methyl) acrylic copolymer.
Present invention also offers a kind of method using above-mentioned cleansing composition to clean reverse osmosis membrane, the method comprises the following steps:
(1) described A agent is mixed with the cleaning fluid L1 that pH value is 2.5-3.5;
(2) described B agent is mixed with the cleaning fluid L2 that pH value is 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 of hydrochloric acid and citric acid composition has dirty class and metal oxide-type deposit and well dissolves removal effect, citric acid easily and iron ion form complex compound, there is stronger de-iron ability compared with other acid solution.Nitrilotriacetic acid trisodium salt is the chelating agent of excellent performance, there is more bonding position can form the complex compound of solubility with calcium, magnesium, iron, barium plasma, contribute to the dirt removed and stable reverse osmosis membrane washes down, and the dissolubility of nitrilotriacetic acid trisodium salt and chelating ability are all better than conventional EDTA quasi-chelate compound, and fully biodegradable, safety and environmental protection.
In the present invention, the cleaning fluid be mixed with by the B agent containing described anion surfactant and described dispersant (polymer class dirt dispersion agent), 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) deposition on reverse osmosis membrane surface, thus stablize, 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 floatingization, the dispersion effect of cleaning fluid to 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 reverse osmosis membrane on the surface, thus can not affect the flux of reverse osmosis membrane.
Therefore, the cleaning fluid be mixed with by described cleansing composition of the present invention can clean reverse osmosis membrane effectively, particularly can solve the metal oxide that reverse osmosis membrane occurs and the pollution of incrustation scale class, and colloid, organic matter and microbiology class that reverse osmosis membrane slowly occurs pollute, the aquifer yield of counter-infiltration system is recovered substantially, significantly can reduce the front and back pressure differential of reverse osmosis membrane, and reduce product electrical conductivity of water.
Accompanying drawing explanation
Fig. 1 is the water treatment process figure of two-stage two-segment counter-infiltration system.
Detailed description of the invention
The invention provides a kind of cleansing composition, wherein, said composition comprises A agent and B agent, and A agent and B agent are independently preserved separately,
A agent contains citric acid, hydrochloric acid and nitrilotriacetic acid trisodium salt;
B agent contains anion surfactant and dispersant, and described anion surfactant is 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, are preferably 6-30: 6; The weight ratio of citric acid and hydrochloric acid can be 0.5-2: 1, is 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, is preferably 375-1500: 3.
Composition according to the present invention, in the process that reverse osmosis membrane is cleaned, better cleaning performance is shown for making described cleansing composition, described anion surfactant is preferably C12-C16 alkylbenzenesulfonate, be more preferably at least one be selected from neopelex, myristyl benzene sulfonic acid sodium salt and cetyl benzenesulfonic acid sodium, most preferably be neopelex.In the present invention, described alkylbenzenesulfonate can be conventionally used as the commercially available prod of anion surfactant for this area.
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 ensure good cleaning performance, described dispersant selects (methyl) acrylic copolymer.Described (methyl) acrylic copolymer can be conventionally used as the various acrylic copolymers of dirt dispersion agent for this area, such as, described (methyl) acrylic copolymer can be bipolymer between (methyl) acrylic acid, (methyl) hydroxypropyl acrylate and 2-acrylamide-2-methyl-propane sulfonic acid and/or terpolymer.Preferably, described dispersant is at least one in (methyl) acrylic acid/(methyl) hydroxypropyl acrylate copolymer, (methyl) acrylic acid/2-acrylamide-2-methyl-propane sulfonic acid copolymer and (methyl) acrylic acid/(methyl) hydroxypropyl acrylate/2-acrylamide-2-methyl-propane sulfonic acid copolymer.Most preferably, described dispersant is (methyl) acrylic acid/(methyl) hydroxypropyl acrylate/2-acrylamide-2-methyl-propane sulfonic acid copolymer.
In more preferably embodiment, described anion surfactant is neopelex, and described dispersant is (methyl) acrylic acid/(methyl) hydroxypropyl acrylate/2-acrylamide-2-methyl-propane 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 to be diluted to respectively the arbitrary concentration being applicable to storing or use.
Present invention also offers a kind of method using above-mentioned cleansing composition to clean reverse osmosis membrane, the method comprises the following steps:
(1) described A agent is mixed with the cleaning fluid L1 that pH value is 2.5-3.5;
(2) described B agent is mixed with the cleaning fluid L2 that pH value is 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 is identical with above-described respectively with described B agent.
The cleaning method of reverse osmosis membrane according to the present invention, its main improvements are to employ the cleaning fluid be 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 requires pH≤12, therefore, the pH value of described cleaning fluid L1 is controlled for 2.5-3.5 in the present invention, the pH value of described cleaning fluid L2 is controlled as 10.5-11.5.
In order to ensure that described method of the present invention has good cleaning performance, in described cleaning fluid L1, the concentration of nitrilotriacetic acid trisodium salt can be 0.2-3 % by weight, is preferably 0.5-1.5 % by weight.In this case, the total concentration of citric acid and hydrochloric acid can be 0.5-5 % by weight, is preferably 1.5-2.5 % by weight.In above-mentioned concentration range, need to add alkali in cleaning fluid in the process of pH value regulating cleaning fluid L1, described alkali can be such as NaOH and/or potassium hydroxide.
Method according to the present invention, described dispersant only need add a small amount of i.e. Absorbable organic halogens, disperse the pollutant that washes down from reverse osmosis membrane, makes cleaning more thorough.Under preferable case, in order to ensure that described method of the present invention has good cleaning performance, in described cleaning fluid L2, the concentration of described anion surfactant can be 0.2-3 % by weight, is preferably 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 pH value regulating cleaning fluid L2, described alkali can be such as NaOH and/or potassium hydroxide.
Method according to the present invention, in order to improve cleaning performance, in step (3), preferably first cleaning described reverse osmosis membrane with described cleaning fluid L1, then cleaning described reverse osmosis membrane with described cleaning fluid L2.More preferably, first with described cleaning fluid L1, cleaning 1-10 hour is carried out to described reverse osmosis membrane, then with described cleaning fluid L2, cleaning 1-10 hour is carried out to described reverse osmosis membrane.
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 booty precipitating again on film like this; Larger dense water flux can ensure more cleaning fluid and wash away reverse osmosis membrane surface, helpful for the pollutant removed on reverse osmosis membrane surface.
Usually, for reverse osmosis water treatment system, water temperature often improves 1 DEG C, and the permeability rate of reverse osmosis membrane can increase about 3%.In the process that reverse osmosis membrane is cleaned, after cleaning fluid is heated to certain temperature, while raising reverse osmosis membrane water permeability, can significantly improve cleaning fluid to the cleaning performance of reverse osmosis membrane; But due to the consideration of reverse osmosis membrane material and the scope of application, the temperature of cleaning fluid is no more than 50 DEG C.
As shown in Figure 1, for the water treatment procedure of two-stage two-segment counter-infiltration system, anti-penetration wastewater disposal process can comprise usually: Jiang Yuanshui carries out pretreatment, first-stage reverse osmosis membrane treatment appts will be injected through pretreated water by high-pressure pump to process, by the injection flush box of purifying waste water obtained after the process of first-stage reverse osmosis film, then inject two-pass reverse osmosis membrane treatment appts by high-pressure pump and carry out after-treatment, the pure water obtained after collecting process.Preferably, former water being carried out pretreated method can adopt conventional method to implement, such as, preprocess method can be included in former water and add flocculant (as aluminium polychloride), the pH value of the clear water obtained after flocculation is adjusted to 6-7, then adds clorox and carry out sterilization, then the water obtained is sent into manganese sand filter and filter, filter through more medium filter and active carbon filter again, add sodium hydrogensulfite afterwards and regulate water body oxidation-reduction potential to neutral.More preferably, before pretreated water injects first-stage reverse osmosis membrane treatment appts by high-pressure pump, antisludging agent (the Flocon135 antisludging agent as purchased from American Biglake chemical Corp) will added in pretreated water.
In the present invention, the cleaning method of described reverse osmosis membrane is applicable to the reverse osmosis membrane to various routine, is particularly applicable to clean PA membrane.When described reverse osmosis membrane is 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 include washing, cleaning fluid wash (comprising cleaning fluid L1 and cleaning fluid L2) and washing three steps.Concrete operating process as:
(1) rinse reverse osmosis membrane with water, preferably rinse 10-15 minute;
(2) above-mentioned cleaning fluid L1 is added in reverse osmosis membrane processing device, wash cycles, preferably cleaning 1-2 hour;
(3) make cleaning fluid rest in reverse osmosis membrane processing device, reverse osmosis membrane is soaked, preferably soak 3-6 hour; Or often soak 20-30 minute, wash cycles 10-30 minute, and make the temporal summation of immersion and wash cycles be 1-6 hour;
(4) discharge cleaning fluid, then rinse reverse osmosis membrane with water, preferably rinse 10-40 minute;
(5) above-mentioned cleaning fluid L2 is added in reverse osmosis membrane processing device, wash cycles, preferably cleaning 1-2 hour;
(6) make cleaning fluid rest in reverse osmosis membrane processing device, reverse osmosis membrane is soaked, preferably soak 3-6 hour; Or often soak 20-30 minute, wash cycles 10-30 minute, and make the temporal summation of immersion and wash cycles be 1-6 hour;
(7) discharge cleaning fluid, then rinse reverse osmosis membrane with water, preferably rinse 10-40 minute.
The invention will be further described by the following examples.
Embodiment 1
The present embodiment is for illustration of 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 70kg deionized water, stir and make it fully dissolve, adding deionized water to solution weight is 100kg, and be 3.0 by NaOH adjust ph, obtain cleaning fluid L1-1.
Take neopelex (purchased from Nanjing Soviet Union as Chemical Co., Ltd.) 1kg, acrylic acid/hydroxypropyl acrylate/2-acrylamide-2-methyl-propane sulfonic acid copolymer is (purchased from Shandong Taihe Water Treatment Co., Ltd., trade mark TH-613) 3.5g, add 70kg deionized water, stirring makes it fully dissolve, adding deionized water to solution weight is 100kg, and is 11.0 by NaOH adjust ph, obtains cleaning fluid L2-1.
According to the process shown in Fig. 1, adopt two-stage two-segment counter-infiltration system to process the former water that water quality parameter is as shown in table 1, water treatment amount is 200L/h, until stop when the front and back pressure differential increase 20% of first-stage reverse osmosis film or pure water output reduce 20%.Then, the reverse osmosis membrane (PA membrane, purchased from Hydranautics Water Management Equipment Ltd., trade mark RE4021-TL) in two-stage two-segment counter-infiltration system is cleaned according to following process according to following:
(1) pressure of first-stage reverse osmosis film is adjusted to 0.4MPa, the dense aquatic products amount regulating first-stage reverse osmosis membrane treatment appts is 160L/h, and primary reverse osmosis water output is 40L/h, closes two-pass reverse osmosis membrane treatment appts.Rinse first-stage reverse osmosis film with counter-infiltration product water, rinse 12 minutes;
(2) described cleaning fluid L1-1 is added first-stage reverse osmosis membrane treatment appts, till displacing original liquid, make described first-stage reverse osmosis membrane treatment appts circular flow 2 hours, then soak 4 hours;
(3) cleaning fluid is discharged;
(4) first-stage reverse osmosis film is rinsed 15 minutes with counter-infiltration product water;
(5) described cleaning fluid L2-1 is added first-stage reverse osmosis membrane treatment appts, till displacing original liquid, make described first-stage reverse osmosis membrane treatment appts circular flow 2 hours, then soak 4 hours;
(6) cleaning fluid is discharged;
(7) first-stage reverse osmosis film is rinsed 15 minutes with counter-infiltration product water;
(8) first-stage reverse osmosis membrane treatment appts is closed.The pressure of two-pass reverse osmosis film is adjusted to 0.4MPa, and the dense aquatic products amount regulating two-pass reverse osmosis membrane treatment appts is 160L/h, and two-pass reverse osmosis aquatic products amount is 40L/h, rinses two-pass reverse osmosis film 12 minutes with counter-infiltration product water;
(9) described cleaning fluid L1-1 is added two-pass reverse osmosis membrane treatment appts, till displacing original liquid, make described two-pass reverse osmosis membrane treatment appts circular flow 1.5 hours, then soak 2 hours;
(10) cleaning fluid is discharged;
(11) two-pass reverse osmosis film is rinsed 15 minutes with counter-infiltration product water;
(12) described cleaning fluid L2-1 is added two-pass reverse osmosis membrane treatment appts, till displacing original liquid, make described two-pass reverse osmosis membrane treatment appts circular flow 1.5 hours, then soak 2 hours;
(13) cleaning fluid is discharged;
(14) two-pass reverse osmosis film is rinsed 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, keep the pressure 0.4MPa of first-stage reverse osmosis film, the pressure of two-pass reverse osmosis film is 0.6MPa, discharges after 20 minutes with counter-infiltration product water circulation cleaning counter-infiltration system.
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 |
Note: the unit of electrical conductivity is μ s/cm, 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 70kg deionized water, stirring makes it fully dissolve, adding deionized water to solution weight is 100kg, and is 3.1 by KOH adjust ph, obtains cleaning fluid L1-2.
Take neopelex (purchased from Nanjing Soviet Union as Chemical Co., Ltd.) 2.8kg, acrylic acid/hydroxypropyl acrylate/2-acrylamide-2-methyl-propane sulfonic acid copolymer is (purchased from Shandong Taihe Water Treatment Co., Ltd., trade mark TH-613) 5.9g, add 70kg deionized water, stirring makes it fully dissolve, adding deionized water to solution weight is 100kg, and is 11.1 by KOH adjust ph, obtains cleaning fluid L2-2.
Method according to embodiment 1 is cleaned the reverse osmosis membrane in two-stage two-segment counter-infiltration system, and difference is, replaces cleaning fluid L1-1 and the cleaning fluid L2-1 of use in embodiment 1 respectively with cleaning fluid L1-2 and cleaning fluid L2-2.
Comparative example 1
Method according to embodiment 1 is cleaned the reverse osmosis membrane in two-stage two-segment counter-infiltration system, and difference is, replaces cleaning fluid L1-1 and the cleaning fluid L2-1 of use in embodiment 1 with cleaning fluid L2-2 respectively.
Comparative example 2
Method according to embodiment 1 is cleaned the reverse osmosis membrane in two-stage two-segment counter-infiltration system, and difference is, replaces cleaning fluid L1-1 and the cleaning fluid L2-1 of use in embodiment 1 with cleaning fluid L1-2 respectively.
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 70kg deionized water, stirring makes it fully dissolve, adding deionized water to solution weight is 100kg, and is 3.2 by NaOH adjust ph, obtains cleaning fluid L1-3.
Take neopelex (purchased from Nanjing Soviet Union as Chemical Co., Ltd.) 1.4kg, acrylic acid/hydroxypropyl acrylate/2-acrylamide-2-methyl-propane sulfonic acid copolymer is (purchased from Shandong Taihe Water Treatment Co., Ltd., trade mark TH-613) 3.9g, add 70kg deionized water, stirring makes it fully dissolve, adding deionized water to solution weight is 100kg, and is 11.2 by NaOH adjust ph, obtains cleaning fluid L2-3.
Method according to embodiment 1 is cleaned the reverse osmosis membrane in two-stage two-segment counter-infiltration system, and difference is, replaces cleaning fluid L1-1 and the cleaning fluid L2-1 of use in embodiment 1 respectively 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 70kg deionized water, stirring makes it fully dissolve, adding deionized water to solution weight is 100kg, and is 3.3 by KOH adjust ph, obtains cleaning fluid L1-4.
Take neopelex (purchased from Nanjing Soviet Union as Chemical Co., Ltd.) 0.6kg, acrylic acid/hydroxypropyl acrylate/2-acrylamide-2-methyl-propane sulfonic acid copolymer is (purchased from Shandong Taihe Water Treatment Co., Ltd., trade mark TH-613) 3.0g, add 70kg deionized water, stirring makes it fully dissolve, adding deionized water to solution weight is 100kg, and is 11.3 by KOH adjust ph, obtains cleaning fluid L2-4.
Method according to embodiment 1 is cleaned the reverse osmosis membrane in two-stage two-segment counter-infiltration system, and difference is, replaces cleaning fluid L1-1 and the cleaning fluid L2-1 of use in embodiment 1 respectively 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 70kg deionized water, stirring makes it fully dissolve, adding deionized water to solution weight is 100kg, and is 3.4 by NaOH adjust ph, obtains cleaning fluid L1-5.
Take neopelex (purchased from Nanjing Soviet Union as Chemical Co., Ltd.) 0.3kg, acrylic acid/hydroxypropyl acrylate/2-acrylamide-2-methyl-propane sulfonic acid copolymer is (purchased from Shandong Taihe Water Treatment Co., Ltd., trade mark TH-613) 2.1g, add 70kg deionized water, stirring makes it fully dissolve, adding deionized water to solution weight is 100kg, and is 11.4 by NaOH adjust ph, obtains cleaning fluid L1-5.
Method according to embodiment 1 is cleaned the reverse osmosis membrane in two-stage two-segment counter-infiltration system, and difference is, replaces cleaning fluid L1-1 and the cleaning fluid L2-1 of use in embodiment 1 respectively 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 70kg deionized water, stir and make it fully dissolve, adding deionized water to solution weight is 100kg, and be 2.9 by KOH adjust ph, obtain cleaning fluid L1-6.
Take myristyl benzene sulfonic acid sodium salt (purchased from Nanjing Soviet Union as Chemical Co., Ltd.) 1.1kg, acrylic acid/hydroxypropyl acrylate copolymer is (purchased from Shandong Taihe Water Treatment Co., Ltd., trade mark T225) 3.4g, add 70kg deionized water, stirring makes it fully dissolve, adding deionized water to solution weight is 100kg, and is 10.9 by KOH adjust ph, obtains cleaning fluid L1-6.
Method according to embodiment 1 is cleaned the reverse osmosis membrane in two-stage two-segment counter-infiltration system, and difference is, replaces cleaning fluid L1-1 and the cleaning fluid L2-1 of use in embodiment 1 respectively 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 70kg deionized water, stirring makes it fully dissolve, adding deionized water to solution weight is 100kg, and is 2.8 by NaOH adjust ph, obtains cleaning fluid L1-7.
Take cetyl benzenesulfonic acid sodium (purchased from Nanjing Soviet Union as Chemical Co., Ltd.) 0.9kg, acrylic acid/2-acrylamide-2-methyl-propane sulfonic acid copolymer is (purchased from Shandong Taihe Water Treatment Co., Ltd., trade mark AA-AMPS) 3.6g, add 70kg deionized water, stirring makes it fully dissolve, adding deionized water to solution weight is 100kg, and is 10.8 by NaOH adjust ph, obtains cleaning fluid L1-7.
Method according to embodiment 1 is cleaned the reverse osmosis membrane in two-stage two-segment counter-infiltration system, and difference is, replaces cleaning fluid L1-1 and the cleaning fluid L2-1 of use in embodiment 1 respectively 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 70kg deionized water, stir and make it fully dissolve, adding deionized water to solution weight is 100kg, and be 2.7 by KOH adjust ph, obtain cleaning fluid L1-8.
Take ten sodium alkyl benzene sulfonates (purchased from Nanjing Soviet Union as Chemical Co., Ltd.) 1.2kg, acrylic acid/hydroxypropyl acrylate copolymer is (purchased from Shandong Taihe Water Treatment Co., Ltd., trade mark T225) 3.3g, add 70kg deionized water, stirring makes it fully dissolve, adding deionized water to solution weight is 100kg, and is 10.7 by KOH adjust ph, obtains cleaning fluid L1-8.
Method according to embodiment 1 is cleaned the reverse osmosis membrane in two-stage two-segment counter-infiltration system, and difference is, replaces cleaning fluid L1-1 and the cleaning fluid L2-1 of use in embodiment 1 respectively 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 70kg deionized water, stirring makes it fully dissolve, adding deionized water to solution weight is 100kg, and is 2.6 by NaOH adjust ph, obtains cleaning fluid L1-9.
Take eight sodium alkyl benzene sulfonates (purchased from Nanjing Soviet Union as Chemical Co., Ltd.) 0.8kg, polyacrylic acid is (purchased from Shandong Taihe Water Treatment Co., Ltd., trade mark PAA) 3.7g, add 70kg deionized water, stirring makes it fully dissolve, adding deionized water to solution weight is 100kg, and is 10.6 by NaOH adjust ph, obtains cleaning fluid L1-9.
Method according to embodiment 1 is cleaned the reverse osmosis membrane in two-stage two-segment counter-infiltration system, and difference is, replaces cleaning fluid L1-1 and the cleaning fluid L2-1 of use in embodiment 1 respectively with cleaning fluid L1-9 and cleaning fluid L2-9.
Test case
At above-mentioned two-stage two-segment counter-infiltration system after cleaning, according to the process shown in Fig. 1, the former water as shown in table 1 to water quality parameter processes again, and water treatment amount is 200L/h.During process, the performance indications of first-stage reverse osmosis film and two-pass reverse osmosis film are as shown in table 2 below again.
Table 2
Note: 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 be 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, significantly can reduce the front and back pressure differential of reverse osmosis membrane, and reduce product electrical conductivity of water.
Claims (14)
1. a cleansing composition, is characterized in that, said composition comprises A agent and B agent, and A agent and B agent are independently preserved separately,
A agent contains citric acid, hydrochloric acid and nitrilotriacetic acid trisodium salt;
B agent contains anion surfactant and dispersant, and described anion surfactant is 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; The weight ratio of citric acid and hydrochloric acid is 0.5-2:1.
3. composition according to claim 2, wherein, in described A agent, the total amount of citric acid and hydrochloric acid and the weight ratio of nitrilotriacetic acid trisodium salt are 6-30:6; The weight ratio of citric acid and hydrochloric acid is 0.8-1.2:1.
4. composition according to claim 1, wherein, in described B agent, the weight ratio of described anion surfactant and described dispersant is 100-4500:3.
5. composition according to claim 4, wherein, in described B agent, the weight ratio of described anion surfactant and described dispersant is 375-1500:3.
6. according to the composition in claim 1,4 and 5 described in any one, wherein, described anion surfactant is be selected from least one in neopelex, myristyl benzene sulfonic acid sodium salt and cetyl benzenesulfonic acid sodium.
7. according to the composition in claim 1,4 and 5 described in any one, wherein, described dispersant is (methyl) acrylic copolymer, and described (methyl) acrylic copolymer is bipolymer between (methyl) acrylic acid, (methyl) hydroxypropyl acrylate and 2-acrylamide-2-methyl-propane sulfonic acid and/or terpolymer.
8. composition according to claim 7, wherein, described dispersant is at least one in (methyl) acrylic acid/(methyl) hydroxypropyl acrylate copolymer, (methyl) acrylic acid/2-acrylamide-2-methyl-propane sulfonic acid copolymer and (methyl) acrylic acid/(methyl) hydroxypropyl acrylate/2-acrylamide-2-methyl-propane sulfonic acid copolymer.
9. use the method that the cleansing composition in claim 1-8 described in any one cleans reverse osmosis membrane, the method comprises the following steps:
(1) described A agent is mixed with the cleaning fluid L1 that pH value is 2.5-3.5;
(2) described B agent is mixed with the cleaning fluid L2 that pH value is 10.5-11.5;
(3) in turn reverse osmosis membrane is cleaned with described cleaning fluid L1 and described cleaning fluid L2.
10. method according to claim 9, wherein, in step (3), first cleans described reverse osmosis membrane with described cleaning fluid L1, then cleans described reverse osmosis membrane with described cleaning fluid L2.
11. methods according to claim 9 or 10, wherein, in described cleaning fluid L1, the concentration of nitrilotriacetic acid trisodium salt is 0.2-3 % by weight.
12. methods according to claim 9 or 10, wherein, in described cleaning fluid L1, the concentration of nitrilotriacetic acid trisodium salt is 0.5-1.5 % by weight.
13. methods according to claim 9 or 10, wherein, in described cleaning fluid L2, the concentration of described anion surfactant is 0.2-3 % by weight.
14. methods according to claim 13, wherein, in described cleaning fluid L2, the concentration of described anion surfactant is 0.5-1.5 % by weight.
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| CN104528964B (en) * | 2014-12-24 | 2016-08-24 | 钟国平 | A kind of without phosphorus compound corrosion inhibiting and descaling agent |
| CN104556426B (en) * | 2014-12-24 | 2016-08-24 | 广州市清顺环保科技有限公司 | The preparation method of without phosphorus compound corrosion inhibiting and descaling agent |
| CN105018241A (en) * | 2015-08-20 | 2015-11-04 | 太仓市金鹿电镀有限公司 | Method for cleaning metal ion pollutants on surface of ultrafiltration membrane and preparation method of cleaning solution used thereof |
| CN105195024A (en) * | 2015-10-19 | 2015-12-30 | 河南大数据环保科技服务股份有限公司 | Cleaning method for nanofiltration membrane and reverse osmosis membrane |
| CN105441197A (en) * | 2015-12-29 | 2016-03-30 | 威海翔宇环保科技股份有限公司 | Cleaning agent applicable to offline washing of reverse osmosis membrane system and preparation method of cleaning agent |
| CN110215846A (en) * | 2019-06-12 | 2019-09-10 | 山东理工大学 | A kind of cleaning agent and cleaning method handling reverse osmosis concentrated water plate nanofiltration membrane |
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| CN113134305B (en) * | 2021-01-27 | 2023-01-03 | 山东九莹环境工程有限公司 | Reverse osmosis cleaning agent for seawater desalination equipment and preparation method and use method thereof |
| CN113862682A (en) * | 2021-08-18 | 2021-12-31 | 广州环投环境服务有限公司 | Cleaning agent, preparation method and cleaning method using cleaning agent |
| CN113789227B (en) * | 2021-09-17 | 2023-05-02 | 自然资源部天津海水淡化与综合利用研究所 | Calcium sulfate scale cleaning agent suitable for aluminum alloy heat transfer tube and preparation method and application thereof |
| CN114504948B (en) * | 2022-02-17 | 2023-05-26 | 嘉戎盛泓(营口)生态环保有限公司 | Reverse osmosis membrane silica scale cleaning agent and preparation method thereof |
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