CN1821117A - Treatment method of waste water - Google Patents

Treatment method of waste water Download PDF

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Publication number
CN1821117A
CN1821117A CNA2006100089754A CN200610008975A CN1821117A CN 1821117 A CN1821117 A CN 1821117A CN A2006100089754 A CNA2006100089754 A CN A2006100089754A CN 200610008975 A CN200610008975 A CN 200610008975A CN 1821117 A CN1821117 A CN 1821117A
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boron
mentioned
liquid
value
iodine
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CN1821117B (en
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高桥诚
宫泽孝明
田中信洋
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Nippoh Chemicals Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/02Treatment of water, waste water, or sewage by heating
    • C02F1/04Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/048Purification of waste water by evaporation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/58Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • C02F11/12Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/13Treatment of sludge; Devices therefor by de-watering, drying or thickening by heating
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/108Boron compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/12Halogens or halogen-containing compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/06Controlling or monitoring parameters in water treatment pH

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Removal Of Specific Substances (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

The process of eliminating boron and iodine from waste water containing high concentration boron and iodine is disclosed. The process includes the following steps: regulating the pH value of waste water containing iodine and/or iodine ion and boron and/or boron ion to 8-14; concentrating to reach boron and/or boron ion concentration to 0.5 wt% or higher; cooling the obtained liquid and regulating pH value to 1-7 so as to separate out boron component; and eliminating the separated matter and separating boron and/or boron ion.

Description

Wastewater treatment method
Technical field
The present invention relates to wastewater treatment method, more particularly, relate to by under alkaline condition, waste water being carried out evaporation concentration, the pH value that will concentrate waste water then is adjusted to acidity, removing the method for wastewater treatment of the boron of separating out, and relate to being included in and remove the wastewater treatment method of further removing the step of iodine after the boron.
Background technology
Boron compound is used to various fields, and owing to comprise boron compound in its waste water that use produced.In Japan, the usage quantity of boric acid is 35000 tons/year, is a kind of comparatively cheap compound, has therefore directly been discarded without recovery mostly.
In this case, revised anti-water quality in calendar year 2001 and polluted method, from then on begun waste water limiting emission boron.Discharge of wastewater benchmark when being discharged into boron in the ocean is 230ppm or following, and is relative therewith, and the discharge of wastewater benchmark when being discharged in the river usually is 10ppm or following, and any method all must be removed boron.As the method for removing boron from general industrial waste water, the method for utilizing the co-precipitation of magnesium salts to remove or make spent ion exchange resin or boron adsorbent to remove is known (consulting patent documentation 1 and patent documentation 2).But when removing the boron of high density, the addition of reagent and the generation of mud are all very big, or the increase of above-mentioned regeneration of ion-exchange resin frequency, thereby are uneconomic.
On the other hand, iodine is widely used in roentgen-ray contrast medium, medicine, sterilization fungicide etc. as the industry raw material relevant with life; As industrial raw material, be widely used in the manufacturing of catalyst stabilizer, photograph raw material, polaroid etc.; As the agricultural raw material, be widely used in fodder additives, weedicide etc.But in these purposes, iodine nearly all is not to use separately, but mixes use with various materials.Be known that in liquid the situation used with organic property stablizer etc. and employed solvent etc. uses in the step of industrial material production situation a lot.
All the time, employed iodine, iodine compound and their aqueous solution fall so that the form of waste water is processed usually in these industries, and because the bactericidal properties that iodine had, the microorganism that processing waste water is used is killed, iodine but also can cause the organic substance of BOD loading also to be discharged not only with the form of waste water, consequently waste water has caused burden to environment, produce with as the relevant problem of the iodine loss of world's precious resources.
Reclaim the method for iodine from the waste water that contains iodine, for example comprise that the iodine that will contain in the water of iodine by oxygenants such as chlorine becomes free iodine, obtain the iodine of precipitation forms, pressurizing melting carries out the purified currently known methods to the water that contains iodine then.But, if in containing the water of iodine, have organism etc., the settling character variation of free-iodine then, the usage quantity of oxygenant increases, in treating processes, expend time in, exist organism to be present in the medium problem of iodine, a kind of good method of therefore can not saying so with the impurity form.
[patent documentation 1] spy opens the 2004-074038 communique
[patent documentation 2] spy opens flat 9-010766 communique
Summary of the invention
Therefore, the object of the present invention is to provide a kind of method of from the waste water that contains high density boron, removing boron efficiently.It is a kind of when waste water also comprises iodine except boron that another object of the present invention is to provide, and effectively removes the method for iodine after removing boron.
The problems referred to above solve by following (1)~(15).
(1) a kind of wastewater treatment method, it comprises: the pH value that will comprise iodine and/or iodide ion and boron and/or boron ionic waste water is adjusted to 8~14 step; Make above-mentioned boron and/or boron ionic concentration (being converted into boron) reach 0.5 quality % or above enrichment step; By in the liquid that obtains in the above-mentioned enrichment step in cooling the pH value of liquid being adjusted to 1~7 step that boron component is separated out; With remove the precipitate that obtains in the above-mentioned step that boron component is separated out, separate boron and/or boron ionic step.
(2) as above-mentioned (1) described method, wherein above-mentioned enrichment step is undertaken by heating evaporation.
(3) as above-mentioned (1) or (2) described method, wherein above-mentioned enrichment step carries out continuously.
(4) as each described method of above-mentioned (1)~(3), wherein above-mentioned enrichment step proceeds to above-mentioned boron and/or boron ionic concentration (being converted into boron) reaches 0.5~4.8 quality %.
(5), wherein the pH value of above-mentioned waste water is adjusted to 8~14 step and is to use at least a kind of an alkali metal salt being selected from sodium hydroxide, potassium hydroxide and calcium hydroxide or alkaline earth salt to carry out as each described method of above-mentioned (1)~(4).
(6) as each described method of above-mentioned (1)~(5), wherein make in the step that boron component separates out above-mentioned, the temperature of cooled liquid is-10~60 ℃, the pH value of liquid is 1~4.
(7) a kind of wastewater treatment method, it comprises: the pH value that will comprise iodine and/or iodide ion and boron and/or boron ionic waste water is adjusted to 8~14 step; Make above-mentioned boron and/or boron ionic concentration (being converted into boron) reach 0.5 quality % or above enrichment step; By in the liquid that obtains in the above-mentioned enrichment step in cooling the pH value of liquid being adjusted to 1~7 step that boron component is separated out; Remove the precipitate that obtains in the above-mentioned step that boron component is separated out, separate boron and/or boron ionic step; With by in the resulting liquid of above-mentioned separating step, adding chlorine, make iodine and/or iodide ion oxidation, reclaim the step of iodine by sedimentation.
(8) as above-mentioned (7) described method, wherein above-mentioned enrichment step is undertaken by heating evaporation.
(9) as above-mentioned (7) or (8) described method, wherein above-mentioned enrichment step carries out continuously.
(10) as each described method of above-mentioned (7)~(9), wherein above-mentioned enrichment step proceeds to above-mentioned boron and/or boron ionic concentration (being converted into boron) reaches 0.5~4.8 quality %.
(11), wherein the pH value of above-mentioned waste water is adjusted to 8~14 step and is to use at least a kind of an alkali metal salt being selected from sodium hydroxide, potassium hydroxide and calcium hydroxide or alkaline earth salt to carry out as each described method of above-mentioned (7)~(10).
(12) as each described method of above-mentioned (7)~(11), wherein make in the step that boron component separates out above-mentioned, the temperature of cooled liquid is-10~60 ℃, the pH value of liquid is 1~4.
(13) as above-mentioned (1) or (7) described method, wherein the above-mentioned pH value of the liquid in the step that boron component separates out that makes is adjusted to 1~7, be to use at least a kind of being selected from sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid or multiple acid to carry out.
(14) as above-mentioned (7) described method, wherein, make in the step that boron component separates out above-mentioned, further comprise in order to remove the organism that liquid comprises, add step with respect to the sorbent material of liquid 0.01~10 quality %.
(15) as above-mentioned (14) described method, wherein above-mentioned sorbent material is gac or acidic white earth.
By the present invention, can from the waste water that comprises high density boron, remove boron effectively, and then when waste water also comprises iodine except boron, can after removing boron, remove iodine effectively.
Embodiment
With reference to the accompanying drawings preferred implementation of the present invention is described.
Fig. 1 is the schema of an embodiment of expression method of wastewater treatment of the present invention.As shown in Figure 1, will comprise iodine and/or iodide ion and boron and/or boron ionic waste water 1 is sent in the pH regulator groove 3, the pH value will be adjusted to 8~14, preferred 11~13 by adding alkaline pH conditioning agent 2.This be for the free of iodine in suppressing waste liquid simultaneously, boric acid can easily not separated out when making subsequently evaporation concentration.At this moment, used alkaline pH conditioning agent is preferably at least a kind that is selected from sodium hydroxide, potassium hydroxide and calcium hydroxide, but is not limited to this.Above-mentioned alkaline pH conditioning agent can use with solid form, also can use with aqueous solution form.From the viewpoint of solubleness, more preferably sodium hydroxide and potassium hydroxide.
The liquid that the pH value is adjusted to alkalescence carries out evaporation concentration, until boron in concentration tank 4 and/or boron ionic concentration (being converted into boron) be 0.5 quality % or more than, preferred 0.5~4.8 quality %, more preferably 1~4.5 quality %.At this moment, as mentioned below, the distillate 5a that the vapour condensation that is produced forms can remove the dilution water 5b of liquid 12 as required as boron.
Liquid to evaporation concentration cools off 6.The temperature regulation that preferably will cool off the liquid after 6 is to being-10~60 ℃, more preferably 0~30 ℃.In order to remove boron subsequently, by acidic ph modifier the pH value is adjusted to 1~7, preferred 1~4, carry out crystallization 9.As employed acidic ph modifier, preferably sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid are if consider subsequent step, more preferably sulfuric acid.In the regulating step of this pH value, because therefore the situation that exists the temperature of liquid to rise behind pH regulator, can further carry out the step of cooling liqs.
At this moment, when having organism in the above-mentioned waste water, may make the settling property that may produce and be included in the free-iodine in the waste water in the chlorine oxidation step when making iodine worsen, the rate of recovery of iodine is reduced.In order to prevent this situation, can preferably add with respect to above-mentioned waste water 0.01~10 quality %, the more preferably sorbent material of 0.05~1.0 quality %.Organism can be removed by this sorbent material, and the settleability of free-iodine can be improved.As above-mentioned sorbent material, preferred gac or acidic white earth.In addition, the opportunity of interpolation sorbent material can be after the step of aftermentioned boron removal 10.
Settled boron and the sorbent material when adding sorbent material remove 10 by boron and be removed the liquid 12 of the boron that has been removed.Remove in 10 at boron, can filter or solid-liquid separation operation such as decant.Can be used in the device of this solid-liquid separation, spiral decanting vessel etc. for example, behind lock out operation, be washed totally by adding dilution water 5b, relaxed the boric acid state of saturation that boron is removed liquid 12 by this dilution water 5b simultaneously, can prevent because the separating out again of the boric acid of the supersaturation that difference the caused part of the gentle outside atmosphere temperature of liquid.
In addition, boron is removed liquid 12 in order to carry out boron recycling step subsequently, can it be diluted to predetermined concentration by dilution water 5b.
Fig. 2 represents another embodiment of wastewater treatment of the present invention.
As shown in Figure 2, in having removed the liquid 32 behind the boron, add dilution water 25b,, then, in this dilution process liquid 33, add chlorine 34, carry out oxide treatment, thereby iodine crystal is separated out with the same dilution of situation of Fig. 1.The liquid of having separated out iodine crystal is sent in the melting kettle 35, the free-iodine of separating out is precipitated out.Supernatant liquor is overflowed as treating water 37, and sedimentary iodine is recovered from the bottom with the form of iodine 36.
Contain iodine and/or iodide ion and boron and/or boron ionic waste water by concentrating, so with the pH value of this concentrated solution be adjusted to 4 or below, improved the adsorption efficiency that organism is removed gac in the process.When the application target of gac is to take out iodine the waste water after removing boron, improve the settleability of iodine crystal in crystallizer tank that obtains by chlorine oxidation.
Embodiment
Below, the present invention will be described in detail by embodiment, but the present invention is not limited to these embodiment.
Embodiment 1
It is 5 that the pH value of concentrating under reduced pressure 804g is adjusted to 12 boron concentration, and the waste water of 915mg/L obtains the 229g concentrated solution.In this concentrated solution of 204g, add the 16g vitriol oil, pH value is adjusted to 4, be cooled to 5 ℃ of stirrings when as follows then, boron is separated out.Then by removing by filter the boron of separating out.
The filtrate of removing behind the boron is 168g, and boron concentration is 5,682mg/L.The absolute magnitude of boron is 4 before processing, 195mg, handling the back be 730mg, reduce to handle preceding below 1/5.
Embodiment 2
Being adjusted to 12 boron concentration by the method concentrating under reduced pressure pH value identical with embodiment 1 is 6, and 000mg/L, iodine concentration are the aqueous solution of 7.8 quality %.Boron concentration in the resulting concentrated solution is 22,000mg/L, and the concentration of iodine is 23.3 quality %.In this concentrated solution of 200g, add the 0.6g Exocarpium cocois (Cocos nucifera L) class Powdered Activated Carbon (egression (registered trademark)) (the 0.1 quality % that is equivalent to the preceding aqueous solution of concentrating under reduced pressure) and the 15.1g vitriol oil, the pH value is adjusted to 3.Behind pH regulator, stirred 30 minutes, and then, stirred 30 minutes by the ice-water bath cooling.The boron and the gac of separating out filtered, obtain 172g filtrate.In this filtrate of 64g, add 126g water and dilute, be blown into chlorine until the ORP of this diluent (redox potential) value above 700mV, the settleability of the free-iodine of separating out by Visual Confirmation.The result is good.
Comparative example
Being adjusted to 12 boron concentration to the pH of 200g value is 6, and 000mg/L, iodine concentration are to add the Exocarpium cocois (Cocos nucifera L) class Powdered Activated Carbon (egression (registered trademark)) and the vitriol oil in the aqueous solution of 7.8 quality %, and the pH value is adjusted to 3~5.The amount of the gac that added of preparation is 0.1~0.5 quality % and with 5 samples altogether of 0.1 quality % interval variation with respect to the above-mentioned liquid of having regulated the pH value of 200g.Regulate the pH value of each sample, at room temperature stirred 30 minutes.Carry out the filtration of gac then, in resulting filtrate, be blown into chlorine and surpass 700mV, the settleability of the free-iodine of separating out by Visual Confirmation until the ORP of this filtrate value.The result is, amounts of activated carbon be 0.5 quality % then can not confirm to improve for good a little, its following amounts of activated carbon for good substantially, 03 quality % for good, 0.4 quality %.
Description of drawings
Fig. 1 is the schema of an embodiment of expression method of wastewater treatment of the present invention.
Fig. 2 is the schema of another embodiment of expression method of wastewater treatment of the present invention.
The explanation of Reference numeral
1,21 ... waste water
2,22 ... the alkaline pH conditioning agent
3,23 ... the pH regulator groove
4,24 ... evaporation concentration
5a, 25a ... distillate
5b, 25b ... dilution water
6,26 ... cooling
7,27 ... acidic ph modifier
8,28 ... the pH value is regulated
9,29 ... crystallization
10,30 ... solid-liquid separation
11,31 ... boron component
12,32 ... boron is removed liquid
33 ... dilution process liquid
34 ... chlorine
35 ... melting kettle
36 ... iodine
37 ... treating water.

Claims (15)

1. wastewater treatment method, it comprises: the pH value that will comprise iodine and/or iodide ion and boron and/or boron ionic waste water is adjusted to 8~14 step; Make above-mentioned boron and/or boron ionic concentration (being converted into boron) reach 0.5 quality % or above enrichment step; By in the liquid that obtains in the above-mentioned enrichment step in cooling the pH value of liquid being adjusted to 1~7 step that boron component is separated out; With remove the precipitate that obtains in the above-mentioned step that boron component is separated out, separate boron and/or boron ionic step.
2. the method for claim 1, wherein above-mentioned enrichment step is undertaken by heating evaporation.
3. method as claimed in claim 1 or 2, wherein above-mentioned enrichment step carries out continuously.
4. as each described method of claim 1~3, wherein above-mentioned enrichment step proceeds to above-mentioned boron and/or boron ionic concentration (being converted into boron) reaches 0.5~4.8 quality %.
5. as each described method of claim 1~4, wherein the pH value of above-mentioned waste water is adjusted to 8~14 step and is to use at least a kind of an alkali metal salt being selected from sodium hydroxide, potassium hydroxide and calcium hydroxide or alkaline earth salt to carry out.
6. as each described method of claim 1~5, wherein make in the step that boron component separates out above-mentioned, the temperature of cooled liquid is-10~60 ℃, the pH value of liquid is 1~4.
7. wastewater treatment method, it comprises: the pH value that will comprise iodine and/or iodide ion and boron and/or boron ionic waste water is adjusted to 8~14 step; Make above-mentioned boron and/or boron ionic concentration (being converted into boron) reach 0.5 quality % or above enrichment step; By in the liquid that obtains in the above-mentioned enrichment step in cooling the pH value of liquid being adjusted to 1~7 step that boron component is separated out; Remove the precipitate that obtains in the above-mentioned step that boron component is separated out, separate boron and/or boron ionic step; With by in the resulting liquid of above-mentioned separating step, adding chlorine, make iodine and/or iodide ion oxidation, reclaim the step of iodine by sedimentation.
8. method as claimed in claim 7, wherein above-mentioned enrichment step is undertaken by heating evaporation.
9. as claim 7 or 8 described methods, wherein above-mentioned enrichment step carries out continuously.
10. as each described method of claim 7~9, wherein above-mentioned enrichment step proceeds to above-mentioned boron and/or boron ionic concentration (being converted into boron) reaches 0.5~4.8 quality %.
11., wherein the pH value of above-mentioned waste water is adjusted to 8~14 step and is to use at least a kind of an alkali metal salt being selected from sodium hydroxide, potassium hydroxide and calcium hydroxide or alkaline earth salt to carry out as each described method of claim 7~10.
12. as each described method of claim 7~11, wherein make in the step that boron component separates out above-mentioned, the temperature of cooled liquid is-10~60 ℃, the pH value of liquid is 1~4.
13. as claim 1 or 7 described methods, wherein the above-mentioned pH value of the liquid of the step that boron component separates out that makes is adjusted to 1~7, is to use at least a kind of being selected from sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid or multiple acid to carry out.
14. method as claimed in claim 7 wherein, makes in the step that boron component separates out above-mentioned, further comprises in order to remove the organism that liquid comprises, and adds the step with respect to the sorbent material of liquid 0.01~10 quality %.
15. method as claimed in claim 14, wherein above-mentioned sorbent material is gac or acidic white earth.
CN2006100089754A 2005-01-28 2006-01-27 Treatment method of waste water Active CN1821117B (en)

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Cited By (6)

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CN103182191A (en) * 2012-01-03 2013-07-03 鸿合环保科技有限公司 Method and apparatus for concentrating iodine-containing solution
CN104364202A (en) * 2012-04-05 2015-02-18 Posco公司 Boron recovery apparatus, boron recovery method, and boron recovery system
CN108083528A (en) * 2016-11-21 2018-05-29 江苏同禾药业有限公司 A kind of method that waste water containing boron is handled in 6- hydroxyl -8- Lipase Catalyzed Resolution of Racemic Ethyl preparation process
CN108947060A (en) * 2017-05-23 2018-12-07 世宗化学株式会社 The method of liquor kalii iodide is regenerated from the waste liquid generated in light polarizing film manufacturing process
CN114956436A (en) * 2022-08-01 2022-08-30 江苏同禾药业有限公司 Method for recovering boron element from production wastewater
TWI805426B (en) * 2022-06-29 2023-06-11 暟豐實業有限公司 Boron resource recovery system for waste liquid

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Publication number Priority date Publication date Assignee Title
CN103182191A (en) * 2012-01-03 2013-07-03 鸿合环保科技有限公司 Method and apparatus for concentrating iodine-containing solution
CN104364202A (en) * 2012-04-05 2015-02-18 Posco公司 Boron recovery apparatus, boron recovery method, and boron recovery system
US9790096B2 (en) 2012-04-05 2017-10-17 Posco Boron recovery apparatus, boron recovery method, and boron recovery system
CN108083528A (en) * 2016-11-21 2018-05-29 江苏同禾药业有限公司 A kind of method that waste water containing boron is handled in 6- hydroxyl -8- Lipase Catalyzed Resolution of Racemic Ethyl preparation process
CN108947060A (en) * 2017-05-23 2018-12-07 世宗化学株式会社 The method of liquor kalii iodide is regenerated from the waste liquid generated in light polarizing film manufacturing process
TWI805426B (en) * 2022-06-29 2023-06-11 暟豐實業有限公司 Boron resource recovery system for waste liquid
CN114956436A (en) * 2022-08-01 2022-08-30 江苏同禾药业有限公司 Method for recovering boron element from production wastewater

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CN1821117B (en) 2012-05-16

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