CN1789153A - Water treatment method - Google Patents
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- CN1789153A CN1789153A CNA2005101285894A CN200510128589A CN1789153A CN 1789153 A CN1789153 A CN 1789153A CN A2005101285894 A CNA2005101285894 A CN A2005101285894A CN 200510128589 A CN200510128589 A CN 200510128589A CN 1789153 A CN1789153 A CN 1789153A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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Abstract
A water treatment germicide is characterized by comprising acids and corrosion inhibitors, besides, it's pH is not more than 4. The object of the invention is to provide a water treatment germicide, a method and equipment. That water treatment germicide has good sterilization effect when be used in seawater desalination membrane separation equipment.
Description
The application is that to be CN02802021.9 (international filing date is on April 2nd, 2002), denomination of invention be dividing an application that the PCT that enters country's stage of " water treatment with sterilant, water treatment method and water treatment device " applies for to application number.
Technical field
The present invention relates to water treatment method.
Background technology
Adopt the isolation technique of film to be used for the extensive fields such as manufacturing, Industrial Wastewater Treatment, foodstuffs industry of the fresh waterization of seawater and salt water, medical industrial pure water, ultrapure water.In these membrane sepn, the pollution of the tripping device that microorganism causes is except making the water quality deterioration of the permeate water that obtains, and the perviousness or the separation performance that also cause microbial growth on face or microorganism and meta-bolites thereof to be attached to the first-class film that causes of face reduce.For fear of great like this problem, the method for disinfection of various membrane separation units has been proposed, the general employing often or off and on added sterilant to supply with in the liquid method.As sterilant, the most generally be added on price, chlorine series bactericidal agent that operating aspect is favourable, make it to reach the concentration of 0.1-50ppm.In addition, also develop, the pH of the supply liquid of membrane separation unit is dropped to below 4, effectively carry out germ-resistant method (EP1031372A) by adding more cheap sulfuric acid.Corrosion-resistant metal such as common use stainless steel during by increase acidity such as interpolation sulfuric acid, because metal enters into the corrosion area of Pourbaix diagram, thereby are easy to cause corrosion of pipe as the pipeline of membrane separation unit.Under the low state of acidity,, when being necessary to increase germ-resistant frequency, there are problems such as sterilization is time-consuming in order to improve sterilization effect.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned background technology, the high water treatment of sterilization effect sterilant and water treatment method are provided.
In order to solve above-mentioned problem, the present invention has following structure.
(1) a kind of water treatment sterilant contains mineral acid, corrosion inhibitor and carbonatoms carboxylic acid or its an alkali metal salt below 8.
(2) a kind of water treatment method, it is characterized in that, in the water treatment operation of using separatory membrane, in any operation before the membrane sepn operation, water treatment is added in the processed liquid with sterilant, and this water treatment contains mineral acid, corrosion inhibitor and carbonatoms carboxylic acid or its an alkali metal salt below 8 with sterilant.
(3) a kind of water treatment method in the water treatment operation of using separatory membrane, in any operation before the membrane sepn operation, is below 4 by making pH with mineral acid being added to processed liquid discontinuous, simultaneously, corrosion inhibitor is added in the processed liquid.
(4) a kind of water treatment device is the water treatment device with membrane separation unit, it is characterized in that, has the aqueous solution that will contain mineral acid and corrosion inhibitor and is added into device in the processed liquid of supplying with this membrane separation unit.
(5) a kind of water treatment device is the water treatment device with membrane separation unit, it is characterized in that, has to supply with in the supply liquid that enters this membrane separation unit to contain the device of aqueous acid and the device of the aqueous solution that supply contains corrosion inhibitor.
Description of drawings
Fig. 1 is the sketch chart of expression water treatment device of the present invention.
Nomenclature
1 water fetching device
2 liquid-feeding pumps
3 pretreating devices
4 middle layers and security filter
5 boosting pumps
6 membrane separation units
7 liquid-feeding pumps
8 after-treatment devices
Embodiment
In the present invention, water treatment be meant the separation in the manufacturing, Industrial Wastewater Treatment, foodstuffs industry of desalination, separation or the fresh waterization of carrying out seawater or salt water, industrial pure water or ultrapure water or concentrate, from the processing of waste water reclamation valuables etc.
In addition, in the present invention, membrane separation unit be meant for distill, concentrate, separation etc., depress treatment solution delivery film assembly adding, be separated into device through liquid and concentrated solution.As membrane module, reverse osmosis membrane assembly, ultrafiltration membrane module, secondary filter membrane module etc. are arranged.Membrane separation unit is divided into reverse osmosis membrane apparatus, ultrafilter membrane device, secondary filter film device according to the kind of the main membrane module that uses.
Describe as example with the reverse osmosis membrane apparatus that preferably uses in the present invention.Reverse osmosis membrane apparatus is made of reverse-osmosis membrane element, pressure vessel, force (forcing) pump etc. usually.The processed liquid of supplying with this reverse osmosis membrane apparatus is adding chemical agents such as sterilant, agglutinant, reductive agent, pH regulator agent usually, carried out that aggegation, precipitation, sand are filtered, polishing (Port リ Star シ Application グ) filtration, activated carbon filtration, secondary filter, ultra-filtration, see through pre-treatment such as security filter after, feedway.For example, when sea water desalinization, get seawater after, at the settling tank separating particle etc., also have sterilant such as chlorine are added to and carry out sterilization in the settling tank.Then, add agglutinants such as iron(ic) chloride, poly aluminium chloride and carry out the sand filtration.Filtrate is stored in the storagetank, behind adjusting pH such as sulfuric acid, carries liquid.Carry in the process of liquid, add reductive agents such as sodium bisulfite, sterilant is removed in reduction, after making it to see through security filter, sees through liquid and is boosted by high-pressure pump, supplies with reverse osmosis membrane assembly.But these pre-treatments can suitably be selected according to kind, the purposes of processed liquid.
At this, so-called reverse osmosis membrane is to make a part of composition in the liquid, and for example solvent sees through, the semipolar linkage that other composition is not seen through.As the material of reverse osmosis membrane, generally use macromolecular materials such as cellulose acetate base polymer, polymeric amide, polyester, polyimide, vinyl polymer.In addition, as its structure, have at least one side to have tight zone at film, have to the surface of film inside or opposite side from this tight zone the aperture that slowly becomes big minute aperture asymmetric membrane and have composite membrane of the extremely thin active coating that forms by other materials etc. at the tight zone of this asymmetric membrane.Wherein, as the form of reverse osmosis membrane, macaroni yarn, flat film etc. are arranged.Usually, the thickness of preferred macaroni yarn peace film is 10 μ m-1mm, and the external diameter of macaroni yarn is 50 μ m-4mm.In addition, as flat film, preferred asymmetric membrane, as composite membrane preferably by the film of substrate support such as fabric, cloth, non-woven fabrics.But, method of the present invention can not rely on reverse osmosis membrane material, membrane structure or form be used, all effective for any one situation.
As representational reverse osmosis membrane, for example can exemplify cellulose acetate class or polyamide-based asymmetric membrane, have composite membrane of polyamide-based, polyureas active coating etc.Wherein, method of the present invention is effective especially for cellulose acetate class asymmetric membrane, polyamide-based composite membrane, and aromatic series class polyamide composite film effect is bigger.
So-called reverse osmosis membrane assembly is the material that makes it shapeization for reality uses above-mentioned reverse osmosis membrane.The form of reverse osmosis membrane is under the situation of flat film, can enroll in the assembly of spirrillum, tubulose or plate and frame and use, and in addition, under the situation of macaroni yarn, can enroll assembly on the basis of bunchy and use.The present invention can not rely on these reverse osmosis membrane assemblies composition-formed be suitable for.
The running pressure of reverse osmosis membrane apparatus is usually in the scope of 0.1MPa-15MPa, can suitably use respectively according to the kind of processed liquid, method of operation etc.When being processed liquid, under relatively low pressure, use, when being treatment solution, under relatively high pressure, use with seawater or trade effluent etc. with the low solution of salt water isosmoticity.
The scope that the operating temperature of reverse osmosis membrane apparatus is preferred 0 ℃-100 ℃.If lower than 0 ℃, then processed liquid probably can freeze, and when higher than 100 ℃, probably causes the evaporation of processed liquid.
The rate of recovery of the processed liquid in the reverse osmosis membrane apparatus can suitably be selected between 5-98% usually.But, must consider pre-treating process and running pressure according to proterties, concentration, the osmotic pressure of processed liquid or concentrated solution, set the rate of recovery.For example, under the situation of seawater fresh waterization, set the rate of recovery of 10-40% usually, under the situation of high efficiency device, set the rate of recovery of 40-70%.Under the situation of salt water fresh waterization or manufacturing ultrapure water, usually with more than 70%, as required can be with the high-recovery running of 90-95%.At this, the rate of recovery is meant that the amount of liquid that sees through reverse osmosis membrane divided by processed liquid measure, multiply by 100 numerical value again.
The formation of reverse osmosis membrane apparatus mainly is made of high-pressure pump and reverse osmosis membrane assembly.High-pressure pump can be selected best pump according to the running pressure of device.
In addition, the arrangement of reverse osmosis membrane assembly can be used 1 grade, but preferably with respect to processed liquid, series connection or multistage in parallel arrangement.During arranged in series, boosting pump can be set between reverse osmosis membrane assembly.During seawater fresh water, from the viewpoint of installation cost, the preferred especially arrangement of using 2 grades of series connection.At this moment, preferably between the reverse osmosis membrane assembly of arranged in series, boosting pump is set, processed liquid is boosted to 1.0-5.0MPa, supply with the assembly of back level.With respect to processed liquid, during with the reverse osmosis membrane assembly arranged in series, because membrane module is long with the time that processed liquid contacts, thereby effect of the present invention is big.
And reverse osmosis membrane assembly also can be with respect to seeing through the liquid arranged in series.This be the quality that sees through liquid for water utilization preferable methods under the inadequate situation and under wanting to reclaim through the situation of the solute composition in the liquid.At this, with respect to seeing through liquid, when the reverse osmosis membrane assembly series connection is provided with, pump is set between reverse osmosis membrane preferably, will see through liquid and pressurize again or apply enough pressure in prime, utilize the residual pressure of back grade to carry out membrane sepn.In addition, with respect to seeing through liquid, when series connection is provided with reverse osmosis membrane assembly,, the adding set of acid is set between reverse osmosis membrane assembly preferably for the sterilization of the reverse osmosis membrane assembly of level after carrying out.
In reverse osmosis membrane apparatus, the part that does not see through film in the processed liquid is taken out from reverse osmosis membrane assembly as concentrated solution.This concentrated solution can utilize or be discarded, also can concentrate with other method again.In addition, concentrated solution also can be circulated in the processed liquid its part or all.See through film see through that liquid can utilize or discarded, also can be circulated in the processed liquid its part or all.
The concentrated solution of reverse osmosis membrane apparatus generally has pressure energy, in order to reduce operating cost, preferably reclaims this energy.As the method for recovered energy, can reclaim with the energy recycle device on the high-pressure pump that is installed to arbitrary portion, preferably reclaim with the special-purpose Scroll-type energy recovery pump between front and back that are installed in high-pressure pump or the assembly.
The processing water yield of processing power preferred every day of the membrane separation unit that the present invention uses is 0.5m
3-100 ten thousand m
3
In addition, in the membrane separation unit that the present invention uses, the pipeline in the device is preferably made and is detained the few structure of part.
In water treatment method of the present invention, mineral acid and corrosion inhibitor are added in the processed liquid of supplying with water treatment device off and on.It is of crucial importance that being added on of mineral acid produces the sterilization effect aspect, and particularly in using the membrane filtration of seawater as processed liquid, this effect is remarkable.The pH of killing microorganisms is that microbial species is distinctive, and under for example colibacillary situation, the lower limit of growth is pH4.6, kills at pH to produce below 3.4.In seawater, there is multiple microorganism, the pH difference that each is killed.But,, just can kill the microorganism of 50-100% if usually processed liquid is remained on the following certain hour of pH4.0.The pH of processed liquid that has added mineral acid and corrosion inhibitor is more preferably below 3.9, further preferably below 3.7, particularly preferably in below 3.4.There is no particular limitation for the lower limit of pH, from prevent mean corrosive viewpoint, preferably more than 1.5, particularly preferably in more than 2.0.
The pH that further makes processed liquid be below 3.0 for the microorganism that comprises the acid resistance bacterium, providing preferred aspect the high sterilization effect.If making pH is below 3.0,, be used to make supply liquid to influence the worry that increases for tart soup expense height and to the pipeline equipment corrosive but exist usually for the high sterilization effect of whole microorganisms demonstrations that comprises the acid resistance bacterium.For this reason, usually during fractional sterilization, make the pH of processed liquid bigger than 3.0, reach the scope of pH 3.0-4.0, however, the residual microorganism for there not being extinction, making the pH of processed liquid with the frequency of every 2-1000 fractional sterilization 1 time is below 3.0, is preferred for effective sterilization.
Preferably by mineral acid and corrosion inhibitor are added in the processed liquid off and on, the viable count survival rate that has carried out in the condensed water after the membrane sepn operation is below 30%, and to make the viable count survival rate 1 time in every 2-1000 time of the operation of adding mineral acid off and on be below 15%.If the viable count survival rate surpasses 30%, then sterilization is insufficient.At this, viable count survival rate (%) is tried to achieve with following formula.
Viable count survival rate (%)=((viable count behind the interpolation mineral acid)/(adding the preceding viable count of mineral acid) } * 100
As the mineral acid that the present invention uses, can adopt hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid etc. any one, if consider economic aspect, preferably adopt sulfuric acid.
The corrosion inhibitor that the present invention uses is for the corrosion of prevention of water treatment unit, and it is important improving sterilization effect.As being used for corrosion inhibitor of the present invention, the preferred compound that is selected from the poly carboxylic acid, ethylenediamine tetraacetic acid (EDTA), nitrous acid and an alkali metal salt thereof that have at least 6 carboxylic acid groups in the molecule that adopts.At this,, preferably adopt at least a compound that is selected from poly-epoxy succinic acid, polyacrylic acid, polymaleic acid and the maleic acid of following general formula (in the formula, n is the integer more than 3, and X, Y are hydrogen or basic metal) expression as poly carboxylic acid.
As corrosion inhibitor, be preferably selected from the compound of poly-epoxy succinic acid, ethylenediamine tetraacetic acid (EDTA), polyacrylic acid and their an alkali metal salt especially.These compounds are owing to have the big atoms of electronegativity degree such as oxygen, nitrogen in molecule, thereby good to the adsorptivity of metallic surface, are preferred.
Wherein, polyacrylic acid is high and corrosion inhibition effect height owing to food safety, thereby most preferably.In water treatment is when making tap water, special optimization polypropylene acid.
Polyacrylic weight-average molecular weight is because of the water treatment condition, for example pH or temperature etc., and optimum range changes, and therefore needs to select the polyacrylic acid with qualified weight-average molecular weight.Polyacrylic weight-average molecular weight is preferably in the scope of 500-10000, more preferably in the scope of 1000-8000.If weight-average molecular weight less than 500, then is difficult to obtain sufficient corrosion inhibition effect, if surpass 10000, then the storage stability of sterilant is easy to deterioration.
For example with the synthetic poly-epoxy succinic acid of following method or its an alkali metal salt.That is, be catalyzer with the sodium wolframate, with the maleate epoxidation, make the epoxy succinic hydrochlorate with hydrogen peroxide.Then, in alkaline aqueous solution, be catalyzer with calcium hydroxide, with the ring-opening polymerization of epoxy succinic hydrochlorate, obtain polyepoxysuccinic acid salt.In addition, as maleic acid, preferably use the multipolymer etc. of multipolymer, toxilic acid and the methylvinylether of toxilic acid and alkene.
When adding to sour and corrosion inhibitor in the processed liquid of supplying with water treatment device, can add respectively, also can make the water treatment sterilant that has mixed both in advance, add then.If make the water treatment sterilant in advance, then can effectively carry out germicidal treatment, thereby preferred.
Water treatment of the present invention with the concentration of mineral acid in the sterilant and corrosion inhibitor separately preferably in the scope of 50ppm (weight)-50 weight %.If one of acid and corrosion inhibitor or both concentration surpass 50%, then the storage stability of sterilant is easy to deterioration.In addition, when one of acid and corrosion inhibitor or both concentration ratio 50ppm are low, then need to increase the addition of water treatment with sterilant, germ-killing efficiency is easy to deterioration.
Be used for the water preferred pure water of water treatment of the present invention with sterilant.If contain impurity in the water that uses, then produce precipitate etc., storage stability deterioration sometimes with acid or corrosion inhibitor reaction.
For the mixture of acid and corrosion inhibitor,, thereby preferably further preserving stabilizer is added to water treatment with in the sterilant because storage stability is also bad sometimes.As preserving stabilizer, in order to reduce damage, sterilization effect is reduced to the separatory membrane of water treatment device, preferably use carboxylic acid or its an alkali metal salt of carbonatoms below 8.At this,, more preferably be selected from least a in acetic acid, lactic acid, succsinic acid, tartrate, citric acid and the oxysuccinic acid as the carboxylic acid of carbonatoms below 8.By adding such preserving stabilizer, even mixing acid and corrosion inhibitor and long-time the preservation also can stably be preserved.The water treatment concentration of the concentration of the preserving stabilizer in the sterilant because of acid in the sterilant and corrosion inhibitor, optimum range changes, but the scope of usually preferred 50ppm (weight)-50 weight %.
Water treatment of the present invention can be used in various water treatment operations with sterilant, preferably uses in the water treatment operation that adopts the big separatory membrane of microbiological effect.
And, as separatory membrane, reverse osmosis membrane, ultrafilter membrane, secondary filter film etc. are arranged, as sterilant, preferred use water treatment sterilant of the present invention in the water treatment operation, this water treatment operation adopts the reverse osmosis membrane that can not use oxygenants such as normally used chlorine.
As the method for sour and corrosion inhibitor being added in the processed liquid of supplying with water treatment device, can add respectively, also can make the water treatment sterilant that has mixed both in advance, add then.If make the water treatment sterilant in advance, then can effectively carry out germicidal treatment, thereby preferred.
Water treatment, is preferably added with the scope of 10ppm (weight)-10 weight % in processed liquid with sterilant.Under the addition that the makes sterilant situation lower than 10ppm, in order to obtain high sterilization effect, need to improve the concentration of acid and corrosion inhibitor in the sterilant, water treatment is with the possible deterioration of the storage stability of sterilant.In addition, make water treatment with the addition of sterilant than the high situation of 10 weight % under, water treatment needs big load with the adding set of sterilant, energy consumption increases, so becomes unfavorable economically.
Water treatment is preferably implemented off and on the interpolation of sterilant.Each interpolation time preferably 0.5-2.5 hour scope, is added preferred 1 day frequency of-1 month 1 time of frequency.Preferably in the change of viable count that monitors the change that sees through the water yield of film, concentrated solution and the organic carbon that contains, the rising of pressure reduction etc., appropriate change adds the time and adds frequency.Degerming about film, when water treatment device stops, also can be by film immersion is carried out in the aqueous solution that contains acid and corrosion inhibitor, Yi Bian carry out membrane sepn, be effectively with water treatment with the method that sterilant adds in the processed liquid on one side, thus preferred.
In water treatment method of the present invention, also can respectively mineral acid and corrosion inhibitor be added in the processed liquid.The addition of mineral acid in processed liquid is from the angle of sterilization effect, more than the preferred 10ppm (weight), from the viewpoint of equipment corrosions such as economy and prevention pipeline, below the preferred 1 weight %.
Sterilant preferred addition in processed liquid changes with the salt concn of processed liquid, and the pH that preferably is controlled to be processed liquid reaches below 4 off and on, and the concentration of the corrosion inhibitor in the processed liquid reaches the scope of 0.1ppm-1%.If the pH of processed liquid is than 4 height, then sterilization effect reduces.In addition, if the concentration of corrosion inhibitor is lower than 0.1ppm, then corrosion inhibition effect reduces.On the contrary, under the high situation of the concentration ratio of corrosion inhibitor 1%, anti-corrosion effects is tendency, becomes unfavorable economically.
When using sulfuric acid as mineral acid, its addition is preferably proportional with the salt concn of processed liquid.For example, (120 ℃ of pressurization sterilizations, 15 minutes) physiological saline (common salt concn 0.9 weight %) in, make pH reduce to 3.2 by the sulfuric acid that adds 50ppm, but using (120 ℃ of pressurization sterilizations, 15 minutes) after the seawater in 3 places and commercially available artificial seawater (the about 3.5 weight % of salt concn) during as processed liquid, even add the sulfuric acid of 100ppm, the pH of processed liquid is 5.0-5.8 just also.Think that this mainly is the influence by the M basicity generation of seawater.For the pH that makes seawater is below 4, usually, preferably add the above sulfuric acid of 120ppm (weight).The upper limit of sulfuric acid addition is from economy and the corrosive angle of prevention to equipment such as pipelines, below the preferred 400ppm, more preferably below the 300ppm.When interpolation vitriolic concentration was 150ppm, 200ppm in above-mentioned seawater, artificial seawater in addition, the pH of processed liquid was respectively pH3.2-3.6 and pH2.8-2.9.That is, increase along with sulfuric acid adds concentration, the pH skew of processed liquid reduces.
In addition, the concentration of the corrosion inhibitor in the processed liquid is because of the kind or the water treatment condition of processed liquid, and optimum range changes, the scope of usually preferred 0.1ppm (weight)-1 weight %.From the easness of economy and water treatment operation, the more preferably scope of 1-500ppm.For example under 35 ℃ of temperature, during the waste water of water treatment pH1.0, salt concn about 8%, corrosion inhibitor is preferably the scope of 1-100ppm in processed liquid.
In the present invention, for mineral acid and corrosion inhibitor, so long as the operation before the processed liquid delivery film tripping device can be added at any place.For the sterilization of membrane separation unit, preferably in front of membrane separation unit, add.And, in processed liquid, add the downstream side of corrosion inhibitor and add mineral acid, preferred aspect the inhibition corrosion of piping.
It also is preferable methods that being added on of corrosion inhibitor added when adding mineral acid simultaneously.Under the high situation of corrosion inhibitor price,, preferably only reach pH3.0 and add when following at processed liquid from the viewpoint of economy.
The preferred interpolation of implementing mineral acid and corrosion inhibitor off and on.Each interpolation time preferably 0.5-2.5 hour scope, is added preferred 1 day frequency of-1 month 1 time of frequency.Preferably in the change of viable count that monitors the change that sees through the water yield of film, concentrated solution and the organic carbon that contains, the rising of pressure reduction etc., appropriate change adds the time and adds frequency.About the degerming of film, when water treatment device stops, also can be by film immersion is implemented in the aqueous solution that contains acid and corrosion inhibitor.
When adding mineral acid and corrosion inhibitor respectively, also can change the frequency of interpolation respectively.For example,, carry out 0.5-2.5 hour interpolation every other day,, carry out the interpolation with the sour identical time, change and add frequency, for example can carry out in 1 week 1 time for corrosion inhibitor for acid.Under particularly high and the situation that its corrosion inhibition effect is good in the corrosion inhibitor price, from the economy aspect, the preferred interpolation frequency that adopts combination to reduce corrosion inhibitor, the methods such as situation of only adding the situation of acid and adding acid and corrosion inhibitor.
Water treatment device with membrane separation unit of the present invention is the device of for example being made up of the structure of A-H shown below.
A. water fetching device.Be the device that obtains as the former water of processed liquid, usually, constitute by water intaking pump, medicine injection device etc.
B. the pretreating device that is communicated with water fetching device.Be that the processed liquid of supplying with the separatory membrane device is carried out pre-treatment, remove outstanding absurd creature in the processed liquid, emulsification etc., drop into the device of a part of medicament.For example, can constitute in the following order.
B-1 aggegation filtration unit.
B-2 polishes filtration unit.
Also can use ultrafiltration unit or secondary filter device to replace these B-1, B-2.
The used device of medicaments such as B-3 agglutinant, sterilant, pH regulator agent.
C. be communicated with pretreating device, as required the medial launder of She Zhiing.Have functions such as regulating pondage, water quality shock absorption.
D. be provided with under the situation of C and medial launder is communicated with, perhaps under the situation that C is not set, the strainer that is communicated with by pretreating device.Function with solid impurity of removing the processed liquid in the delivery film tripping device.
E. membrane separation unit.Constitute by high-pressure pump and separating film module.
A plurality of membrane separation units are set, can be arranged in parallel them, the setting of also can connecting.Series connection is when being provided with, and can be provided with between membrane separation unit in order to improve the pump of the hydraulic pressure when processed liquid supplied with the membrane separation unit of back grade.
F. with the after-treatment device that the liquid exit portion is communicated with that sees through of membrane separation unit.For example following illustrative device.
The F-1 de-gassing vessel.Function with decarbonate.
F-2 calcium tower.
F-3 chlorine injection device.
G. with the partially communicating after-treatment device of former water side outlet of membrane separation unit.For example following illustrative device.
The G-1 snubber assembly.Neutralising arrangement for example.
The G-2 equipment of releasing.
H. other.
The treatment unit of waste water etc. also can suitably be set.
Water treatment device of the present invention can be provided with pump in arbitrary site.In addition, the device that adds mineral acid and the corrosion inhibitor or their aqueous solution preferably is arranged on before the pretreating device or pretreating device of the water fetching device of A, B, and any one the above place before the strainer of D or after the strainer.Before membrane separation unit, that is, and before the strainer of D or after the strainer.
In addition, in order to improve effect of the present invention, the device that water treatment preferably can be controlled automatically with the adding set of sterilant, mineral acid and corrosion inhibitor preferably is equipped with the pump that can suitably control injection rate.In addition, the processed liquid of mensuration supply and the device of the pH of concentrated solution and the concentration of corrosion inhibitor etc. preferably are installed in device.In addition, in order to control water treatment with adding the intermittence of sterilant etc., preferably have can minute device.The automatic control device that further preferably possesses the water treatment device integral body that to turn round automatically.
The member of formation of water treatment device of the present invention, for example pipeline, valve etc. preferably use and be difficult to the corrosive member under the conditions below the pH4.The pH of the processed liquid by making supply is below 4, when obtaining high sterilization effect, also can obtain removing the such effect of incrustation in the pipeline.For the film deterioration that prevents to cause by oxide compounds such as chlorine, add sodium bisulfite sometimes, by adopting water treatment sterilant of the present invention, can significantly reduce its addition.
The interpolation of the chlorine series bactericidal agent in the pretreatment procedure is effectively to sterilization, can generally use.Have under the situation of treatment unit of membrane separation unit, for example in any operation of the device of above-mentioned A-D, implement injecting continuously or intermittently of chlorine series bactericidal agent.By this method, the processed liquid of supply is not as long as sterilization fully haply appears in resistant bacterium.At this, the chlorine series bactericidal agent often makes reverse osmosis membrane chemical deterioration, takes place for preventing it, and generally adding with the sodium bisulfite in front of membrane separation unit is the reductive agent of representative.But, become the state that microorganism can breed easily except that the processed liquid behind the dechlorination with the reductive agent reduction.And for example, the former water of seawater before adding sterilant is not miscellaneous microorganism, but quite screened micropopulation exists therein, wherein might comprise many acid resistance bacterium.For this problem, the interpolation of the chlorine series bactericidal agent by implementing pretreatment procedure respectively off and on and the injection of the reductive agent in front of the membrane separation unit just can solve.This method also is effective for the deterioration that prevents film simultaneously.The injection of chlorine series bactericidal agent at interval for example with the water quality of the former water of seawater, promptly the existence of microorganism adapts, and carries out 1 time in preferred 1 day-6 months, carries out 30 minutes-2 hours at every turn.Adapt period with the interpolation of this chlorine series bactericidal agent, further consider moving of the water that contains chlorine class additive, reductive agent is supplied between pretreating device and the membrane separation unit, preferably with chlorine series bactericidal agent deactivation.In addition, can adapt, respectively water treatment of the present invention be added in the aqueous solution of delivery film tripping device with acid with sterilant or corrosion inhibitor, implement the sterilization of membrane separation unit with above-mentioned period.
This method of injecting the chlorine series bactericidal agent intermittence to pretreatment procedure is compared with continuous injection sterilant, has the remarkable effects that reduce of handling such as drug expenditure.This effect is owing to exist employing water treatment of the present invention to realize first that with the water treatment method of sterilant or acid and corrosion inhibitor method for disinfection in the past is insufficient because of sterilization effect, in any case thereby can not realize.
Water treatment method of the present invention and device go for adopting the water treatment of membrane separation unit.Particularly go for the refining step etc. of water such as height processing of turbidity removal, water drain of manufacturing, the former water of water drain of manufacturing, pharmaceutical pure water of manufacturing, ultrapure water or pure water of fresh waterization, the process water of fresh waterization, the salt water of seawater.In addition, in the concentrated grade of food, the organism that will be easy to decompose with oxidizing bactericide in the past etc. separate or when concentrated, also can concentrate or reclaim the organism that not have decomposition etc., and effect of the present invention is big.In addition, when making tap water, the effect of the generation that can prevent the haloform that produced by the chlorbenside microbial inoculum is arranged.Further, water treatment method of the present invention be owing to can only use the high compound of food safety to carry out sterilization, thereby is particularly suitable for the manufacturing of tap water.
Embodiment
In an embodiment, specify the present invention, but the present invention is not subjected to the restriction of these embodiment.
At first, narration is used for soup etc. synthetic of embodiment.
The synthesis example of＜polyepoxysuccinic acid salt 〉
According to the synthetic method of (J.Org.Chem., 24,54 (1959)) such as Payne, following synthesizing epoxy succinate.
280g maleic anhydride and 428mL ultrapure water are put into the three-necked flask of 2L and made it dissolving.Be maintained until room temperature simultaneously at refrigerative, 500g 48 weight % potassium hydroxide aqueous solutions be added drop-wise in this aqueous solution with dropping funnel.Then, behind the interpolation 18.8g sodium wolframate, drip 332g35 weight % aqueous hydrogen peroxide solution.Behind the stir about 30 minutes, slowly add 115g 48 weight % potassium hydroxide aqueous solutions.At this moment, flask is sharply cooled off, temperature of reaction is remained on 55-65 ℃.Afterwards, kept 30 minutes down, obtain the Epoxysuccinic acid aqueous solutions of potassium at 65-60 ℃.After being cooled to room temperature, this aqueous solution is concentrated into about 300mL, is injected in the 1L acetone, filter the throw out that produces, separating ring oxydisuccinic acid potassium.
Then, in the 200mL round-bottomed flask, put into this Epoxysuccinic acid potassium of 10.4g and 50g ultrapure water, add 48 weight % potassium hydroxide, regulate the pH to 10.3 of the aqueous solution.Further add 0.41g calcium hydroxide, under 80 ℃, carry out reaction in 6 hours.Then, be cooled to room temperature after, filter insolubles, adopt rotatory evaporator, remove down for 40 ℃ and anhydrate bathing temperature, obtain the solid substance of white.
Adopt gel permeation chromatography (GPC) to measure the molecular weight of the polyepoxysuccinic acid salt that obtains.Specifically, under the concentration of 200ppm, prepare sample, adopt the known polyoxyethylene glycol of molecular weight as reference material production standard curve, the molecular weight of calculation sample.The molecular weight of the polyepoxysuccinic acid salt that obtains is weight-average molecular weight Mw=20900 (n=100, Mw/Mn=1.00).
Embodiment 1-3
In pure water (specific conductivity 10 μ S/cm), add the corrosion inhibitor 0.1 weight % shown in 20 weight % sulfuric acid and the table 1, regulate water treatment sterilant (pH0.6).Adopt ultrasonic washer, with the pure water washing with No. 320 file milled processed the stainless steel test film of surperficial SUS316L system (behind 20mm * 30mm * 1mm) 60 minutes, usefulness washing with acetone 60 minutes, air-dry.With seawater (specific conductivity 100mS/cm) above-mentioned water treatment is diluted to 100 times (concentration of sterilant 1 weight %) with sterilant,, puts into the poly-container of 100mL, flood above-mentioned stainless steel test film singly all as the experimental liquid (pH1.2) of 100mL.Prepare 10 and should gather container, in 80 ℃ thermostatic chamber, leave standstill.From dipping, took out test film at the 4th day and the 7th day, carry out weight determination.Test film with pure water washing 5 seconds after, with washing with acetone 5 seconds, air-dry after, in the silica dehydrator environment, but carry out weight determination with weighing to the electronic balance of 0.01mg, try to achieve 5 mean value.The effect that corrosion inhibitor causes is added in following evaluation.
Following respectively trying to achieve from the dipping beginning until the 4th day weight minimizing (a) with from the weight minimizing (b) until the 7th day in the 4th day.
Weight reduces (a) (g/m
24 days test film weight of test film weight-Di before the)=(dipping)/the test film surface-area
Weight reduces (b) (g/m
27 days the test film weight of test film weight-Di of the 4th day)=()/the test film surface-area
Then, reduce (a) and (b) with regard to above-mentioned weight respectively, following weight of trying to achieve when adopting corrosion inhibitor reduces the ratio that the weight when not adopting corrosion inhibitor reduces.
Weight reduces (a) compare=has the weight of weight minimizing (a)/no corrosion inhibitor of corrosion inhibitor to reduce (a)
Weight reduces (b) compare=has the weight of weight minimizing (the b)/no corrosion inhibitor of corrosion inhibitor to reduce (b)
Reduce the mean value of (a) ratio and weight minimizing (b) ratio as the weight decrement with weight.The result is as shown in table 1.(in the table, poly-epoxy succinic acid sylvite is abbreviated as PES, and tetrasodium ethylenediamine tetraacetate is abbreviated as EDTA, and polyacrylic acid is abbreviated as PA.)
Comparative example 1
Except that not adding corrosion inhibitor, with embodiment 1 the same experimentizing.The result is as shown in table 1.This comparative example that does not add corrosion inhibitor compares with embodiment 1-3, and the weight decrement is big, and test film has corroded.
Table 1
| Corrosion inhibitor | The weight decrement | |
| Embodiment 1 | PES | 0.37 |
| Embodiment 2 | EDTA | 0.58 |
| Embodiment 3 | PA | 0.67 |
| Comparative example 1 | Do not have | 1.00 |
Embodiment 4-7
In the seawater (specific conductivity 100mS/cm) that adds sulfuric acid adjusting pH to 1, add the corrosion inhibitor 10ppm shown in the table 2 and regulate experimental liquid.Adopt ultrasonic washer, with the pure water washing with No. 320 file milled processed the stainless steel test film of surperficial SUS304 system (behind 20mm * 30mm * 1mm) 60 minutes, usefulness washing with acetone 60 minutes, air-dry.In the poly-container of 100mL, put into the above-mentioned experimental liquid of 100mL, flood above-mentioned stainless steel test film singly.Preparing 5 should poly-container, in 35 ℃ thermostatic chamber, leave standstill 3 days after, be warming up to 80 ℃, continued to leave standstill 17 hours.Take out test film, after 30 seconds, use washing with acetone 10 seconds with the pure water washing.Following mensuration is reduced by the weight that corrosion causes.Weight reduces tries to achieve with following formula, as the mean value of 5 samples.
Weight reduces (g/m
2The test film weight of test film weight-dipping after 3 days before the)=(dipping)/the test film surface-area
The result is as shown in table 2.
(in the table, poly-epoxy succinic acid sylvite is abbreviated as PES, and tetrasodium ethylenediamine tetraacetate is abbreviated as EDTA, and ethylene-dimalonic acid is abbreviated as BTC.)
Comparative example 2
Except not adding corrosion inhibitor, with embodiment 4 the same experimentizing.
Can learn, under the such strong acidic condition of pH1, when adding corrosion inhibitor, compare when not adding corrosion inhibitor to have high corrosion inhibition effect from table 2.
Table 2
| Corrosion inhibitor | Concentration (ppm) | Weight reduces (g/m 2) | |
| Embodiment 4 | PES | 10 | 0.19 |
| Embodiment 5 | EDTA | 10 | 0.14 |
| Embodiment 6 | PA | 10 | 0.38 |
| Embodiment 7 | BTC | 10 | 17.9 |
| Comparative example 2 | Do not have | - | 27.9 |
Embodiment 8, comparative example 3 and 4
In pure water (specific conductivity 10 μ S/cm), add the corrosion inhibitor 0.1 weight % shown in 20 weight % sulfuric acid, the table 3, regulate the sterilant of water treatment device.For embodiment 8, further add each 0.5 weight % of Trisodium Citrate and oxysuccinic acid as preserving stabilizer.Adopt ultrasonic washer, with the pure water washing with No. 320 file milled processed the stainless steel test film of surperficial SUS304 system (behind 20mm * 30mm * 1mm) 60 minutes, usefulness washing with acetone 60 minutes, air-dry.Afterwards, in 50 ℃ 20% aqueous nitric acid, put into the stainless steel test film, carry out taking out test film, with washing with acetone and air-dry after mobilism was handled in 1 hour.With seawater (specific conductivity 100mS/cm) above-mentioned sterilant is diluted to 100 times (concentration of sterilant 1wt%),, puts into the poly-container of 100mL, flood above-mentioned stainless steel test film singly as experimental liquid (pH1.4).Prepare 5 and should gather container, in 80 ℃ thermostatic chamber, leave standstill.Take out test film from the dipping beginning at the 6th day, carry out weight determination.Test film with pure water washing 5 seconds after, with washing with acetone 5 seconds, air-dry after, in the silica dehydrator environment, but carry out weight determination with weighing to the electronic balance of 0.01mg, the same with embodiment 4, calculated weight reduces.Its result is as shown in table 3.
In addition, the seawater with salt concn 6.9 weight % under 30 ℃ leaves standstill an evening, make viable count stable after, be diluted to 3.5 weight % (being referred to as A liquid) with aqua sterilisa.In seawater (specific conductivity 100mS/cm), add the sterilant 0.1 weight % (pH3.1) shown in the table 3, under 30 ℃, leave standstill 30 minutes (being referred to as B liquid).Viable count is measured and is adopted maritime bacteria-measuring substratum, after cultivating 6 days under 30 ℃, the colony number that occurs is counted, and the viable count survival rate of the viable count of (A liquid) is represented when using with respect to no pH regulator.That is, viable count survival rate (%) is tried to achieve with following formula.
Viable count survival rate (%)=[viable count of { reaction back (B liquid) }/viable count of (A liquid) during no pH regulator] * 100
The result is as shown in table 3.
Above-mentioned sterilant left standstill in 25 ℃ thermostatic chamber in addition, confirmed solution state at the 19th day.Its result is as shown in table 3.
(in the table, polyacrylic acid is abbreviated as PA, and Trisodium Citrate is abbreviated as CA, and oxysuccinic acid is abbreviated as MA.)
As known from Table 3, compare with the comparative example 3 that does not add preserving stabilizer, the embodiment 8 that has added preserving stabilizer also has higher storage stability except having corrosion inhibition effect.In addition, the weight of not adding comparative example 4 test films of corrosion inhibitor reduces big.
Table 3
| Corrosion inhibitor | Preserving stabilizer | Weight reduces (g/m 2) | Viable bacteria survival rate (%) | Solution state | |
| Embodiment 8 | PA | CA，MA | 0.19 | 0.12 | Do not separate out |
| Comparative example 3 | PA | Do not have | 0.24 | 0.08 | White opacity a little |
| Comparative example 4 | Do not have | Do not have | 1.08 | 0.16 | Do not separate out |
Industrial applicibility
According to the present invention, in the water treatment of adopting membrane separation device, can in the restraining device corrosion of piping, effectively carry out sterilization. For this reason, might increase the sterilization frequency, perhaps further reduce pH, bactericidal effect is strengthened.
In addition, when in water treatment usefulness bactericide of the present invention, adding preserving stabilizer, can under the state that keeps bactericidal effect and corrosion-suppressing effect, realize high storage stability.
The present invention is specially adapted in the operations such as seawater desalination, salt water desalination.
Claims (14)
1. water treatment method, in the water treatment operation that adopts separatory membrane, in any operation the membrane sepn operation before, making pH off and on by interpolation mineral acid in processed liquid is below 4, simultaneously, adds corrosion inhibitor in processed liquid.
2. water treatment method as claimed in claim 1 adds mineral acid in each 0.5-2.5 hour scope.
3. water treatment method as claimed in claim 1 adds mineral acid with 1 day frequency of-1 month 1 time.
4. water treatment method as claimed in claim 1 is that making pH with every 2-1000 time 1 time frequency is below 3, under situation in addition, makes pH bigger than 3 in the operation below 4 making pH off and on.
5. water treatment method as claimed in claim 1, mineral acid is a sulfuric acid.
6. water treatment method as claimed in claim 1, corrosion inhibitor is a polyacrylic acid.
7. water treatment method as claimed in claim 6, polyacrylic molecular weight is more than 500, below 10000.
8. water treatment method as claimed in claim 1 adds mineral acid in the scope of 10ppm (weight)-1 weight %, add corrosion inhibitor in the scope of 0.1ppm (weight)-1 weight %.
9. water treatment method as claimed in claim 1 is adding the downstream side interpolation mineral acid of corrosion inhibitor to processed liquid.
10. water treatment method as claimed in claim 4 is 3 to add corrosion inhibitor when following at the pH that makes processed liquid.
11. water treatment method as claimed in claim 1, separatory membrane are reverse osmosis membranes.
12. water treatment method as claimed in claim 1 is a water treatment method of making tap water.
13. water treatment method as claimed in claim 1 as processed liquid, adopts seawater.
14. water treatment method, in the water treatment operation that adopts separatory membrane, in any operation before the membrane sepn operation, to make the viable count survival rate be below 30% by add mineral acid and corrosion inhibitor on processed liquid discontinuous ground, and add off and in the operation of mineral acid at this, the viable count survival rate is reached below 15% with every 2-1000 time 1 time frequency.
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| CN104548938A (en) * | 2014-12-03 | 2015-04-29 | 长沙中联重科环卫机械有限公司 | Membrane module pressure protection structure and reverse osmosis system, sewage treatment device |
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| CH673225A5 (en) * | 1986-04-22 | 1990-02-28 | Sanosil Ag | |
| JPH09891A (en) * | 1995-06-21 | 1997-01-07 | Nitto Denko Corp | Method for treating raw water using membrane module |
| CN1106355C (en) * | 1998-06-26 | 2003-04-23 | 朱锦棠 | Compound treating agent for water treatment |
| ES2300149T3 (en) * | 1998-07-21 | 2008-06-01 | Toray Industries, Inc. | PROCEDURE FOR THE INHIBITION OF THE DEVELOPMENT OF BACTERIA IN THE NEIGHBORHOOD OF A MEMBRANE OF SEPARATION AND STERILIZATION TECHNIQUE OF THIS. |
| JP2000167554A (en) * | 1998-10-02 | 2000-06-20 | Toray Ind Inc | Water making and membrane separator |
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