CN1068549A - The method of purifying waste water - Google Patents
The method of purifying waste water Download PDFInfo
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- CN1068549A CN1068549A CN 91104651 CN91104651A CN1068549A CN 1068549 A CN1068549 A CN 1068549A CN 91104651 CN91104651 CN 91104651 CN 91104651 A CN91104651 A CN 91104651A CN 1068549 A CN1068549 A CN 1068549A
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Abstract
The method of purifying waste water comprises that Xiang Shuizhong adds that a kind of the galvanic corrosion dispersion is made in water with ferrous metal, and sorbent material one suspension, stirring and the solid phase of carrying out in succession that magnet content is no less than 3% (weight) are separated.Be added to the quantity of the suspension in the water, by dry-matter, every purification one gram impurity needs 3-120 grams.
Description
The method that the present invention relates to purify waste water.Heavy metal that this method is used for purifying waste water and light metal ion, radionuclide, nitrate, phosphorus compound, petroleum products traces etc.
Known electricity coagulates purifying sewage method (B.M.MakapoB, IO. П .SenNyeHko N II Pypue. " Pa II NOHanbHoe Ncnonb30BaHue N OYNCTKa BONBI Ha Ma III UHOCTPOCTPOUTeNbHbZX Npe III PURTURX ", MockBa, Ma III uHOCTPOeHue, 1988, C.159-170) be in the sewage of containing metal impurity, to add sodium-chlor, electrolysis generation ironic hydroxide absorption beavy metal impurity is carried out in energising between the ferroelectric utmost point then, and the agglomerative throw out is just separated from water.
The characteristics of described method are the efficient height, per minute consumes about iron 10 grams from 1 gram impurity, but this method can only be removed some metal ion, and as chromium, nickel, and other most of impurity (phosphoric acid salt, nitrate, muriate, copper, mercury, aluminum compound) can not be removed from water.The sodium-chlor that uses during electrolysis has increased water and sedimentary pollution again.The characteristics of electrocoagulation are that current consumption is big, for example contain 40 gram/rice in purification
3During the sewage of chromium (VI) compound, current consumption is 12 kilowatt-hours/meter
3Because the passivation of impurity counter electrode, the stability of water treatment procedure is damaged.
Another known method is the Sirofloc flow process that Australia is used for purifying drinking water.（"Water treatment using magnetite，astudy of a sirofloc pilot plant Gregory R.，Maloney R.J.，Stocklev M.，J，Inst.water and Environ.Manag.，1988，V.2，N5，pp.532-544）。In this flow process, use the mechanical disintegration natural magnetite, make high dispersive magnetite powder as sorbent material.Heavy metal ion is attracted on the magnetite ore particles and is filled in the hole of its lattice vacancy.The magnetite powder is about 3 minutes with the water that is cleaned duration of contact.By magnetic field powder is separated from water then.The effect of aforesaid method depends on the quality of sorbent used-magnetite.But magnetic iron powder standing storage and any distance transportation, quality does not have substantive the deterioration.The time length of purifying waste water is short.
But when stating flow process on the implementation, need purity level high, and the magnetite powder of granularity minimum (about 1-10 micron).This makes this method complicated and expensive.The natural magnetite powder can not purge all detrimental impurity in the water in addition.The adsorptive power of the natural magnetite of pulverizing is far smaller than its theoretical value, because be lattice vacancy and hole participation water purification that those magnetites that are ground into powder expose.
Known method is from containing 20-40%(weight) FeCl
3Ferric chloride in aqueous solution in remove heavy metal (chromium, copper, mercury, arsenic, cadmium, lead) (JP.A, 53-82696).This method is that the pH value of the aqueous solution that will purify with hydrochloric acid or sulfuric acid transfers to about 3, and adds dried iron powder.Stir after trembling filtering the ferric chloride in aqueous solution of throw out after purifying.
Because the adsorptivity of iron powder is low, the water purification degree is not high.For example, containing the chromium (VI) of 18 mg/litre before ferric chloride in aqueous solution purifies, is 6 mg/litre after the purification.Need consume a large amount of iron powders (every liter of aqueous solution that will purify needs 400-600 gram iron powder) by described method.
The known method that the middle heavy metal of purifying waste water (cadmium, zinc, copper, lead, mercury, iron and arsenic) arranged (JP, A, 52-45665).When pH=5-7, in sewage, add sorbent material-dried iron powder, stir the gained mixture, and with the filtering of solid phase precipitation thing.Between Powdered iron and heavy metal ion, absorb-coprecipitation reaction.
It is higher to remove in the water degree of above-mentioned metal in this way.
Adopt this method, do not need to build complicated purification facility and use the equipment of producing powder.Because can use industrial 100-400 order (25-150 micron) granulometry iron powder to get final product.But the characteristics of aforesaid method are the iron powder consumptions too big (whenever purge 1 gram impurity, consume iron 60-300 gram).
Iron powder consumption senior general causes the volume and weight of residue after the sewage purification to increase, and this will aggravate the pollution to surrounding environment.In addition, the characteristics of this method are that production efficiency is low and process duration is long, because churning time is no less than 60 minutes.Can this method can only be removed some heavy metal ion, and remove more ubiquitous chromium ion and tin, nitrate, sulfate ion and petroleum products no data still at present from the sewage that electroplate to produce.
Task of the present invention is that development is a kind of by the method for selecting a kind of iron-based sorbent material to purify waste water.
This sorbent material is keeping higher water purification degree and is enlarging under the condition of separating impurity kind, can reduce the consumption of iron and improve flow process speed and production efficiency.
This task is to solve by proposing a kind of method of purifying waste water.This method is included in and adds the iron-based sorbent material in the water, stirs and also carries out the solid phase separation subsequently.According to the present invention, use the ferrous metal suspension that the galvanic corrosion dispersion method obtains in water as sorbent material, and magnetite content is not less than 3(weight in the solid phase) %.
The method energy that is proposed:
-reducing the consumption of from the water that will purify, removing the per unit impurity iron, the iron consumption of for example removing the per unit heavy metal is a 3-26 gram/gram.
-reduce the pollution of residue by being reduced in the formed residue quantity of purification per unit volume water to surrounding environment.
-by the speed that improves purification process with shorten necessary churning time improved the water purification process to 3-5 minute production efficiency.
-increase and from water, remove the kind of detrimental impurity, thus the spendable scope of institute's proposition method enlarged.
The above-mentioned advantage of present method is owing to being not less than 3(weight with magnetite content) the iron powder aqeous suspension of % guaranteed as sorbent material.This is because ferrous metal (iron, carbon steel, the pig iron) galvanic corrosion in water disperses obtained powder particle to have special metal construction, is characterized in the big and chemically reactive height of lattice vacancy density.As everyone knows, lattice vacancy can become adsorption center.This may be to improve one of active reason of described adsorbents adsorb.Should be pointed out that in the galvanic corrosion dispersion process carbon in the steel and the pig iron and other impurity are burnt.
The existence of magnetite also is the condition that improves the powder adsorption activity.Magnetite forms owing to galvanic corrosion disperses active iron and water intensive chemical action that obtains and the result who follows release hydrogen.This newly-generated magnetite and common iron are still compared with common magnetite, all have higher adsorption activity.Magnetite content is lower than 3(weight in the suspension) %, can not greatly guarantee to improve water purification speed.
Iron powder also is that powder polymolecularity (0.1-10 micron) determines than high absorbability in the suspension.Dispersed raising cause specific surface area long-pending increase and with water in the speed of response of impurity accelerate.Currently known methods (JP, A, 52-45665) described in so the dry iron powder of polymolecularity (less than 10 microns) can not be used to purify waste water because its can nature or oxidation rapidly in air, thereby be transformed into the inertia rhombohedral iron ore of impurity in the planar water not.
In order to guarantee the best purification condition of water, preferably in the water that is cleaned, add suspension, its quantity adds dry-matter 3-120 gram by each gram impurity of dry-matter.The lower value 3 gram/grams of above-mentioned scope equal the loading capacity of suspension, surpass higher limit 120 gram/grams and then can not guarantee to improve greatly water purification speed and degree.
For speed and the production efficiency that improves scavenging process, preferably suspension and the water that is cleaned are stirred under 20 ℃ of-70 ℃ of temperature, temperature is higher than 70 ℃ of reductions that will cause purification speed.
Suggestion will be no less than 50%(weight) iron content, magnetite and the solid phase isolate of the impurity that is adsorbed send in the water and in the mixture at suspension in the suspension adding stage and be used as sorbent material, owing to improved the utilising efficiency of suspension, can effectively utilize suspension like this.
Before suspension was added in the water that is not cleaned, the most handy ultrasonic agitation can destroy suspension like this at the coagulated lumps that stores and form between the delivery period, to guarantee to improve the iron powder specific surface area that participates in adsorption process.
Suggestion is magnetized the suspension magnetite ore particles by magnetic field and is realized the solid phase separation, thereby the very fast integrated package with fixed attention of these particles, thereby improves the efficient of cleaning sections such as follow-up clarification and/or filtration.
Suggestion suspension before being added to and being cleaned in the water boils suspension, so that sterilization before using.For example, more should be like this when purifying drinking water or suspension standing storage.Boiling part can greatly improve the speed of the generation of magnet, can significantly reduce the release of hydrogen between the shelf lives after boiling.
Below in conjunction with synoptic diagram, describe the present invention-water purification method in detail, to implementing the device of present method, make a schematic illustration in the synoptic diagram.
This cover is connected to each other and comprises array apparatus down by the technical process installed device: storage tank 1, transport pipe 2, pump 3, the suspension and the stirring container 4 of will purifying waste water, hydrocyclone 5, magnetization device 6, settling bath 7, working shaft 8, strainer 9, collector 10.On transport pipe 2, valve 11 is housed in the exit of storage tank 1.Container 13 and the suspension stirring ultrasonication suspension device 14 through pipeline 12 process sequence installed in the exit of working shaft 3 are connected on the pipeline 2.On device 14 exit transport pipes 12, valve 15 is housed.The outlet of hydrocyclone 5 is connected on the pipeline 2 of pump 3 ingress through pipeline 16.Residue receiving tank 17 is housed below settling bath 7, and the settling bath top is equipped with switch 18.
For water purification, get the iron suspension that galvanic corrosion makes after disperseing in water, this suspension is by SU, and A installs preparation described in 663515, and device does not provide in the drawings.This device is to be made by insulating material, and by forming with the container of two plain plate electrodes, is added with pulsed voltage thereon.The iron ore particle of specification for 10mm pelletizing reduction (metallization) in filling between the two poles of the earth.At container bottom mesh is arranged, through mesh feedwater stirring particles layer.After the energising, in water, produce electric charge along granuloplastic loop.It is the galvanic corrosion dissemination of generation granular metal and electrode as a result.The unit power consumption amount of dissemination is 4 kilowatt-hours on every kilogram of metal.The suspension that the galvanic corrosion product is made up of the iron powder that is suspended in the high dispersive (smaller or equal to 1 micron) in the water.The galvanic corrosion product is taken out of container by current and is assembled in settling bath, and its residence time is till not releasing hydrogen bubble and surface formation foam.At this moment, the iron in the suspension begins to change into magnetite.The magnetite amount of the residence time and generation is listed in table 1.The suspension that will accumulate in settling bath bottom is then poured in the container and it is sent to and purifies waste water.Suspension is used to purify electroplates the sewage that produces, and its chemical ingredients is listed in the table 1.
Carry out in the equipment shown in the water purification in the diagram.The water that purifies is collected in the storage tank 1, and suspension is added in the container 13.The ratio of solid phase and liquid phase (T: G) as shown in table 1.Start pump 3, slowly open valve 11 and 15, mix up set discharge Q
1With corresponding suspension flow Q
2Deliver in the device 14 from container 13 with the continuous stirred suspension of stirrer and through pipeline 12, and carry out ultrasonication, so that its all even raising adsorption activity.Then, with pump 3 suspension (along pipeline 12,2) and the water (along pipeline 2) that will purify are delivered to each container in three containers 4 successively.In these containers, use upwelling stirred suspension and water.T in container 4: G ratio is listed in table 1.At this moment the ion of the metal ion in the water and other impurity is attracted on the particle of suspension.The cubic capacity of container 4 should equal the volume of the water that this device purified in 3 minutes.From last container of container 4, the water of water and band suspension is delivered to hydrocyclone 5, throw out is concentrated pulping here.Flow is Q
3Slurries through pipeline 16 from hydrocyclone flow ipe 2 and further drawn by pump 3, then dilute original suspension.T in the slurries: G ratio is listed in the table 1.Clarifying water and suspension residue are from hydrocyclone 5 accesss to plant 6, and here the particle of suspension is magnetized and enters magnetic field, thereby partial coagulation takes place.Water enters settling bath 7 from installing 6, and suspension precipitates into throw out here rapidly, and throw out constantly is discharged in the receiving tank 17 through switch 18.These throw outs will be buried and utilization of waste material.Clarifying water is delivered to the strainer 9 of being with the linen canvas filter cloth through pump 8 from settling bath 7, and here water separates with the suspension residue.Water enters the water purification receiving tank 10 from strainer 9.
Before in following table 1, having listed various parameters, suspension properties and the purification of flow process, purify the content of impurity in the water of back.
Embodiment 1
Get 8 0.5 liter sewage sample, the chemical ingredients of its impurity is listed in table 2.For removing the middle impurity that anhydrates, add 12 suspension of making by above-mentioned technology in the measuring cup that fills this sewage (0.5 liter), its dissimilarity is the carbon steel piece to be carried out galvanic corrosion disperse, the concentration of suspension (T: G) be 1: 2, listed in magnetite content such as the table 2 in the solid phase.The quantity that splashes into suspension in the water that need to purify is listed in the table 2.Every is about 0.3 milliliter.Stir with glass stick then and tremble contained material in the cup, churning time is as shown in table 2, water is left standstill 10 minutes then, after this, clarifying water carefully poured out and on funnel through filter paper filtering, resulting purifying waste water analyzed with photocolorimetry and polarography, test-results is listed in the table 2.
Embodiment 2
Get 5 and contain 90sr radionuclide and 90Y, and radioactivity be (1-8) * 10 Curie/liter 0.5 premium on currency sample.
Whole purification processes of water are identical with embodiment 1, and its dissimilarity is, purify in capacity is 0.05 liter measuring cup.Suspension is made with containing sulphur pig iron galvanic corrosion dispersible tablet in water.Solid load is 30 milligrams in the every suspension, and the various parameters that water purifies are with the results are shown in Table 3.
Embodiment 3
Said apparatus with shown on the synoptic diagram purifies two batches of tap water.But pour into the water that need purify in the container 1 and will pour in the container 13 with the Armco Armco magnetic iron suspension that galvanic corrosion disperses to make in water by above-mentioned technical process, its difference is that suspension boiled earlier one hour before pouring container 13 into, to remove contained bacterium and other microorganism.The various parameters of purification process are with the results are shown in Table 4.
Present method be used for purifying waste water heavy metal and light metal ion, radionuclide, nitrate, phosphorus compound ion and petroleum products traces.
Table 1
Parameter is pressed currently known methods by the inventive method
Suspension parks 3 24-
Time, hour
In the suspension solid phase
Magnetite content, (weight) % 3 10-
T in the suspension: G ratio
Weight hour 1: 91: 6-
The flow Q of water
I, rice
3/ hours 8 17-
Suspension flow Q
2, rise/hours 143 226-
The churning time of suspension and water,
Minutes 63 60
The consumption of iron, gram:
Have and purify 1 meter
3Water 1,785 1,902 180000
From water, remove 1 gram impurity 36 300
The flow Q of return oar liquid
3
Rice
3/ hours 24
Solid concentration in the return oar liquid,
Grams per liter 21.4 44.5
Solid concentration in the container 4, grams per liter 5.7 10.0
Impurity concentration in the water, mg/litre
Continuous table 1
1 2 3 4
Before purifying/after purifying:
Chromium 234/0.07 180/0.01 234/180
Cadmium 78/0.43 1.8/0.01 78/0.5
Zinc 25/0.28 17/0.005 25/0.9
Aluminium 16/0.05 13/0.05 16/12
Tin 7/0.09 4.4/0.05 7/5
Plumbous 3/0.2 0.45/0.03 3/0.3
Nickel 26/0.18 56/0.05 26/20
Copper 150/0.69 425/0.05 149/6
Iron 53/0.5 2.4/0.005 55/50
Petroleum products 8/0.1 6/0.1
Table 2
Sample
1 2 3 4 5 6 7 8
1 2 3 4 5 6 7 8 9
Magnet in the suspension solid phase
The content %(weight in ore deposit) 30 30 40 50 50 50 50 50
The amount 3222 25 17 14 of dripping of suspension
Churning time, minutes 13333333
The iron consumption, milligram:
1 cubic decimeter of water 180 120 120 120 1,500 60 420 820 of every purification
Whenever remove 1 milligram of impurity 85553 12 32
Impurity is concentration in water,
1 liter of milligram
Before purifying/after purifying
Continuous table 2
1 2 3 4 5 6 7 8 9
Chromium (6
+) 22/0.1
22/0.5
Nickel 32/0.1
Plumbous 30/0.03
Copper 500/0.1
Mercury 4.95/0.0062
Iron 0/0.1 0/0.05 0/0.08 0/0.05 0/0.1 0/0.05 13/0.05 0.8/0.3
Table 3
The parameter sample
1 2 3 4 5
1 2 3 4 5 6
The radioactivity of water * 10
7
Curie/liter
Purify preceding 1.66 1.55 1.61 1.6 1.5
Purify back 0.07 0.05 0.05 0.04 0.04
Table 4
Each batch of parameter result is to the requirement of tap water
1 2
1 2 3 4
The suspension storage period,
Hour:
Boil preceding 1,000 24
Boil back 1000
Magnet in the suspension solid phase
Mineral content, %(weight)
Boil preceding 40 8
Boil back 60 20
The release of gas from suspension
Speed: milliliter/hour kilogram:
Boil preceding 0.1 2.3
Boil back 0.05 0.2
T in the suspension: G ratio: 1: 91: 9
Weight hour
Discharge Q
1, rice
3/ hours 88
Suspension flow Q
2, kilogram/hours 16 8
Suspension and water churning time,
Minutes 36
Continuous table 4
1 2 3 4
The iron consumption, gram:
1 meter of every purification
3Water 200 100
From water, purge 1 gram impurity 10 5
Return oar flow quantity Q
3,
Rice
3/ hours 11
Solid phase in return oar liquid
Concentration, grams per liter 10 20
Solid concentration in the container 13,
Grams per liter 2.4 2.3
The characteristic of water
Before purifying/after purifying:
Turbidity, mg/litre 19/0.9 19/0.9＜1.5
Transparency, centimetre 7,/30 7,/30 30
pH 6.7/7.0 6.7/7.2 6.0-9.0
Hardness, equivalent parts per million 3.8/2.9 3.8/3.0＜7.0
Impurity concentration, mg/litre
Iron 3.6/0.2 3.6/0.1＜0.3
Manganese 0.425/0.02 0.425/0.01＜0.1
Copper 0.65/0.02 0.65/0.01＜0.1
Plumbous 0.1/0.001 0.1/0.002＜0.03
Aluminium 1.2/0.01 1.2/0.008＜0.02
Zinc 4.0/0.03 4.0/0.02＜5.0
Continuous table 4
1 2 3 4
Mercury 1.2/0.0007 1.2/0.0006＜0.001
Chromium (6
+) 1.0/0.005 1.0/0.004＜0.05
Petroleum products 2.0/0.05 2.0/0.1＜1.9
Chlorine 0.1/0.001 0.1/0.005
Fluorine 0.63/0.2 0.63/0.25＜0.2
Nitrate 4.5/3.9 4.5/4＜40
Claims (7)
1, a kind of method of purifying waste water, this method is included in and adds the iron-based sorbent material in the water, stirs and separate with the capable solid phase of going on, it is characterized in that making sorbent material with the ferrous metal suspension that galvanic corrosion disperses to make in water, wherein magnetite content is not less than 3% (weight) in the solid phase.
2, according to the method for claim 1, the quantity that it is characterized in that being added to the suspension in need purifying waste water is by dry-matter, and every purification one gram impurity needs the 3-120 gram.
3,, it is characterized in that suspension and the water that will purify stir under 20-70 ℃ of temperature according to the method for claim 1.2.
4,, it is characterized in that iron content, magnetite and be adsorbed the 50%(weight of the solid phase that separate impurities comes out according to the method for claim 1) more than deliver to suspension and add entry scala media section, and in being mixed with the mixture of suspension, be used as sorbent material.
5, according to the method for claim 1, it is characterized in that described suspension joins in the water that will purify before, carry out agitation treatment with ultrasonic wave.
6,, it is characterized in that carrying out solid phase by magnetic separates according to the method for claim 1.
7, according to the method for claim 1, it is characterized in that described suspension joins in the water that will purify before, boil earlier.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91104651 CN1068549A (en) | 1991-07-13 | 1991-07-13 | The method of purifying waste water |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91104651 CN1068549A (en) | 1991-07-13 | 1991-07-13 | The method of purifying waste water |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102390880A (en) * | 2011-07-18 | 2012-03-28 | 中国科学院新疆理化技术研究所 | Method for performing ultrasonic separation on oily wastewater with oil-soluble ferroferric oxide nanoparticles |
| CN103754952A (en) * | 2014-01-22 | 2014-04-30 | 同济大学 | Preparation method and application of iron-based material for removing heavy metal in wastewater synchronously |
| CN104507548A (en) * | 2012-06-27 | 2015-04-08 | 阿尔戈耐德公司 | Aluminized silicious sorbent and water purification device incorporating the same |
-
1991
- 1991-07-13 CN CN 91104651 patent/CN1068549A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102390880A (en) * | 2011-07-18 | 2012-03-28 | 中国科学院新疆理化技术研究所 | Method for performing ultrasonic separation on oily wastewater with oil-soluble ferroferric oxide nanoparticles |
| CN104507548A (en) * | 2012-06-27 | 2015-04-08 | 阿尔戈耐德公司 | Aluminized silicious sorbent and water purification device incorporating the same |
| US9707538B2 (en) | 2012-06-27 | 2017-07-18 | Argonide Corporation | Aluminized silicious powder and water purification device incorporating same |
| CN103754952A (en) * | 2014-01-22 | 2014-04-30 | 同济大学 | Preparation method and application of iron-based material for removing heavy metal in wastewater synchronously |
| CN103754952B (en) * | 2014-01-22 | 2015-08-19 | 同济大学 | A kind of iron preparation method of synchronous removal heavy metal in waste water and application |
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