ॺฃ࣑ଡଲणী୪Ջւ֜
ଲ෮శ
 ࢢլ
 ছଭઽ
A Study on Removal of Aqueous Arsenic using the Carbonation Process
Hyun-Cheol Lee, Kyoung-Won Min and Eui-Young Seo
Abstract :The carbonation process, one of the calcium carbonate precipitating methods, consists of a reaction of Ca(OH)2, CO2, and water. In this study, laboratorial tests were conducted to remove the arsenic from the abandoned mine drainage and ground water using the carbonation process. As (III) and As (V) were removed up to 26.5% and 90.6%, respectively in the preliminary test and up to 38.7% and 95.1%, respectively in the second test with an increased amount of hydrated lime. Final pH’s of reacted solutions were 6.0 to 6.5, which are satisfying with the water standard and Eh’s range between -330 mV and +50 mV. Calcite peak was observed in the reaction precipitates of the follow-up test by XRD analysis and also, hexahedral structures of calcite crystals were identified by SEM analysis. As (III) and As (V) were detected in the range of below 0.04% and 0.060.07%, respectively by EDS scanning. Consequently, the carbonation process can remove aqueous As (V) efficiently, but As (III) insufficiently.
Key words : Arsenic, Carbonation process, Mine drainage, Hydrated lime, Calcite
څ أԓজѪڹࠞÌՁԓࠥ֜ں܃ܓॠəѓѪۆॠǣͿCa(OH)2, CO2,Нںъڿ֨ࡈԓࠥ֜ں܃ܓ ॠəѓѪںϊॢɰ. ٍ҆ĵقԴə্ · दġԓġԓѕսфݓॠսˣقܕۦॠəҼՙε܃äॠşڦॢѓѪڷ ͿԓজѪںۺڌॠي֬ॹں֬֨ॠٕɰ. 1֬ॹĀę, As(III)ə߯ʂ26.5% ܃äʼؽČ, As(V)ə߯ʂ
90.6%ūݓ܃äʼؽɰ. ՙԵধ࣊ۓ͟ںݒÀ֨ࡈ֬֨ॢ2֬ॹĀę, As(III)ə߯ʂ38.7%, As(V)ə߯ʂ
95.1% ܃äʼؽɰ. ъڿڌؚۆ߯ܛpHə6.06.5 ѩڦͿսݗşܵںχܔॠٕČ, Ehə-330 mV+50 mV ѩڦεǣࢍǻɰ. 2֬ॹۆъڿԦՁНقʂॢXRD қԵں֬֨ॢĀęѓ३ԵpeakÀঝۍʼؽČ, SEM қԵںࣀ३گϸߕۆĀ܁ںÍəѓ३Եےںঝۍॠٕɰ. ̚ॢEDS ֟ࠪɮںࣀ३As(III) 0.04% ۋॠ, As(V) 0.060.07%ÀԦՁʽѓ३ԵशϸقܕۦॠəìڷͿঝۍʼؽɰ. ĀęۺڷͿԓজѪقۆॢҼՙ܃
äəAs(III)ۆąڍҼমڱۺۍìڷͿǣࢍǮڷ϶, As(V)ۆąڍমڱۺۍ܃äÀÀɠॢìڷͿǣࢍǮɰ.
ܳڅر Ҽՙ, ԓজѪ, ġԓѕս, ՙԵধ, ѓ३Ե
2012ț12ښ14ێۿս, 2013ț1ښ11ێ֮ԐٰΒ 2013ț2ښ14ێóۦঝ܁
1) Ìڙʂॡİėęʂॡقȃݓ · ۙڙėॡę
*Corresponding Author(лąڙ) E-mail; [email protected]
Address; Department of Energy & Resources Engineering, Kangwon National University, Chuncheon, Gangwon-do 200-701, Korea
ISSN 2287-4321(Online) Vol. 50, No. 1 O2013PGpp. 70-79
Դ
ҼՙəÌͳॢʫՁںÀݕŚ՚ęҼ֦ॢՁݗںǣ
ࢍǴəܵŚ՚ڙՙ(metalloid)ͿԦϼߕ, ʂş, Н, ݓÁ
ˣق й͟ڷͿ ġѩڦॠó қपʼر ەڷ϶, थŒȬʪ
1.8mg/kgڷͿ22ѥݫͿψڹڙՙۋɰ(Demayo, 1985).
ҼՙəٍۙսقԴAs(III)ٮAs(V)ۆͿܕۦॠ϶,
As(III)əH2AsO3 ͿܕۦॠČ, As(V)əH2AsO4-
, HAsO42-
ٮ Ïڹ ڼۋ٣ Ϳ ܕۦॢɰ. ێъۺڷͿ
As(III)əঞڙঞąقԴ؋܁ॠČ, As(V)əԓজঞąق Դ؋܁ॠ϶, As(V) ҃ɰAs(III)ÀۋʴʪÀȭڹݜ ںǣࢍǶɰ(Dutre and Vandecasteele, 1995; Yan et al., 2000). Ҽՙقۆॢ١ّڹۍÂۆটʴقۆ३ԴьԦ ʼäǣ(Morin and Calas, 2006), ɰتॢąͿεࣀ३ۙ
ٍۺڷͿьԦॣսʪەɰ(Bang and Meng, 2004). ۙ
ٍۺڷͿəডҼߏԵ(arsenopyrite, FeAsS)ęÏڹ॥Ҽ ՙġНقۆ३ьԦʼ϶, জԓটʴۋǣݓĵজॡۺԓ জфঞڙۚڌقۆ३Ҽՙ١ّۋьԦʼČەɰ. ۍ ۆটʴقۆॢҼՙۆ١ّڹԕ߿܃, ܃ߣ܃, ؋Β, ড়
֥܃ˣۆڙΒͿԐڌʽҼԓǬ, Ҽԓࠥ֜ˣقۆॢ١
ّęġԓটʴۆĀęͿьԦʽġНީƃş, ࠞս, ԓ Ձġԓѕս(Acid Mine Drainage) ˣقۆ३Ҽՙ١ّۋ
ٍĵȦЛ
ьԦʼČەɰ(Lee, 2011). Ҽՙ١ّڹѓŘ͆ʚ֨, ۍʪ, ʂχ, ܼĶˣۆ؉֨؉ݓًфϮ֨ࡑ, ʫێ, йĶˣۻ ՃćۺڷͿ ьԦʼČ ەڷ϶(Smedley and Kinniburgh, 2002; Driehaus, 2002), ০ѓŘ͆ʚ֨əՃćقԴÀۤ
֮Áॢڦॹقߌ३ەČأ3ߎ5іχϼۋ50ppb ۋԜۆ
Ҽՙ١ّڼڌսευ֨ČەəìڷͿܓԐʼؽɰ(BGS and DPHE, 2001). ڍνǣ͆ۆąڍʪٚٽÀ؉ɦ϶ڐ ԓݓًۆݓॠս١ّ(Ahn et al., 2005), ۻĶ700يĖۆ
ݓॠսսݗܓԐ(Korean Ministry of Environment, 2005), ġԓܳѺݓًҼՙ١ّ(Ko et al., 2010; Ko et al., 2003;
Lee et al., 2000) ˣقʂॢԐͻÀ҃Čʼؽɰ. ҼՙͿ
١ّʽݓॠսεڼڌսͿԐڌॣąڍÂ, ࡘं, द, क़ҙ
ؒˣۋьԦॣսەڷ϶, ܼ߸֪ąфйՃঈěۆυҼ ݒՃÀǣࢍǨսەɰ(Wang et al., 2002). ۋ͠ॢҼՙۆ
ʫՁфڮ३ՁڷͿۍ३йĶঞąߔ(USEPA)قԴəҼ ՙۆڼڌսѪۺşܵں50 ppbقԴ10 ppbͿǰ߸ؽڷ
϶ ĶǴۆ ąڍʪ 10 ppbͿ ॠॳܓ܁ ʼؽɰ(Korean Ministry of Environment, 2011).
Ҽՙε ߌνॠə şցقə ڿݚ, ߏ·ϐÂ ԓজ, Եধ
ٍսজˣۆşցںۋڌॢࠞۻߌνşց, ݓॠսεъ
࣊φۋǣϱҵͪۍںࣀę֨ࡈҼՙε܃äॠəϱҵͪ
ۍߌνşց, ۋ٣İঞսݓٮ١ّНݗÂۆتۋ٣ۋǣ
ڼۋ٣ۆİঞںࣀ३ڌܕۋ٣Нݗں܃äॠəۋ٣İ ঞşց, ڌܕՁНݗۋČߕۆशϸęۿߤॢНͿҙ ࢢ܃äʼرড়܃शϸقҙʼəড়şցˣۋە ɰ. ۋ͠ॢɰتॢҼՙ܃äşց˞ۋٍĵʼČەڷǣ
ą܃ۺۋČমڱۺۍşցͿथÀыČەəড়фė
ࠞşցۋܳͿψۋۋڌʼČەɰ(Bang et al., 2005).
߯ŖĶǴقԴəйԦНںۋڌॢҼՙۆ܃äфڌ
قěॢٍĵ(Han et al., 2011; Kim et al., 2011a; Kim et al., 2011b), ড়НݗںۋڌॢҼՙ܃äقěॢٍ
ĵ(Oh et al., 2010; Lee et al., 2011; Kim et al., 2009) ˣҼՙ܃äقěॢٍĵÀ টьॠó ҃ČʼČ ەɰ.
ٍ҆ĵقԴəԓࠥ֜ۆ܃ܓѓѪۆॠǣۍ ԓ জѪںۋڌॠيսܼقܕۦॠəҼՙε܃äॠČۙॠ
ٕɰ. ܼŚ՚ܼজߌνقȇνԐڌʼəՙԵধ(Ca(OH)2) εۋڌॠيCO2ٮۆъڿںࣀ३CaCO3 ۆԓ
ّġНͿۻঞ֨ࢅČ, ԓّġНۋCaCO3ÀՁʼə
ę܁قԴড়, ࠞۻˣقۆॢAs(III), As(V)ۆ܃äي ҙε ěॠٕɰ.
ٍĵѓѪфĀę
ԓজѪ
ԓࠥ֜(CaCO3)ڹ ܁нজॡėغۆ şъں ۋΘə
ۙڙڷͿіԟʪÀȭČَۺфজॡۺڷͿ؋܁ॢқ ߕͿԴ, ԵধԵںНνۺѓѪقۆ३қթॠي܃ܓॠ əܼݗԓࠥ֜ęজॡۺѓѪقۆ३܃ܓʼəࠞÌՁ
ԓࠥ֜ڷͿĵқʽɰ. ࠞÌՁԓࠥ֜ں܃ܓॠəѓ ѪقəՙɰѪ(soda process), Եধ-ՙɰѪ(lime-soda process),
ԓজѪ(carbonation process) ˣۋەڷ϶ԓজѪۋ
ÀۤȇνԐڌʼČەɰ(Shin, 1984). ԓজѪڹCa(OH)2
սڌؚقCO2εܳۓॠيࠞÌՁԓࠥ֜ںԦՁ֨ࢅ
əCO2(g), H2O(l), Ca(OH)2(s)ۆ3Ԝںप॥ॠəҝŒ ێ ъڿۋ϶(Juvekar and Sharma, 1973), ɰڼę Ïڹ
ъڿ֩ںÀݕɰ.
(i) Ca(OH)2 (s) + H2O (l) 侟Ca2+ (aq) + 2OH- (aq) (ii) CO2 (g) + H2O (l) 侟CO2 (aq) + H2O (l) (iii) CO2 (aq) + OH- (aq) 供HCO3-
(aq) (iv) HCO3-
(aq) + OH- (aq)供CO32-
(aq) + H2O (l) (v) Ca2+ (aq) + CO32-
(aq) 供CaCO3 (s)
ڦۆ (i)(v)ūݓۆ ъڿܼ (iii)ҙࢢ (v)ūݓۆ ъڿڹ
ϔڍӇβóێرǣ϶, ٣ʪ, ъڿ֨Â, CO2 ܳۓ͟, İ ъ՚ʪˣۆъڿܓæق˰͆ۓʪǣۓۙۆԜфĀ
܁ ˣۋɵ͆ݕɰ(Ha et al., 1992).
ٚҼ֬ॹ
Ҽՙڌؚڹ As(III)(NaAsO2, Sigma-Aldrich), As(V) (Na2HAsO4, Sigma-Aldrich)εۋڌॠي܃ܓॠٕɰ. ڌ
ؚۆߣşȬʪəAs(III), As(V) ÁÁ1 mg/LͿ܃ܓॠ
ٕڷ϶, 0.01 M NaClںۋڌॠيѕąڌؚۆۋ٣Ìʪ εܓۼॠٕɰ. ԓࠥ֜܃ܓقԐڌʽۦΒəԦԵধ
҃ɰڌ३ʪÀȭČ٣ʪÀǰںսڌ३ʪÀݒÀॠə
ՁںÀܐڷ϶, 20قԴН100 gق0.165 gۆपজ
ڌ३ʪ(National Lime Association, 2007)εÍəՙԵ ধ(Ca(OH)2)ε Ԑڌॠٕɰ. ՙԵধə ՙÁͿقԴ Ԑڌ ʼəČъڿՙԵধٮێъսߌνфदսߌνڌڷͿ
ԐڌʼəėغڌՙԵধÀەəʚٍ҆ĵقԴəĶǴ
TԐۆսߌνڌՙԵধ(Ca(OH)2, 325mesh, CaO > 95%) εԐڌॠٕɰ. CO2À֟ə99% տʪۆCO2À֟εԐ ڌॠٕČ, 3ݒΪսεԐڌॠيԓࠥ֜܃ܓεڦॢ
֬ॹں ֬֨ॠٕɰ. ܃ܓʽ 1 mg/L Ȭʪۆ Ҽՙڌؚ
500 gق ćԓʽ ՙԵধ पজ͟ 0.825 gں ֨ۚڷͿ
0.165 gݒÀ֨ࡈ0.99 g, 1.155 gۆՃÀݓܓæڷͿ
࣊ۓ͟ںɵνॠٕڷ϶, CO2ܳۓ͟ڹ0.1 L/min, 0.3 L/min ۆ˃Àݓܓæ, İъ՚ʪə200, 300, 400 rpmڷͿۺ ڌॠٕɰ(Fig. 1). ъڿ֨ÂڹşܕٍĵԐͻ(Park et al.,
Fig. 1. Schematic diagram of carbonation reactor.
Table 1. Arsenic concentrations(mg/L) of the carbonated solutions* in various experimental conditions of the preliminary test
No CO2 injection rate (L/min)
Stirring speed (rpm)
As(III) As(V)
A B C D E F
0 1.000 1.000 1.000 1.000 1.000 1.000
1
0.1
200 0.946 0.804 0.778 0.190 0.139 0.162
2 300 0.867 0.742 0.769 0.195 0.141 0.107
3 400 0.771 0.846 0.735 0.212 0.160 0.094
4
0.3
200 0.937 0.894 0.791 0.285 0.239 0.120
5 300 0.980 0.941 0.919 0.291 0.234 0.193
6 400 0.987 0.899 0.858 0.275 0.219 0.170
Added hydrated lime (g) 0.825 0.990 1.155 0.825 0.990 1.155
* solutions of 500 g containing either As(III) or As(V) of 1.00 mg/L were reacted.
Fig. 2. Arsenic concentration variations of reacted solutions in various experimental conditions of the preliminary test such as amounts of added hyrated lime, CO2 injection rate, and stirring speed. Numerical numbers in the legend denote stirring speeds (rpm).
1995; Lee et al., 2012)ق ˰͆ 20қڷͿ Ժ܁ॠٕČ, Ԝ٣·ԜؓܓæقԴ֬ॹں֬֨ॠٕڷ϶, ՙԵধ࣊ۓ
͟ں߯ՙपজȬʪۋԜڷͿԺ܁ॠٕş˺ЛقÌ؎ࠥ
νՁںǣࢍǷìڷͿٚԜʼرҼՙڌؚۆpHəČͲ ॠݓ ؍ؕɰ.
ъڿę܁قԴCO2À֟ۆқԓমڱфߕΪ֨Âںȭ ۋşڦॠيࣷ͆ज़ζڷͿҼۋ࠶Ԝҙεнद֨ࡎڷ϶, ъڿۋݕॱʼəʴ؋1қÂüڷͿpHεࠑ܁ॠٕɰ.
֬ॹܛΒ0.45 μm يęݓεۋڌॠيČߕٮؚߕ εқνॠٕڷ϶қνʽؚߕεICP-OES(OPTIMA 7300 V, PerkinElmer)ε ۋڌॠي ҼՙȬʪε қԵॠٕɰ.
֬ॹĀę(Table 1, Fig. 2) As(III)ۆąڍՙԵধ࣊ۓ
͟ۋݒÀ॥ق˰͆ҼՙȬʪÀأÂÇՙॠəąॳں
ٕ҃ڷǣێěՁەəĀęεصݓЇॠٕČ, ՙԵধ࣊
ۓ͟1.155 g ܓæقԴ߯ʂ26.5% ܁ʪ۹Çʼəìڷ ͿǣࢍǮɰ. ֬ॹѺսقԴİъ՚ʪقۆॢٖॳڹä ۆػؽڷ϶, CO2ܳۓ͟ق˰͆Ҽİॠٕں˺0.3 L/min
Fig. 3. pH variations of reacted solutions in various experimental conditions of the preliminary test such as amounts of added hydrated lime, CO2 injection rate, and stirring speed. Numerical numbers in the legend denote CO2 injection rates (L/min) and stirring speeds (rpm) in order.
ܓæ҃ɰ0.1 L/min ܳۓॢܓæقԴҼՙȬʪÀǰó
ࠑ܁ʼرCO2 ܳۓ͟ق˰δٖॳۋʌڎࢀìڷͿǣ
ࢍǮɰ. As(V)ۆąڍϿ˜ܓæقԴ70% ۋԜ܃äʼ رAs(III)҃ɰښˣॠóȭڹ܃äমڱںٕ҃ڷ϶, ՙ Եধε1.155 g ࣊ۓॢܓæقԴ߯ʂ90.6%ūݓ܃ä ʼؽɰ. As(V) ̚ॢAs(III)ߌͤİъ՚ʪقۆॢٖॳ
҃ɰəCO2 ܳۓ͟ۆٖॳۋʌڎࢀìڷͿǣࢍǮə
ʚ, ۋəAs(III), As(V) Ͽ˃Ca(OH)2ٮCO2ۆъڿۋ
ܛΒʽ ۋقʪ CO2À ć՚ܳۓʼϸԴ Нق ڌ३ʽ
CO2ÀH2CO3ͿۻঞʼČH2CO3À३νʼϸԴHCO3-
ٮH+εьԦॠş˺ЛقCO2 ܳۓ͟ق˰͆ԴpHق
ࢀٖॳںǛ࠘ş˺Лۍ ìڷͿ ߸܁ʽɰ(Ahn et al., 2011). 1қÂüڷͿpHεࠑ܁ॢĀę(Fig. 3) CO2 ܳ ۓ͟ۋ0.3 L/minۍąڍÀ0.1 L/min ҃ɰؘقԴցʽ
цٮÏۋH+ۆьԦ͟ۋʌψş˺ЛقܓŚʌśü ০ ǰ؉ݓə ąॳں ǣࢍǻڷ϶, ۻߕۺڷͿ ъڿ֨Â
10қ ۋҙࢢə ێ܁ॢ Éں ڮݓॠٕɰ.
2֬ॹ
1֬ॹĀęİъ՚ʪəҼՙȬʪ۹Çقࢀٖॳں
й࠘ݓ؍əìڷͿǣࢍǮڷ϶, CO2 ܳۓ͟ęՙԵধ
࣊ۓ͟ۋҼՙȬʪقٖॳںй࠘əìڷͿǣࢍǮɰ. 2
֬ॹقԴə1֬ॹĀęεцڷͿCO2 ܳۓ͟
0.1 L/min, İъ՚ʪ300 rpmε߯ۺۆܓæڷͿԸ܁
ॠي ֬ॹں ֬֨ॠٕɰ. ՙԵধۆ ࣊ۓ͟ڹ As(III)ۆ
ąڍ1֬ॹ͟ۆ˃ѕۍ1.65 g, 1.815 g, 1.98 gں
࣊ۓॠٕČ, As(V)ۆąڍ1֬ॹ͟ق0.165 gݒÀ
֨ࢇ1.32 g, 1.485 g, 1.65 gں࣊ۓॠٕɰ. ߣşҼՙȬ ʪə1֬ॹęÏڹ1 mg/LͿԺ܁ॠٕČ, 1қÂü ڷͿъڿę܁ۆpH, Ehεࠑ܁ॠٕڷ϶, Ԝ٣ · Ԝؓق Դ20қÂъڿ֨ࡎɰ. ߸ÀۺڷͿ1֬ॹۆpH Ѻজ قԴъڿ֨Âأ10қںşܵڷͿ10қۋقpH É ۋێ܁ॠóڮݓʼؽş˺Лقъڿ֨Â10қę20қ قԴۆڌؚںࠄॠيҼՙȬʪεқԵॠٕČъڿܛΒ
ČߕεқνॠيXRD, SEM-EDS қԵں֬֨ॠٕ
ɰ. 2֬ॹقԴə֪ʪεȭۋşڦॠيъ҄֬ॹں
֬֨ॠٕڷ϶, ъ҄֬ॹۆ थŒÉں ۋڌॠٕɰ.
ҼՙȬʪф pH, Eh қԵ
2֬ॹۆҼՙȬʪεқԵॢĀę(Table 2, Fig. 4) As(III)ۆąڍ1֬ॹقԴ҃ɰ˃ѕۆՙԵধε࣊
ۓॠٕڼقʪҝĵॠČҼՙȬʪقԴəࢀۋε҃ۋ ݓ؍ؕČՙԵধε1.98 g ࣊ۓ॰ں˺ъڿ֨Â10қ قԴ߯ʂ38.7%ۆ܃äڱںٕ҃ɰ. 1֬ॹقԴ߯
ʂ90.6%ۆ܃äڱںǣࢍǻʏAs(V)ə2֬ॹĀę
ՙԵধε1.65 g ࣊ۓ॰ں˺ъڿ֨Â10қقԴ߯ʂ
95.1%ۆҼՙ܃äڱںٕ҃ɰ. As(III), As(V) Ͽ˃ъ ڿ֨Â10қێ˺ۆҼՙȬʪÀ20қقԴۆҼՙȬʪ҃
ɰأ0.01 mg/L ܁ʪǰóࠑ܁ʼؽڷ϶, As(V)ۆą ڍ2֬ॹܓæϿ˃ĶǴսݗ١ّНݗۆѕॴڌş
ܵ(Korean Ministry of Environment, 2012)ںχܔॠə
0.05 mg/L ۋॠۆȬʪεǣࢍǻɰ. ۋə1֬ॹĀę
Table 2. Arsenic concentrations (mg/L) of the carbonated solutions* with various experimental conditions of the follow-up test
No CO2 injection rate (L/min)
Stirring speed (rpm)
Reaction Time (min)
As(III) As(V)
A B C D E F
0 1.000 1.000 1.000 1.000 1.000 1.000
1
0.1 300 10 0.760 0.741 0.613 0.046 0.045 0.038
2 20 0.805 0.777 0.742 0.059 0.056 0.049
Added hydrated lime (g) 1.650 1.815 1.980 1.320 1.485 1.650
* solutions of 500 g containing either As(III) or As(V) of 1.00 mg/L were reacted.
Fig. 4. Arsenic concentration variations of reacted solutions in various experimental conditions of the follow-up test such as amounts of added hydrated lime, CO2 injection rate, and stirring speed. Numerical numbers in the legend denote reaction times (min).
Fig. 5. pH variations of reacted solutions in various experimental conditions of the follow-up test such as amounts of added hydrated lime, CO2 injection rate, and stirring speed. Numerical numbers in the legend denote added hydrated limes (g).
Fig. 6. Eh variations of reacted solutions in various experimental conditions of the follow-up test such as amounts of added hydrated lime, CO2 injection rate, and stirring speed. Numerical numbers in the legend denote reaction times (min).
قԴԴցॢцٮÏۋCO2Àڌؚقपজʿق˰͆pH Àॠ͇ॠϸԴҼՙÀۦڌʼرъڿ֨Â10қێ˺ۆ
ҼՙȬʪÀ ʌڎ ǰó ࠑ܁ʽ ìڷͿ ࣺɳʽɰ.
2֬ॹۆpH ࠑ܁Āę(Fig. 5) ՙԵধ࣊ۓ͟ۋψ ڹAs(III)ÀAs(V)҃ɰȭڹpHεǣࢍǻڷ϶, 11 ۋԜ ۆًٖقԴݓ՚ʼə֨ÂۋʌţóǣࢍǮɰ. 2֬
ॹĀęقԴʪ 1 ֬ॹĀęقԴߌͤ ъڿ֨Â 10қں
şܵڷͿ10қۋقێ܁ॢÉڷͿ؋܁জʼəąॳ ںǣࢍǻɰ. ߯ܛڌؚۆpHə66.5 ѩڦͿڮݓʼؽ ş˺ЛقşܕۆܼজߌνѪۆЛ܃۾ۋؽʏѕսۆ
ȭڹpH Л܃ε३ĀॣսەںìڷͿٚԜʼ϶, սݗ ١ّНݗۆ ѕॴڌşܵق ˰δ pH ѩڦ 5.88.9 (Korean Ministry of Environment, 2012)εχܔॠəì ڷͿ ǣࢍǮɰ.
ԓজѪقۆॢҼՙ܃ä֬ॹۆԓজ·ঞڙঞąں
қԵॠşڦ३֬֨ॢEh ࠑ܁Āę(Fig. 6), Eh Ŕ॒͒ əpHٮڮԐॢѺজتԜںǣࢍǻɰ. ъڿę܁قԴۆ
Fig. 7. XRD patterns of reaction precipitates. Ca: calcite
As(III), 1.65 g As(III), 1.815 g As(III), 1.98 g
As(V), 1.32 g As(V), 1.485 g As(V), 1.65 g
Fig. 8. SEM analysis of the reaction precipitates in the follow-up test of As(III) or As(V) containing solutions with various amounts of hydrated lime.
ڿ֨Â 5қ ۋق śüॠó ॠ͇ॠي ъڿ֨Â 10қ
ۋقə(+)ًٖڷͿۻঞʼؽڷ϶, 50 ۋॠۆێ܁ॢ
ÉڷͿ ڮݓ ʼؽɰ.
XRD қԵ
ԓজъڿق˰͆ԦՁʽԓࠥ֜(CaCO3)ڹѓ३ Ե(calcite, گϸߕ), ؉͆Čǣۋ࣡(aragonite, ࠞԜ, ܳ
Ԝ), цࢬ͆ۋ࣡(vaterite, ĵ, ࢍڙ)ۆՃÀݓ
ͿԦՁʽɰ(Lyu et al., 1998). ۋͩóԦՁʽԓࠥ
֜ڹXRD, SEMںࣀॠيঝۍॣսەəʚ, 2֬ॹ قԴ֬֨ॢԓজъڿقқνʽČߕεۋڌॠي
XRD(X쨓pert PRO MPD, PANalytical) қԵں ֬֨ॢ
Āę(Fig. 7) 6Àݓ ܓæ Ͽ˃ ʴێॢ ۆ XRD patternں ǣࢍǻڷ϶, ՙԵধۆ patternęə ɰβó ѓ ३ԵۋܳĵՁġНͿǣࢍǣԓজъڿقۆ३ѓ३Ե ۋՁʼؽڼںঝۍॠٕɰ. Ŕ͠ǣҼՙε॥ڮॢ॥
ҼՙġНڹěʼݓ؍ؕəʚ, ۋə֬ॹقۺڌॢҼ ՙۆߣşȬʪÀ1 mg/LͿϔڍǰ؉ġНԜںǣࢍǴ şقə ϔڍ ǰڹ Ȭʪۋş ˺Лۍ ìڷͿ߸܁ʽɰ.
SEM-EDS қԵ
2֬ॹۆъڿԦՁНقʂॢSEM(S-4300, Hitachi) қԵĀę(Fig. 8) XRD қԵĀęقԴǣࢍǦìߌͤگ ϸߕۆѓ३ԵĀ܁ۋěʼؽɰ. ۋεࣀ३ԓ জѪقۆ३֬֨ʽҼՙ܃ä֬ॹقԴ20қÂۆݥڹ
ъڿ֨ÂڷͿʪٰۻॢۆԓࠥ֜Ā܁ۋՁʾ
սەɰəìںঝۍॠٕɰ. Ŕ͠ǣԦՁʽĀ܁ۆՁқ ںқԵॠşڦ३֬֨ॢEDS қԵقԴə1Ò֨Βɾ
10ধۆEDS қԵں֬֨ॠٕڼقʪ1.65 gۆՙԵধε
Fig. 9. SEM-EDS analysis of reaction precipitates in the follow-up test of As(V) containing solution with added hydrated lime of 1.65 g.
Table 3. SEM-EDS analysis of the reaction precipitates in the follow-up test of As(III) or As(V) containing solutions with various amounts of hydrated lime
Element
(wt%) As(III) As(V)
C 52.14 40.60 38.15 37.22 36.80 32.70
O 39.27 45.09 46.89 45.95 46.84 47.87
Al 0.21 ND 0.22 0.22 0.17 0.27
Ca 08.36 14.31 14.70 16.55 16.13 19.09
As 0.02 ND 0.04 0.06 0.06 0.07
Total 100 100 100 100 100 100
Added hydrated lime (g) 1.65 1.815 1.98 1.32 1.485 1.65
ܳۓॢAs(V)(Fig. 9)ε܃ٽॢǣϢݓ֨ΒقԴəҼՙ Àьþʼݓ؍ؕɰ. ۋəߣşҼՙۆȬʪÀϔڍǰş
˺Лۍ ìڷͿٚԜʼر, Table 3ۆ Ԑݕę Ïۋ ێ܁
ًٖۆ֟ࠪɮںࣀॢҼՙ܁͟қԵں֬֨ॠٕɰ. қ ԵĀę(Table 3) As(III)ۆąڍN.D0.04%ۆҼՙÀ
ࠑ܁ʼؽČ, As(V)ۆąڍ0.060.07%ۆҼՙÀࠑ܁
ʼر As(III)҃ɰ ȭó ࠑ܁ʼؽɰ. EDS қԵĀęقԴ
Al Ձқۋêʽڙۍڹ֬ॹقԐڌʽՙԵধقй͟
ڷͿ ॥ڮʽ(أ 0.5%) Al2O3ق ۆॢ ìڷͿ ߸܁ʽɰ.
2֬ॹۆĀęεܛ०ۺڷͿČ३҇˺, As(III) ۆąڍCO2Àܳۓʿق˰͆pHÀॠ͇ॠيH3AsO3
ۆҼŕՁڷͿܕۦॠş˺ЛقԦՁʽѓ३Եशϸق
ড়ʼݓЇॠي܃äʼݓ؍ڹìڷͿࣺɳʼ϶, şܕ ۆٍĵԐͻٮÏۋѓ३ԵقۆॢAs(III)ۆড়̚ə
ėࠞڹййॢìڷͿǣࢍǮɰ(SǛ et al., 2008; Yokoyama et al., 2009). ъϸAs(V)ۆąڍpHÀǰ؉ݙق˰͆
AsO43-
, HAsO42-
, H2AsO4-
ͿѺজॠيŕՁںǣࢍ
Ǵş˺ЛقҼŕՁںǣࢍǴəAs(III)قҼ३ԦՁʽ
ѓ३Եशϸড়ۋʌڎڌۋॠ϶, Ca(OH)2Ϳęपজ ʽڌؚقԴڌ३ʽCa2+ۋ٣ęCaHAsO4 ̚əCaAsO4-
ۆজ०НںՁॠي܃äʽìڷͿ߸܁ʽɰ(Dutre et al., 1999; Moon et al., 2004; Yokoyama et al., 2012).
Ā
սćقܕۦॠəҼՙε܃äॠşڦॢѓѪڷͿࠞÌ Ձԓࠥ֜܃ܓѪۆॠǣۍԓজѪںۋڌॠيAs(III), As(V)قʂॢ܃ä֬ॹں֬֨ॠٕɰ. 1֬ॹںࣀ३
ՙԵধ࣊ۓ͟, CO2 ܳۓ͟, İъ՚ʪεɵνॠيÀۤ
মڱۺۍ ܓæں Ը܁ॠٕČ, Ը܁ʽ ܓæں цڷͿ
ÁÁۆҼՙܛۋşܵ࠘ۋॠͿ܃äʾսەʪ2
֬ॹں ֬֨ॠي ɰڼę Ïڹ Āںصؽɰ.
1. Ԝ٣ · ԜؓقԴ1 mg/L ȬʪۆAs(III), As(V) Ҽՙ ڌؚ500 gقՙԵধε0.825 g1.155 gͿ࣊ۓॠي
İъ՚ʪ(200, 300, 400rpm)ٮCO2 ܳۓ͟(0.1 L/min, 0.3 L/min)ںɵνॠي1֬ॹں֬֨ॢĀę, As(III) ۆ ąڍ߯ʂ26.5% ۹ÇʼؽČ, As(V)ۆąڍ߯ʂ
90.6% ۹Çʼؽڷ϶, İъ՚ʪقۆॢٖॳ҃ɰəCO2
ܳۓ͟قۆॢٖॳںψۋыəìڷͿǣࢍǮɰ. 1 қÂüڷͿࠑ܁ʽpHəߣşҙࢢ10қūݓśüॠ óॠ͇ॠɰÀ10қۋҙࢢ؋܁জʼرێ܁ॢÉ ں ڮݓॠə ìڷͿ ǣࢍǮɰ.
2. 1֬ॹĀęεцڷͿCO2ܳۓ͟0.1 L/min, İ ъ՚ʪ300 rpmں߯ۺۆܓæڷͿԸ܁ॠٕČ, ՙ Եধ࣊ۓ͟ںݒÀ֨ࡈ2֬ॹں֬֨ॠٕɰ. ъ ڿ֨Â10қ, 20қڷͿǣɀرҼՙȬʪεࠑ܁ॢĀ ęAs(III), As(V) Ͽ˃10қقԴۆȬʪÀ20қقԴ ۆȬʪ҃ɰǰóࠑ܁ʼؽČ, As(V)ə߯ʂ95.1%, As(III)ə߯ʂ38.7% ܃äʼؽڷ϶, As(V)əъڿ֨
Â10қقԴۆϿ˜ܓæۋѕşܵ(0.05 mg/L)ں
χܔॠٕɰ.
3. 2֬ॹقԴ1қÂüڷͿpHٮEhεࠑ܁ॢĀę
1֬ॹĀęٮڮԐॠóъڿ֨Â10қūݓॠ͇
ॠɰÀ10қۋͿ؋܁জʼəεٕ҃ڷ϶, ߯ ܛpHə6.06.5 ԐۋͿǣࢍǣսݗ١ّНݗۆѕ
şܵںχܔॠəìڷͿǣࢍǮɰ. Ehəঞڙঞą (-)ں ǣࢍǴɰÀ 10қ ۋҙࢢə ԓজঞą(+)ڷͿ
ۻঞʼؽɰ.
4. 2֬ॹܛΒқνʽъڿԦՁНںæܓॠيXRD қԵں֬֨ॢĀęՙԵধ(Ca(OH)2)قԴܳĵՁġ НͿ ǣࢍǮʏ portlanditeÀ ěʼݓ ؍Č ѓ३Ե (calcite) peakÀ ǣࢍǮڷ϶, 6Ò ֨Β Ͽ˃ ʴێॢ
peakε ǣࢍǴԓজѪق ۆ३ ѓ३Եۋ Ձʼؽ ڼںঝۍॠٕɰ.
5. ъڿԦՁНۆ Ā܁ ф Ā܁ۆ Ձқں қԵॠş
ڦ३֬֨ॢSEM қԵĀę6Ò֨ΒϿ˃گϸߕ
ۆĀ܁ۋěʼؽČ, EDSεۋڌॢՁққԵĀ ęѓ३ԵĀ܁ےںঝۍॠٕɰ. ҼՙȬʪÀϔڍǰ
؉ێ܁ًٖںݓ܁ॠيEDS ֟ࠪɮںࣀॢҼՙȬ ʪқԵں֬֨ॢĀęAs(III)ۆąڍN.D.0.04%, As(V)ۆąڍ 0.060.07%ۆ ҼՙÀ êʼؽɰ.
6. ԓজѪں ۋڌॠي ڌܕ Ҽՙ ܃ä֬ॹں ֬֨ॢ
Āę As(III)ə মڱۺۋݓ Їॢ ìڷͿ ǣࢍǮČ, As(V)əমڱۺڷͿ܃äÀÀɠॢìڷͿǣࢍǮɰ.
০ܼজߌνۆЛ܃۾ڷͿݓۺʼرٵʏѕսۆ
ȭڹpH Л܃εCO2 ܳۓфԓّġНՁقۆ ३३ĀॣսەںìڷͿǣࢍǮڷ϶, ՙԵধͿۍॢ
֟ࡀێইԜʪߣşԓّġНՁфࠞۻقۆ३
Ԝɾҙқ३ĀʾսەںìڷͿࣺɳʽɰ. ̚ॢড়
ߌνѪقҼ३20қǴٽۆԜɾ০ݥڹߌν֨Âę
߸ÀۺۍَęؓͳۆėśۋػəÂɳॢߌνė܁
ںÍəìۋԓজѪۆÀۤࢀۤ۾ۍìڷͿࣺ
ɳʽɰ. ٍ҆ĵقԴəҼİۺǰڹȬʪۆҼՙεʂ ԜڷͿٍĵεݕॱॠٕڷǣ, ČȬʪۆҼՙфɰت
ॢՁқۋėܕॠəঞąقԴۆۺڌՁф֬ڌՁê ݒںڦॢ߸ÀٍĵÀज़څॠ϶, ০CO2ۆՙҼε
߯ՙজॠČٍ՚ъڿ֨֟ࢰˣںࣀॢCO2 ۦট ڌ ѓ؋ۋ څĵʽɰ.
ČЛॶ
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ইۦ Ìڙʂॡİ قȃݓۙڙėॡę чԐę܁
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ࢢլ
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