CN102531128A - Ferric salt-sodium alga acid combination anterior filming water treatment agent, production and application thereof - Google Patents
Ferric salt-sodium alga acid combination anterior filming water treatment agent, production and application thereof Download PDFInfo
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- CN102531128A CN102531128A CN2012100265658A CN201210026565A CN102531128A CN 102531128 A CN102531128 A CN 102531128A CN 2012100265658 A CN2012100265658 A CN 2012100265658A CN 201210026565 A CN201210026565 A CN 201210026565A CN 102531128 A CN102531128 A CN 102531128A
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Abstract
The invention relates to a ferric salt-sodium alga acid combination anterior filming water treatment agent, a production and an application thereof. The ferric salt-sodium alga acid combination anterior filming water treatment agent consists of raw materials according to the mass ratio of 1 part of sodium alga acid and 1-50 parts of ferric salt coagulant which takes the mass of ferrum into account; the sodium alga acid and the ferric salt coagulant are respectively prepared into solutions and are added with water to be treated successively. The ferric salt coagulant solution and the sodium alga acid solution are put into use successively with an interval of 30-50s. The combination anterior filming water treatment agent integrates the advantages of high molecular weight of the sodium alga acid, strong absorption bridging capability to colloidal substances, good coagulation effect of the inorganic ferric salt coagulant, good ultrafiltration effect and wide application scope, and also has the advantages of simple production technology and wide application scope after being applied in the water treatment field.
Description
Technical field
The present invention relates to the preceding water conditioner of film and the application thereof of molysite-sodium-alginate combination, belong to environmental chemistry water conditioner technical field.
Background technology
In recent years; Because shortage, the deterioration of water surrounding, the raising of drinking water standard and the limitation of traditional drinking water treatment technology of water resources are developed new drinking water safety safeguards technique to transform or to replace the conventional process technology to become the important topic that the municipal water supply industry faces.Membrane technique is called as the water technology of 21 century, and it all has certain advantage at aspects such as technology, economy, operational managements with respect to traditional technology, is that the combination process of core technology is called as third generation urban drinking water purification process with the ultrafiltration.The core of ultra-filtration technique is a ultra-filtration membrane, and it mainly removes the pollutent in the water body with the physics crown_interception.With common process relatively, ultra-filtration membrane technology has the following advantages: 1. go turbid rate high, stable effluent quality is reliable, its delivery turbidity is stable can be below 0.1NTU, can reach more than 99.9% to the clearance of particulate matter; 2. can effectively remove pathogenic micro-organism, ultrafiltration technology can effectively be removed pathogenic micro-organism and pathogenic virus such as giardia lamblia in the water, Cryptosporidium, bacterium; 3. water factory's floor space is little.Although ultra-filtration technique has numerous advantages, film pollutes the principal element that becomes its widespread use of restriction and development.Film pollutes the lasting decline can cause water flux, and the irreversible pollution of film is difficult to waterpower and cleans and recover, and makes film shorten work-ing life, and this will increase maintenance cost, the raising water producing cost of film.Therefore, when membrane process uses in reality, often unite use with other water technologies.
In order to improve the removal effect of ultrafiltration to water pollutant; Alleviate Pollution of Ultrafiltration Membrane; Increase the ultra-filtration membrane flux, adopt surface properties that various pretreatment modes change water pollutant usually and have form, like coagulation, sand coarse aggregate ratio, add Powdered Activated Carbon or PAC etc.In numerous pretreatment technology, coagulation pretreatment because easy, be prone to row, remove numerous advantages of water pollutant with the ultrafiltration combination and receive much concern.There is the research expression to adopt the coagulation-ultrafiltration combination process can reduce the amount of pollutant that gets into the ultrafiltration fenestra; Improve the character of ultra-filtration membrane surface deposition layer; Thereby the pollution abatement thing is in the absorption deposition on ultra-filtration membrane surface; Increase the ultra-filtration membrane permeation flux, can effectively reduce cake layer resistance and concentration polarization resistance, improve cycle physics cleaning performance.
Iron salt coagulant is widely used in the industries such as desliming processing of water purification processing and sewage, and it is strong to have a turbidity removal decoloring ability, to suspended substance removal rate advantages of higher.Research shows that in the selection of coagulating agent, molysite has more advantage.Because the souring ability of molysite is stronger than aluminium salt, the pH value is lower than aluminium salt during coagulation, thereby has improved the positive charge density of coagulating agent hydrolysate; Reduce the coagulating agent demand; Help organism and be adsorbed onto on the metal hydroxides, secondly, the ironic hydroxide amount that iron salt hydrolysis produces is much higher than the white lake that the aluminium salt hydrolysis is produced; And there is toxic problem in aluminum salt, is not very desirable at some occasion purifying water effect.Iron salt coagulant exists cost high, and corrodibility is big, and organic coagulating agent makes limited use because of its hydrolysis or degraded produce toxic substance.Based on the complementarity between inorganic, organic coagulating agent action effect, inorganic-organic coagulating agent becomes the focus of concern.
Sodium-alginate (SA) claim sodiun alginate, sodium alginate, algin again, and molecular formula is (C
6H
7Na) n is the sodium salt of the polyanionic polysaccharide (Lalgine) that extracts a kind of sea-tangle or sargassun from phaeophyta.Found sodium-alginate from 1883 in by sea-tangle, nineteen twenty-nine begins to be applied to industrial production in the U.S., and nineteen forty-four is applied to foodstuffs industry, and nineteen eighty-three directly is used for medicine industry as the composition of food through FDA Food and Drug Administration (FDA) approval.Sodium-alginate has advantages such as thickening property is good, good film-forming property, gel-strength is high, ropiness is good.Sodium-alginate is widely used in the aspects such as pollution of food, engineering in medicine, coating-film fresh-keeping and heavy metal, and sodium-alginate and inorganic salt coagulating agent are used for the patent of water treatment and do not appear in the newspapers so far.
CN101913714A discloses a kind of reverse osmosis water treatment agent and preparation method thereof; This reverse osmosis water treatment agent prescription is made up of following component: the mixture 10～40% of two kinds of organic phospho acid compounds; ROHM and/or its sodium salt 1～10%, HPMA 2～9%, sulfonic acid copolymer 2～20%; Dodecyl benzyl dimethyl ammonium chloride 0.1～3%, all the other are water.When product of the present invention is used for reverse osmosis water treatment system, can prevent CaCO
3, CaSO
4, Ca
3(PO
4)
2, BaSO
4, SrSO
4Deng dirt and ironic hydroxide, the deposition of zinc salt on reverse osmosis membrane, prolong the matting cycle and the work-ing life thereof of reverse osmosis membrane.
Summary of the invention
In order to remedy the deficiency that prior art exists, the present invention is main to provide water conditioner and preparation and application before the combined film of a kind of molysite-sodium-alginate.Water conditioner can strengthen coagulation effect before this film, and the membrane flux, the reduction film that improve in the subsequent handling pollute.
Technical scheme of the present invention is following:
Water conditioner before a kind of combined film, raw materials quality part is formed as follows:
1 part of sodium-alginate, iron salt coagulant is in 1～50 part of the quality of iron;
Described sodium-alginate is mixed with the solution use that concentration is 0.1～0.2g/L, and this sodium alginate soln is that sodium-alginate is placed softening water, and first swelling is dissolved and made under magnetic agitation;
Said iron salt coagulant places softening water to be made into the solution use that Fe (III) quality percentage composition is 0.5g/L.
Said iron salt coagulant is the trivalent iron salt coagulating agent, is selected from iron(ic)chloride (FeCl
3), poly-ferric chloride (PFC) or bodied ferric sulfate (PFS).
Preferably, Fe in described poly-ferric chloride or the bodied ferric sulfate (III) quality percentage composition is 5%～15%, and the basicity 0.5～1.5 of described poly-ferric chloride or bodied ferric sulfate, pH are 0.3～0.7, and molecular weight is 1000Da～50000Da.
Preferred according to the present invention, water conditioner raw materials quality part is formed as follows before the combined film:
1 part of sodium-alginate, iron salt coagulant is in 3～20 parts of the quality of iron.
According to the present invention, the preparation method of water conditioner before the combined film of a kind of molysite-sodium-alginate, step is following:
(1) sodium-alginate is placed 60-65 ℃ softening water, first swelling 5～15 minutes is carried out magnetic agitation again; 200-400 revolutions per second of churning time 25～30 minutes; Sodium-alginate is dissolved fully, be made into the sodium alginate soln of 0.1～0.2g/L, subsequent use in 4 ℃ of storages.
(2) get iron salt coagulant and at room temperature place softening water, being made into Fe (III) quality percentage composition is the solution of 0.5g/L.
(3) use before, get the iron salt coagulant solution of step (2), the sodium alginate soln of step (1) by 1 part of sodium-alginate, iron salt coagulant in the proportioning of 1～50 part of the quality of iron, add respectively in the pending water.
The application of water conditioner before the combined film of molysite-sodium-alginate of the present invention is used for feedwater, wastewater treatment, the water treatment of oil production, papermaking, mining, daily-use chemical industry.Application method is: by iron salt coagulant solution, sodium alginate soln at interval the order of 30-50 second successively drop in the pending water, sodium alginate soln adds that aftertreatment got final product in 20～30 minutes in the pending water.And then continue follow-up ultrafiltration membrane treatment technology.
The application of water conditioner before the combined film of molysite-sodium-alginate according to the present invention; Compare with traditional coagulation process, sodium alginate soln adds to be handled in the pending water 20～30 minutes, can obviously increase the coagulation flco; Obviously strengthen flco intensity; Improve the water treatment effect, alleviate Pollution of Ultrafiltration Membrane, increase the ultra-filtration membrane flux.
Water conditioner is made up of iron(ic)chloride or poly-ferric chloride (basicity=0.5) and sodium-alginate before the film of the present invention.Itself has negative charge sodium-alginate, and Zeta potential is at-60mV ± 3mV, and pH is the water white transparency thick liquid of 7.73-7.86.The staple of sodium-alginate is a polysaccharose substance, contains carboxyl and exists with the form of-COO-and COOH respectively.According to prior art for preparing.
Sodium-alginate is a kind of polymeric anion type flocculation agent, and it contains multiple organo-functional group, and wherein representative functional group is carboxyl and hydroxyl etc.; Can form synergy with the adsorption bridging effect of iron salt coagulant; The linear macromolecule structure of sodium-alginate strengthens the effect that its absorption volume is swept, because when adopting molysite and sodium-alginate composite, can be passed moisture film; Pass through the functional group contained, adsorption bridging between particle and particle.It is high, strong and inorganic molysite coagulating agent coagulation effect is good, ultrafiltration is effective and advantages of wide application range to the adsorption bridging ability of colloidalmaterial that the present invention combines the sodium-alginate molecular weight; Provide the combined film of a kind of molysite-sodium-alginate preceding water conditioner; Be applied to water treatment field simple and direct, economic, the applied widely advantage that has production technique.
The present invention compared with prior art has following excellent results:
1, the present invention compares with independent use inorganic molysite coagulating agent treatment effect, adds sodium-alginate and helps the effect of coagulating, and in surface water is handled, removes the organism effect and in more wide in range scope, has all obtained tangible improvement;
2, the present invention compares with independent use iron salt coagulant treatment effect, and formed flco obviously increases behind the interpolation sodium-alginate, and settling property significantly improves, and has effectively shortened the cycle of operation;
3, the present invention compares with synthetic organic polymers such as SEPIGEL 305s, and sodium-alginate has safety non-toxic as the extracting substance of sargassun, readily biodegradable, the advantage of non-secondary pollution;
4, after water conditioner passes through iron salt coagulant and the composite use of sodium-alginate before the film of the present invention, can strengthen the effect of coagulation, follow-up membrane process played the effect that improves membrane flux, alleviates the film pollution.
Description of drawings
Fig. 1 is that embodiment 3 adopts iron(ic)chloride-sodium-alginate coagulating agent, ferric chloride coagulant to carry out membrane flux and treatment time graph of a relation that coagulation-ultrafiltration is handled the humic acids simulated water sample.The iron(ic)chloride dosage is counted 5mg/L with the quality of Fe (III), and the sodium-alginate dosage is 0.3mg/L.Coagulation-ultrafiltration is handled the humic acids simulated water sample
Fig. 2 is that embodiment 4 adopts poly-ferric chloride-sodium-alginate coagulating agent, poly-ferric chloride coagulant to carry out membrane flux and treatment time graph of a relation that coagulation-ultrafiltration is handled the humic acids simulated water sample.The iron(ic)chloride dosage is counted 5mg/L with the quality of Fe (III), and the sodium-alginate dosage is 0.3mg/L.
Embodiment
Below in conjunction with embodiment, application examples the present invention is further specified.
The experiment water sample: the preparation method of water sample is referring to Xu Xiuming etc.: Al in the Poly aluminum Chloride (PAC)
bForm is removed the effect and the Mechanism Study of humic acid, Environmental Science and Engineering institute of Shandong University, environmental science; 2008,29 (11): 3064-3070: take by weighing the 1g humic acid, be in harmonious proportion with small amount of deionized water; And add a certain amount of NaOH regulator solution pH; Promote dissolving, constant volume is mixed with the simulated water sample stock solution of 1g/L to 1L behind the magnetic agitation 0.5h.During coagulation experiment, be in harmonious proportion with tap water, being made into concentration is 10mg/L humic acid simulated water sample.
In following application example one to four, all use above-mentioned water sample.The raw material that uses among the embodiment is the commercially available prod.
Embodiment 1: sodium-alginate and ferric chloride coagulant combination
Sodium-alginate: ferric chloride coagulant (in iron)=1: 3～20 combination quality ratios.
(1) takes by weighing a certain amount of sodium-alginate; Make its preliminary swelling 10 minutes with 60-65 ℃ softening water; Under magnetic stirring apparatus, stirred 25-30 minute, it dissolved fully with 200-400 revolutions per second speed, the sodium alginate soln that is made into 0.1g/L be put in 4 ℃ subsequent use.
(2) take by weighing a certain amount of ferric chloride coagulant, at room temperature as in the softening water, being made into Fe (III) quality percentage composition is the solution of 0.5g/L.
(3) get the ferric chloride coagulant solution of step (2), the sodium alginate soln of step (1), earlier iron salt coagulant was added in the pending water coagulating treatment 30 seconds, the sodium alginate soln of step (1) is added in the water sample handled 20-30 minute again.The dose that adds of sodium-alginate is 0.3mg/L (in the sodium-alginate solid masses), and ferric chloride coagulant adds dose and is respectively 1mg/L, 2mg/L, 3mg/L, 4mg/L, 5mg/L, 6mg/L in the quality of iron (III).
Application example one:
The inorganic iron of embodiment 1 preparation is mixed-the composite film of sodium-alginate before water conditioner (iron(ic)chloride-sodium-alginate); (it is the quality of iron(ic)chloride in iron that table 1 adds dose to be used for the coagulating treatment of humic acids simulated water sample; The dosage of sodium-alginate is 0.3mg/L water), handle contrasting simultaneously with iron(ic)chloride coagulation list.The raw water quality situation is following: the pH value is 7.37-7.40, and turbidity is 5.6-5.0NTU, UV
254Be 0.327-0.268cm
-1, DOC is 4.948-5.116mg/L.Result is listed in table 1:
Water conditioner is handled the effect of humic acids simulated water sample before the composite film of table 1 iron(ic)chloride/iron(ic)chloride-sodium-alginate
Visible from above result; The coagulation effect of the composite aftertreatment humic acids of iron(ic)chloride and sodium-alginate simulated water sample obviously is superior to the processing that ferric chloride coagulant is applied to water sample separately; As when molysite dosage during greater than 2mg/L, the coagulation water outlet water sample after iron(ic)chloride and sodium-alginate are composite, its residual turbidity is reduced to below the 0.98NTU; And iron(ic)chloride is done the time spent separately all greater than 1NTU, UV
254Do the time spent with the clearance of DOC separately than iron(ic)chloride the raising of 3%-9% is all arranged.
Embodiment 2: sodium-alginate and poly-ferric chloride coagulant combination
Take by weighing a certain amount of sodium-alginate; Make its preliminary swelling for some time with 60-65 ℃ softening water; Under magnetic stirring apparatus,, it is dissolved fully with stirring between 200-400 revolutions per second the speed 25-30 minute, the sodium alginate soln that is made into 0.1g/L be put in 4 ℃ subsequent use.
Iron salt coagulant poly-ferric chloride and sodium-alginate were successively added pending simulated water sample in 30 seconds at interval carry out coagulating treatment, the dose that adds of sodium-alginate is 0.3mg/L, and iron salt coagulant adds dose and is respectively 1mg/L in the quality of iron; 2mg/L, 3mg/L, 4mg/L; 5mg/L, 6mg/L.
Application example two:
With water conditioner (poly-ferric chloride-sodium-alginate) before the composite film of inorganic poly-ferric chloride-sodium-alginate of preparation among the embodiment 2; (it is the quality of iron(ic)chloride in iron that table 2 adds dose to be used for the coagulating treatment of humic acids simulated water sample; The sodium-alginate dosage is 0.3mg/L), contrast with the poly-ferric chloride individual curing simultaneously.The raw water quality situation is following: the pH value is 7.42-7.50, and turbidity is 6.5-5.3NTU, UV
254Be 0.275-0.332cm
-1, DOC is 4.639-3.763mg/L.Result is listed in table 2.
The effect of humic acids simulated water sample is handled in the composite film pre-treatment of table 2 poly-ferric chloride/poly-ferric chloride-sodium-alginate
Visible from above result; Poly-ferric chloride is compared as the time spent separately with poly-ferric chloride coagulant with the coagulation effect of the composite aftertreatment humic acids of sodium-alginate simulated water sample; No matter hanging down under the situation that dosage still is high dosage; Can both improve coagulation effect, especially effect is more obvious under low dosage.
Application example three: coagulation-ultrafiltration coupling water treatment experiment
Water conditioner before the composite film of iron(ic)chloride-sodium-alginate of embodiment 1 is carried out coagulation pretreatment to the humic acids simulated water sample; Its dosage is that the iron(ic)chloride (in iron) among the embodiment 1 is 5mg/L; With the ultrafiltration coupling; Compare the variation of membrane flux and as shown in Figure 1 with independent when using iron(ic)chloride to use as coagulating agent: the water conditioner coagulation-ultrafiltration is handled the film consumption of humic acids simulated water sample before the composite film of iron(ic)chloride/iron(ic)chloride-sodium-alginate.The result of Fig. 1 is visible, when coagulating agent uses iron(ic)chloride as coagulating agent more separately before the composite film of iron(ic)chloride-sodium-alginate, the flux of ultra-filtration membrane is significantly improved, and is in service in actual water treatment, can reduce cost of water treatment.
Application example four: coagulation-ultrafiltration coupling water treatment experiment
Water conditioner before the composite film of poly-ferric chloride-sodium-alginate of embodiment 2 is carried out coagulation pretreatment to the humic acids simulated water sample; Its dosage is that the poly-ferric chloride (in iron) among the embodiment 2 is 5mg/L; With the ultrafiltration coupling; Compare when using poly-ferric chloride to use as coagulating agent with independent, the variation of membrane flux is as shown in Figure 2: the water conditioner coagulation-ultrafiltration is handled the film consumption of humic acids simulated water sample before the composite film of poly-ferric chloride/poly-ferric chloride-sodium-alginate.Visible by the result of Fig. 2, when coagulating agent uses iron(ic)chloride as coagulating agent more separately before the composite film of poly-ferric chloride-sodium-alginate, the flux of ultra-filtration membrane there is raising; In service in actual water treatment, not only cost of water treatment can be reduced, and environmental protection can be realized.
Claims (5)
1. water conditioner before the combined film is characterized in that raw materials quality part forms as follows:
1 part of sodium-alginate, iron salt coagulant is in 1～50 part of the quality of iron;
Described sodium-alginate is mixed with the solution use that concentration is 0.1～0.2g/L, and this sodium alginate soln is that sodium-alginate is placed softening water, and first swelling is dissolved and made under magnetic agitation;
Said iron salt coagulant places softening water to be made into the solution use that Fe (III) quality percentage composition is 0.5g/L;
Said iron salt coagulant is the trivalent iron salt coagulating agent, is selected from iron(ic)chloride (FeCl
3), poly-ferric chloride (PFC) or bodied ferric sulfate (PFS).
2. water conditioner before the combined according to claim 1 film is characterized in that raw materials quality part composition as follows:
1 part of sodium-alginate, iron salt coagulant is in 3～20 parts of the quality of iron.
3. water conditioner before the combined according to claim 1 film; It is characterized in that Fe in described poly-ferric chloride or the bodied ferric sulfate (III) quality percentage composition is 5%～15%; The basicity 0.5～1.5 of described poly-ferric chloride or bodied ferric sulfate; PH is 0.3～0.7, and molecular weight is 1000Da～50000Da.
4. the preparation method of water conditioner before the said combined film of claim 1, step is following:
(1) sodium-alginate is placed 60-65 ℃ softening water, first swelling 5～15 minutes is carried out magnetic agitation again; 200-400 revolutions per second of churning time 25～30 minutes; Sodium-alginate is dissolved fully, be made into the sodium alginate soln of 0.1～0.2g/L, subsequent use in 4 ℃ of storages;
(2) get iron salt coagulant and at room temperature place softening water, being made into Fe (III) quality percentage composition is the solution of 0.5g/L;
(3) use before, get the iron salt coagulant solution of step (2), the sodium alginate soln of step (1) by 1 part of sodium-alginate, iron salt coagulant in the proportioning of 1～50 part of the quality of iron, add respectively in the pending water.
5. the application of water conditioner before each said combined film of claim 1～3 is used for feedwater, wastewater treatment, the water treatment of oil production, papermaking, mining, daily-use chemical industry; Application method is: by iron salt coagulant solution, sodium alginate soln at interval the order of 30-50 second successively drop in the pending water, sodium alginate soln adds that aftertreatment got final product in 20～30 minutes in the pending water.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103964644A (en) * | 2014-05-19 | 2014-08-06 | 国家电网公司 | Advanced domestic wastewater treatment method |
| CN103964643A (en) * | 2014-05-19 | 2014-08-06 | 国家电网公司 | Method for deeply treating reclaimed water for supplementary water of circulating cooling water for heat-engine plants |
| CN103964610A (en) * | 2014-05-19 | 2014-08-06 | 国家电网公司 | Industrial wastewater deep treatment method |
| US9359228B2 (en) | 2013-03-15 | 2016-06-07 | Ndsu Research Foundation | Iron-functionalized alginate for phosphate and other contaminant removal and recovery from aqueous solutions |
| CN106186227A (en) * | 2016-08-31 | 2016-12-07 | 严建泗 | A composition for inhibiting algae production |
| CN106315711A (en) * | 2016-09-26 | 2017-01-11 | 国家海洋局天津海水淡化与综合利用研究所 | Layer-by-layer slow release water treatment agent for delaying sea water membrane pollution and preparation method thereof |
| CN114590877A (en) * | 2022-03-10 | 2022-06-07 | 华北水利水电大学 | Construction method of a compound coagulation system for efficiently removing bromate and its application in water treatment |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9359228B2 (en) | 2013-03-15 | 2016-06-07 | Ndsu Research Foundation | Iron-functionalized alginate for phosphate and other contaminant removal and recovery from aqueous solutions |
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| CN103964643A (en) * | 2014-05-19 | 2014-08-06 | 国家电网公司 | Method for deeply treating reclaimed water for supplementary water of circulating cooling water for heat-engine plants |
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| CN106315711A (en) * | 2016-09-26 | 2017-01-11 | 国家海洋局天津海水淡化与综合利用研究所 | Layer-by-layer slow release water treatment agent for delaying sea water membrane pollution and preparation method thereof |
| CN114590877A (en) * | 2022-03-10 | 2022-06-07 | 华北水利水电大学 | Construction method of a compound coagulation system for efficiently removing bromate and its application in water treatment |
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Application publication date: 20120704 |