CN1247469C - Method of removing As from water - Google Patents
Method of removing As from water Download PDFInfo
- Publication number
- CN1247469C CN1247469C CN 03130727 CN03130727A CN1247469C CN 1247469 C CN1247469 C CN 1247469C CN 03130727 CN03130727 CN 03130727 CN 03130727 A CN03130727 A CN 03130727A CN 1247469 C CN1247469 C CN 1247469C
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- China
- Prior art keywords
- arsenic
- water
- sulfide
- crystallization
- carrier
- Prior art date
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Abstract
The present invention discloses a method of removing As from water, which comprises that inlet flowing water containing As is mixed with a monosulfide aqueous solution or a metal brine solution in a reactor with a carrier fluidized bed and a preset pH value, and As sulfide crystallization or arsenic acid metal salt crystallization and processed water with low AS content are formed on the carrier. The processed water is separated from the reactor, particles generated from the crystallization are periodically taken out from the reactor, and a new carrier is supplied to the reactor.
Description
Technical field
The invention relates to a kind of method that from water, removes arsenic, especially relevant a kind of water treatment method that from water, removes arsenic by the fluidization crystallization.
Background technology
The gallium arsenide component application often utilizes arsine gas to carry out surperficial organic process in crystalline region of heap of stone in communication and photodiode (LED) opto-electronics in these factory's processing procedures.Handle the back exhaust gas discharged and produce arsenic-containing waste water through washing tower washing collection.Most of at present employing chemical coagulation-sedimentation method is handled, and comprises and adds sinking agent, coagulating agent and polymer coagulant aids.The flowing water arsenic concentration that goes out after the processing is tens of mg/L, is difficult for reaching the water quality standard of releasing below the 0.5mg/L, and produces a large amount of harmful mud and bring puzzlement in the disposal, presses for the treatment technology of exploitation to the environment friendliness.
The U.S. the 4th, 861, No. 493 patents disclose in a kind of waste water metal particularly heavy metal and strontium by mixing with water-soluble sulfide with the method for metal removal, be included under fluidized-bed kenel reactive tank and the proper pH value, metallic wastewater is mixed with water-soluble sulfide, on the carrier of this fluidized-bed, form the metallic sulfide crystallization, usually water-soluble sulfide is to use alkali metalsulphide or basic metal sulfohydrate or ammonium sulfide or Iron sulfuret, especially likes using sodium sulphite, Sodium sulfhydrate, potassium sulphide or potassium bisulfide.The metal species that may remove according to this method: nickel, strontium, zinc, copper, iron, silver, lead, cadmium, mercury, cobalt, manganese, tellurium, tin, indium, bismuth, antimony.Mercury is removed from water in the embodiment of this patent, and this proper pH value is 4～10.
The U.S. the 5th, 348, No. 662 patent is via the heavy metal (arsenic, antimony, lead) in the coprecipitation mode removal aqueous solution (underground water), utilize oxygenant (ozone or hydrogen peroxide) and sulfuric acid, nitric acid, hydrochloric acid to increase the metal valence mumber and precipitate stiffeners (calcium sulfate, white arsenic, Tricalcium arsenate and cupric oxide) to make deposit seeds become big, pass through solid-liquid separation at last.This patented method can produce the mud of water ratio about 60～80%, and this mud not only Heavy Weight, volume is big, and impurity is difficult for recycling more.
Summary of the invention
A main purpose of the present invention is to provide a kind of method that removes arsenic from water of not having a Prior Art shortcoming.
Another object of the present invention is to provide a kind of method that arsenic in the water is removed from water with crystallized form.
A kind of method that removes arsenic from water of finishing according to content of the present invention comprises for achieving the above object: an arsenical influent stream water and the monosulphide aqueous solution or an aqueous metal salt are had in the carrier fluidized bed reactor in one in a predetermined pH scope mix, so form arsenic sulfide crystallization or the crystallization of arsenic acid metal-salt and form the fs treating water that an arsenic content reduces on this carrier; Isolate this fs treating water from this reactor; And periodically take out the crystalline particle that includes carrier that is produced from this reactor.
Preferable, this influent stream water contains III valency arsenic and mixes in pH＜4 with this sulfide solution, comprises AsS or As so form on this carrier
2S
3Crystallization.Better, this influent stream water that contains arsenic (III) mixes in pH=0.8～1.2 with this sulfide solution.Better, this sulfide solution is to carry out under sulphur is 1: 1 to 3: 1 situation the mol ratio of arsenic with the mixing of influent stream water that this contains arsenic (III).
The sulfide that is suitable for the inventive method includes, but is not limited to be alkali metalsulphide, alkaline earth sulfide, and ammonium sulfide, Iron sulfuret (FeS), hydrogen sulfide or sulfurous gas, wherein with sodium sulphite, sodium bisulfide, potassium sulphide and potassium hydrogen sulfide are preferable.
Preferable, this influent stream water contains V valency arsenic and mixes in pH＞7 with this aqueous metal salt, so form M on this carrier
x(AsO
4)
y(OH)
zCrystallization, wherein M is the metal of the contained price m of this aqueous metal salt, and
m
·x-3y-z＝0，
X＞0 wherein, y＞0 and z 〉=0.Better, the contained metal M of this aqueous metal salt is a calcium, this influent stream water that contains arsenic (V) is to mix in pH=11～13 with this aqueous metal salt, and this crystallization is Ca
5(AsO
4)
3(OH).Better, this aqueous metal salt is at this M concentration of metal and AsO with the mixing of influent stream water that this contains arsenic (V)
4 3-The product of concentration greater than carrying out under this crystalline solubility product.
Preferable, this carrier is a sand.Better, this sand has the particle diameter between 0.1～0.5mm.
Description of drawings
Fig. 1 is the process block diagram according to the arsenic-containing water treatment process of one embodiment of the invention.
Fig. 2 is the process block diagram according to the arsenic-containing water treatment process of another embodiment of the present invention.
Reference numeral
11. contain arsenic emulation waste water 12. sodium sulphite medicaments
13. contain the even waste water 14. solvability sodium sulphite medicaments of arsenic
16. fs treating water 17. subordinate phase treating water
21. calcium chloride medicament 22. solvability calcium chloride medicaments
25. carrier 26. recirculation waters
27. cycle discharging crystalline particle (dotted line is represented discontinuity)
31. concentrate partly (dotted line is represented discontinuity)
32. sodium hydroxide (dotted line is represented discontinuity)
33. waste water 41. hydrochloric acid
51. 52. fs of sodium hydroxide treating water
53. iron(ic) chloride medicament 54. salt acid treatments
55. throw out 56. subordinate phase treating water
Embodiment
The invention provides a kind of fluidized-bed crystallizing treatment process of arsenic-containing water, may further comprise the steps:
(1) the arsenic-containing water introducing is contained carrier fluidized bed reactor;
(2) simultaneously the sulfide of water dissolvable or the salt of calcium or other metal are added this reactor, so on this carrier, form arsenic sulfide crystallization or the crystallization of arsenic acid metal-salt and form the fs treating water that an arsenic content reduces;
(3) the fs treating water that arsenic content is reduced is drawn this reactor.
In the treatment process of arsenic-containing water of the present invention, can further the fs treating water be bestowed subordinate phase in the mode of gravity settling or membrane filtration or coagulating sedimentation handles, with the arsenic content in the further removal water, and obtain to meet the release subordinate phase treating water of water quality standard of rules.Subordinate phase is handled the concentrated waste water produced if contain and concentrate nucleus then after dissolving tank adds acid or alkali dissolution, or without dissolving tank, is back to this fluidized-bed reactor and handles again.
This fs treating water also can adopt absorption, ion-exchange, ion flotation, electrocoagulation or extracting process in this subordinate phase is handled, further remove the arsenic contamination thing.
The inventive method can further comprise: (4) periodically take out the crystalline particle that includes carrier that is produced from this reactor, and carrier is replenished this fluidized-bed reactor of adding.
According to first scheme of the present invention arsenic contamination thing in the water is removed with the sulfide crystallization, this sulfide crystallization can be different kenel pozzuolite things, for example As
2S
3, AsS, and As
2S
5On xln.The present inventor finds to influence the main factor of crystalline to be had: S/As mol ratio, volume load (kg/m
2H) (volumetric loading), pH value and influent stream concentration as if being pointer with the water water quality of finally releasing, have the greatest impact with the pH value.As shown in table 1, effectively removing institute's palpus pH value need be less than 4.When pH3.6 when percent crystallization in massecuite 15%, pH2 when percent crystallization in massecuite 71%, pH1 percent crystallization in massecuite then be promoted to 93%.When pH value 7.2, xln can be estimated and be peeled off and dissolution phenomena again.The above results finds effectively to remove institute's palpus pH value need be less than 4, and optimal ph is 1.0 ± 0.2.Next influences the crystalline factor is the S/As mol ratio, and best ratio is 2.0 ± 0.3.
Table 1 removes the test conditions and the result of arsenic from arsenic-containing water
| Condition | The result | ||||
| The arsenic concentration of arsenic-containing water (mg/L) | pH | S/As (mole/mole) | The arsenic concentration of fs treating water (mg/L) | The arsenic concentration of subordinate phase treating water (mg/L) | Percent crystallization in massecuite (%) |
| 611 | 1.0 | 2.0 | 7.2 | 0.5 | 93 |
| 734 | 2.0 | 2.0 | 36.0 | 0.4 | 71 |
| 1,182 | 3.6 | 2.0 | 100.6 | 10.0 | 15 |
| 250 | 7.2 | 2.0 | 107.5* | 14.1 | -16 |
* dilute the result who is produced because of medicament.
According to alternative plan of the present invention arsenic contamination thing in the water is removed with the crystallization of arsenic acid metal-salt, comprised and add the different metal medicament to produce the different arsenates of low solubility, person for example as shown in table 2.The metal species of the arsenate in the table 2 comprises: the classes of compounds of silver, calcium, strontium, magnesium, nickel, zinc, cobalt, manganese, cadmium, lead, copper, barium, iron, chromium, aluminium, bismuth or generation arsenate comprises: UO
2HAsO
4, NH
4UO
2AsO
4, KUO
2AsO
4, and NaUO
2AsO
4
Table 2 is enumerated the arsenic compound of part low solubility or the solubility product of arsenate (solubilityproduct)
| Compound | Ksp | Compound | Ksp |
| Ag 3AsO 3 | 4.5×10 -19 | C u3(AsO 4) 3 | 8.0×10 -36 |
| Ag 3AsO 4 | 1.1×10 -20 | Ba 3(AsO 4) 2 | 7.7×10-51 |
| Ca 3(AsO 4) 2 | 6.0×10 -19 | FeAsO 4 | 1.0×10 -20 |
| Ca 5(A sO 4) 3(OH) | 9.1×10 -39 | CrAsO 4 | 7.8×10 21 |
| Sr 3(AsO 4) 2 | 1.6×10 -18 | AlAsO 4 | 1.6×10 -16 |
| Mg 3(AsO 4) 2 | 2.1×10 -30 | As 3S 3 | 4.0×10 29 |
| Ni 3(AsO 4) 2 | 3.0×10 -26 | BiAsO 4 | 4.4×10 -10 |
| Zn 3(AsO 4) 2 | 1.6×10 -28 | UO 2HAsO 4 | 3.2×10 -11 |
| Co 3(AsO 4) 2 | 8.0×10 -29 | NH 4UO 2AsO 4 | 1.7×10 -24 |
| Mn 3(AsO 4) 2 | 2.0×10 -29 | KUO 2AsO 4 | 2.5×10 -23 |
| Cd 3(AsO 4) 2 | 2.0×10 -33 | NaUO 2AsO 4 | 1.3×10 -22 |
| Pb 3(AsO 4) 2 | 4.1×10 -36 |
For above-mentioned purpose of the present invention, feature and advantage can be become apparent, preferred embodiment cited below particularly, and cooperate appended graphicly, be described in detail below:
See also first embodiment of Fig. 1, arsenic-containing water treatment process of the present invention is contained in the silica sand carrier 25 of filling with water in the fluidized-bed crystallization reactor (FBC) of diameter 2cm, height 160cm and filling particle diameter 0.2～0.5mm, activates recirculation water 26 again and makes wherein silica sand carrier 25 fluidizations.With concentration 611mgAs/L sodium metaarsenite (NaAsO
2) trivalent contain arsenic emulation waste water 11 and introduce the even groove of arsenic-containing waste waters.Uniform arsenic-containing waste water 13 is introduced the aforementioned fluidized-bed crystallization reactor (FBC) that contains carrier with flow 5ml/min, and add the solvability sodium sulphite medicament 14 of inbound traffics 27ml/min, sulphur concentration is 100mg/L, and making middle sulphur of fluidized-bed crystallization reactor (FBC) and arsonium ion molar ratio is 2: 1.The potential of hydrogen and the redox potential (ORP) of mixing solutions in the while monitoring reaction device.With the interpolation of control hydrochloric acid 41 on the pH controller line, what make mixing solutions in this reactor maintains pH value 1.0 ± 0.2, ORP value demonstration this moment 315-325mV.Generate the yellow crystal body after reaction for some time on carrier, through after one period reaction times, the xln color transition becomes orange again.When treating that a bed bottom crystalline particle particle diameter reaches about 1～3mm, these greater particle size crystalline particles are shifted out from reactor, replenish novel vector simultaneously than small particle size.The stage processing water 16 of can winning after the processing with its sampling and add the solid that alkali dissolution wherein suspends, and adds to give and analyzes to such an extent that total arsonium ion concentration is 7.2mg As/L.The orange xln is through after adding alkali dissolution, and solution carries out the arsenic quantitative analysis with induction coupled plasma atom spectrum analysis instrument (ICP-AES Analysis) and colorimetry is carried out the sulphur quantitative analysis, and calculating sulphur and arsenic mol ratio is 1.16: 1.We infer that the orange xln is a blended arsenic sulfide, comprise molecular formula AsS (realgar, Realgar) and As
2S
3(orpiment, Orpiment).
Fs treating water 16 is introduced into ultra-filtration (UF) film further handles, obtain subordinate phase treating water 17 by the UF film.Through sampling analysis, the arsonium ion concentration of subordinate phase treating water 17 is 0.5mg/L, can carry out water and recycle or directly release.Under same pH value, the S/As mol ratio is increased to 2.2 from 2, the arsonium ion concentration of this subordinate phase treating water is reduced to 0.22mg As/L.The nucleus that contains by the UF film concentrates partly and 31 is not sent to a dissolving tank, is dissolved by sodium hydroxide 32 in nucleus wherein, and the waste water 33 that is obtained is admitted to the even groove of this arsenic-containing waste water again.
Calculate via mass balance, the crystallization of arsenic in the water in the arsenic-containing water treatment process of pH1.0 ± 0.2, precipitation and dissolving ratio are respectively 92.7%, 6.8% and 0.5%.
Fig. 2 illustrates second embodiment of arsenic-containing water treatment process of the present invention.Use is same as the fluidized-bed crystallization reactor (FBC) of first embodiment.With concentration 302mg As/L sodium arseniate (Na
2HAsO
47H
2O) pentavalent contains arsenic emulation waste water 11 and introduces the even groove of arsenic-containing waste water.Uniform arsenic-containing waste water 13 is introduced the aforementioned fluidized-bed crystallization reactor (FBC) that contains carrier with flow 4ml/min, and add the solvability calcium chloride medicament 22 of inbound traffics 11ml/min, calcium ion concn is 250mg/L, and making middle calcium of fluidized-bed crystallization reactor (FBC) and arsenic molar ratio is 2.5: 1.With the interpolation of control sodium hydroxide 51 on the pH controller line, the pH value of keeping the interior mixing solutions of this reactor (FBC) is 12.On carrier, generate the white crystals body after reaction for some time.When treating that a bed bottom crystalline particle particle diameter reaches about 1～3mm, these greater particle size crystalline particles are shifted out from reactor, replenish novel vector simultaneously than small particle size.The stage processing water 52 of can winning after the processing with its sampling and add the solid that the acid dissolving wherein suspends, and adds to give and analyzes to such an extent that total arsonium ion concentration is 22mg As/L.This white crystals body is through x-ray bombardment spectrum analysis instrument (XRD) qualitative analysis, and the standard value of reference standards is by sample d value 2.81 , 1.99 , the relative intensity I/I of 3.49 , light
0100,50,41, with 31.8 ° at 2 θ angles, 45.5 °, data such as 25.5 ° learn that this white crystals body is the Tricalcium arsenate subsalt, Ca
5(AsO
4)
3(OH).
Fs treating water 52 is introduced a settling bath, add iron(ic) chloride 53, the Fe/As mol ratio is 6, and adjusts pH value to 5.5 with salt acid treatment 54 and carry out further coagulating treatment, obtains subordinate phase treating water 56.Arsonium ion concentration through this subordinate phase treating water 56 of sampling analysis is 0.4mg/L, can carry out water and recycle or directly release.Can further handle according to currently known methods as for 55 of sludge settling things that produce.
Claims (11)
1. method that from water, removes arsenic, comprise an arsenical influent stream water and the monosulphide aqueous solution or an aqueous metal salt had in the carrier fluidized bed reactor in one in a predetermined pH scope and mix, so on this carrier, form arsenic sulfide crystallization or the crystallization of arsenic acid metal-salt and form the fs treating water that an arsenic content reduces; Isolate this fs treating water from this reactor; And periodically take out the crystalline particle that includes carrier that is produced from this reactor.
2. the method for claim 1, wherein this influent stream water contains III valency arsenic and mixes in pH＜4 with this sulfide solution, comprises AsS or As so form on this carrier
2S
3Crystallization.
3. method as claimed in claim 2, wherein this influent stream water that contains III valency arsenic mixes in pH=0.8～1.2 with this sulfide solution.
4. method as claimed in claim 2, wherein this sulfide solution is to carry out under sulphur is 1: 1 to 3: 1 situation the mol ratio of arsenic with the mixing of influent stream water that this contains III valency arsenic.
5. method as claimed in claim 2, wherein this sulfide is alkali metalsulphide, alkaline earth sulfide, ammonium sulfide, Iron sulfuret FeS, hydrogen sulfide or sulfurous gas.
6. method as claimed in claim 5, wherein this sulfide is sodium sulphite, sodium bisulfide, potassium sulphide or potassium hydrogen sulfide.
7. the method for claim 1, wherein this influent stream water contains V valency arsenic and mixes in pH＞7 with this aqueous metal salt, so form M on this carrier
x(AsO
4)
y(OH)
zCrystallization, wherein M is the metal of the contained price m of this aqueous metal salt, and
m·x-3y-z＝0，
X＞0 wherein, y＞0 and z 〉=0.
8. method as claimed in claim 7, wherein the contained metal M of this aqueous metal salt is a calcium, this influent stream water that contains V valency arsenic is to mix in pH=11～13 with this aqueous metal salt, and this crystallization is Ca
5(AsO
4)
3(OH).
9. method as claimed in claim 7, wherein this aqueous metal salt is at this M concentration of metal and AsO with the mixing of influent stream water that this contains V valency arsenic
4 3-The product of concentration greater than carrying out under this crystalline solubility product.
10. the method for claim 1, wherein this carrier is a sand.
11. method as claimed in claim 10, wherein this sand has the particle diameter between 0.1～0.5mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03130727 CN1247469C (en) | 2003-05-08 | 2003-05-08 | Method of removing As from water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03130727 CN1247469C (en) | 2003-05-08 | 2003-05-08 | Method of removing As from water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1548381A CN1548381A (en) | 2004-11-24 |
| CN1247469C true CN1247469C (en) | 2006-03-29 |
Family
ID=34322662
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03130727 Expired - Lifetime CN1247469C (en) | 2003-05-08 | 2003-05-08 | Method of removing As from water |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538094B (en) * | 2009-04-10 | 2010-12-08 | 天津大学 | Method for processing waste liquid of regenerated arsenic removal ionic sieve |
| CN102120636B (en) * | 2011-01-21 | 2012-07-04 | 哈尔滨工业大学深圳研究生院 | Method and device for removing heavy metals in industrial wastewater |
| CN103253791B (en) * | 2013-05-02 | 2015-04-01 | 中国科学院生态环境研究中心 | High-concentration arsenious acid wastewater treatment method and device |
| CN103304059A (en) * | 2013-06-30 | 2013-09-18 | 金川集团股份有限公司 | System and method for treating acidic wastewater in metallurgical off-gas acid-making process |
| CN106746011A (en) * | 2016-12-30 | 2017-05-31 | 四川师范大学 | The processing method of heavy metal-containing waste water |
| CN106698632A (en) * | 2016-12-30 | 2017-05-24 | 四川师范大学 | Treatment method of mercury-containing wastewater |
| CN106587311A (en) * | 2016-12-30 | 2017-04-26 | 四川师范大学 | Treatment method of mercury-containing wastewater |
| CN111377527A (en) * | 2018-12-31 | 2020-07-07 | 中国石油化工股份有限公司 | Treatment method of high-salt-content organic wastewater |
| CN113443738A (en) * | 2021-06-22 | 2021-09-28 | 南京晟嘉实验设备科技有限公司 | Processing system that organophosphorus pesticide waste water sodium sulfide removed arsenic |
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2003
- 2003-05-08 CN CN 03130727 patent/CN1247469C/en not_active Expired - Lifetime
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