potensi penggunaan hidrotalsit dalam remediasi air asam tambang di lahan gambut
DESCRIPTION
POTENSI PENGGUNAAN HIDROTALSIT DALAM REMEDIASI AIR ASAM TAMBANG DI LAHAN GAMBUT. Oleh Sri Juari Santosa Jurusan Kimia FMIPA UGM. Introduction. ACID MINE. Acidity: Oxidation of pyrite. 2. Dissolution of humic and fulvic acids. Introduction. - PowerPoint PPT PresentationTRANSCRIPT
Oleh
Sri Juari SantosaJurusan Kimia FMIPA UGM
ACID MINEAcidity:
1.Oxidation of pyrite
FeS(s) + O2(aq) + 2 H2O(l) Fe2+(aq) + SO4
2-(aq) + 4 H+
(aq) )(24
1gO
Fe3+(aq) + SO4
2-(aq) + 3 H+
(aq) + ½ H2O(l)
2. Dissolution of humic and fulvic acids
Humic Substances are traditionally fractionated according to their solubilities
Fulvic acids: are those organic materials that are soluble in water at all pH values
Humic acids: are those materials that are insoluble at acidic pH values (pH < 2) but are soluble at higher pH values
Humin: is the fraction that is insoluble in water at all pH values
Negative Effect of Acid Mine
Attach and erode soil and minerals to result the dissolution of metals, like Fe, Cd, Mn, and Zn
Environmental pollution
Utilization of Hydrotalcite to remediate acid mine
Study on the ability of Mg/Al hydrotalcite in neutralize the acidity through
exchanging its interlayer hydroxide (OH-), carbonate (CO32-), and
bicarbonate (HCO3-) anions with polluting anions of SO4
2-, humic acid (HA),
and fulvic acid (FA) in aqueous solution
OH- H O2 CO32- HCO3
-
M , M2+ 3+
M , M2+ 3+
OH
OH
OH
OH
Hydrotalcite (layered double hydroxide anionic clay)
1) General formula: [M2+1-xM3+
x(OH)2]x+(An-)x/n . yH2O
where: M2+ is divalent cation M3+ is trivalent cation An- is interlayer anion (1-x/x) varies from 1 to 5
2) Structure:
No Name Empirical formula Crystal system Image Origin
1 BarbertoniteNot Radioactive
Mg6Cr2(CO3)(OH)16·4(H2O)Molecular Weight = 654.01 gm
Hexagonal - Dihexagonal Dipyramidal
Nevada Creek, Tasmania, Australia
2 BechereriteNot Radioactive
Zn4.5Cu1.5Zn2(OH)132(S0.75)2(Si0.25)2(O3)2(OH)Molecular Weight = 933.60 gm
Trigonal - Pyramidal
Color: Light green
Tonopah-Belmont mine, Osborne silver-gold district, Maricopa County, Arizona USA
3 Carbonate-cyanotrichite
Not Radioactive
Cu4Al2(CO3)0.66(SO4)0.34(OH)12·2(H2O)Molecular Weight = 620.53 gm
Orthorhombic Widowmaker mine, Fry Canyon, San Juan Co., Utah, USA
4 CaresiteNot Radioactive
Fe2+4Al2(CO3)(OH)12·3(H2O)
Molecular Weight = 595.49 gmTrigonal -
Trapezohedral
Poudrette quarry, Mt Saint-Hilaire, Rouville Co., Québec, Canada
5 CarrboyditeNot Radioactive
Ni10Cu4Al9(SO4)4(CO3)2(OH)43·7(H2O)Molecular Weight = 2,445.61 gm
Hexagonal Carr-Boyd Nickel Mine, Western Australia, Australia
6 ChalcoalumiteNot Radioactive
CuAl4(SO4)(OH)12·3(H2O)Molecular Weight = 525.67 gm
Monoclinic – Sphenoidal
Lavender Pit, Bisbee, Cohchise County, Arizona, USA
7 Charmarite-2H & Charmarite-3T
Not Radioactive
Mn2+4Al2(CO3)(OH)12·3(H2O)
Molecular Weight = 591.86 gmHexagonal –
Trapezohedral
Color: Orange brown, Pale brown, Pale blue, Colorless
Mt. St.-Hilaire, QUE, Canada
8 ChlormagaluminiteNot Radioactive
Mg3.5Fe2+0.5Al2(OH)12Cl(CO3)0.5·2(H2O)
Molecular Weight = 472.53 gmHexagonal Color: Colorless,
Yellow brown
Kapaev explosion pipe, Angara River, southern Siberian Platform, Russia
9 CyanotrichiteNot Radioactive
Cu4Al2(SO4)(OH)12·2(H2O)Molecular Weight = 644.33 gm
Orthorhombic Grandview mine, Grand Canyon, Coconino County, Arizona, USA
10 GlaucoceriniteNot Radioactive
Zn3Cu2Al3(SO4)1.5(OH)16·9(H2O)Molecular Weight = 982.56 gm
Trigonal Mina Serpieri, Laurium, Attiki, Greece
11 HydrombobomkuliteNot Radioactive
Ni0.75Cu0.25Al4(NO3)1.5(SO4)0.5(OH)12·14(H2O)Molecular Weight = 765.17 gm
Monoclinic Color: Sky blue Mbobo Mkulu cave, Nelspruit district, South Africa
12 HydrowoodwarditeNot Radioactive
Cu0.5Al0.5(OH)2(SO4)0.25·0.75(H2O)Molecular Weight = 116.81 gm
Trigonal – Hexagonal Scalenohedral
St Christoph Mine, Bärenhecke, Glashütte, Erzgebirge, Saxony, Germany
13 ManasseiteNot Radioactive
Mg6Al2(CO3)(OH)16·4(H2O)Molecular Weight = 603.98 gm
Hexagonal – Dihexagonal Dipyramidal
Jacupiranga mine, Jacupiranga, Sao Paolo, Brazil
14 MbobomkuliteNot Radioactive
Ni0.75Cu0.25Al4(NO3)1.5(SO4)0.5(OH)12·3(H2O)Molecular Weight = 567.00 gm
Monoclinic – SphenoidalH
Jomac Uranium mine, White Canyon, San Juan Co., Utah, USA
15 NickelalumiteNot Radioactive
Ni0.7Cu0.3Al4(SO4)1.5(NO3)(OH)12·3(H2O)Molecular Weight = 632.31 gm
Monoclinic – Sphenoidal
Color: Sky blue Mbobo Mkulu cave, eastern Transvaal, South Africa
16 Quintinite-2HNot Radioactive
Mg4Al2(OH)12(CO3)·4(H2O)Molecular Weight = 487.34 gm
Hexagonal – Trapezohedral
Jacupiranga Mine, São Paulo, Southeast Region, Brazil
17 Quintinite-3TNot Radioactive
Mg4Al2(OH)12(CO3)·4(H2O)Molecular Weight = 487.34 gm
Trigonal – Trapezohedral
Jacupiranga Mine, São Paulo, Southeast Region, Brazil
18 SpangoliteNot Radioactive
Cu6Al(SO4)(OH)12Cl·3(H2O)Molecular Weight = 797.91 gm
Trigonal – Ditrigonal Pyramidal
Blanchard mine, Bingham, Socorro County, New Mexico, USA
19 WoodwarditeNot Radioactive
Cu4Al2(SO4)(OH)12·3(H2O)Molecular Weight = 662.34 gm
Hexagonal Green River Formation, Uintah Co., Utah, USA
20 ZaccagnaiteNot Radioactive
Zn3.9Al2.1(OH)12(CO3)·3(H2O)Molecular Weight = 629.83 gm
Hexagonal – Dihexagonal Dipyramidal
Hilarion Mine, Agios Konstantinos, Lavrion District, Attikí Prefecture, Greece
21 ZincaluminiteNot Radioactive
Zn6Al6(SO4)2(OH)26·5(H2O)Molecular Weight = 1,278.62 gm
Hexagonal Kamariza Mine, Laurium, Attiki, Greece
22 ZincowoodwarditeNot Radioactive
Zn0.47Al0.38(OH)2(SO4)0.18(H2O)0.6
Molecular Weight = 103.10 gmTrigonal -
Rhombohedral
Hilarion Mine, Agios Konstantinos, Lavrion District, Attikí Prefecture, Greece
23 Zincowoodwardite-1TNot Radioactive
Zn0.66B0.3Al0.33(OH)2(SO4)0.155·0.96(H2O)Molecular Weight = 121.50 gm
Trigonal - Rhombohedral
Color: Pale blue, Bluish white
Laurion (Lavrion,Laurium), Greece
24 Zincowoodwardite-3RNot Radioactive
Zn0.5B0.33Al0.33(OH)2(SO4)0.2·0.59(H2O)Molecular Weight = 109.02 gm
Trigonal - Hexagonal Scalenohedral
Color: Pale bluish white, Bluish white
Laurion (Lavrion,Laurium), Greece
50 mL mixed solution of Mg2+
and Al 3+
NaOH 0,5 M
Synthesis of Mg/Al hydrotalcite
pH
pH
oC120
7.00
XRD
IR
Synthesis of Mg/Al hydrotalcite (continued)
Stability Test
pH3; 5; 7; 9;
11; 13
50 mL
Aquadest
0.1 g Mg/Al
hydrotalcite
Shaker bath, 2 hours
Stability Test (countinued)
oC120
mg
198
Purified Peat Soil or Humus
Humin(Insoluble fraction)
Fulvic Acid(Soluble)
Purified HumicAcid
Humic Acid(Precipitation)
Humic Substances(Soluble fraction)
Pure Humic Acid(Solid)
Humic Acid(MIBK phase)
Humic Acid(Aqueous phase)
Humin(MIBK phase)
Humic Acid & Humin(MIBK phase)
Fulvic Acid(Aqueous phase)
Peat Soil or Humus
Solvent ExtractionAlkaline Extraction
Purification
Shaking in NaOH Solvent extraction with MIBK
Ad. HClBack extractioninto NaOH
Solvent extraction with MIBK
Washing & Evap. MIBKPurification
Isolation of Humic and Fulvic Acids
Effect of Medium Acidity on the Adsorption
50 mL Humic acid 150 mg/L
pH3; 5; 7; 9; 11; 13
0.1 g Mg/Al hydrotalcite
Shaker bath, 2 hours
Effect of Medium Acidity on the Adsorption (continued)
filtrateseparation
UV-Vis 400 nm
Aads Vs pH
Rate of Adsorption
50 mL Humic acid
150 mg/L
9.00
0.1 g Mg/Al hydrotalcite
Shaker bath
minute
10, 20, 40, 60, 180, 300
Rate of Adsorption (continued)
filtrate UV-Vis 400 nm Aads Vs t
Adsorption Capacity
50 mL Humic acid
ppm120, 150, 180, 210, 240
0.1 g Mg/Al hydrotalcite Shaker bath
minute
t optimum
Adsorption Capacity (continued)
filtrate UV-Vis 400 nm Aads Vs A0
Ceq/m Vs Ceq
25 mL NaOH 0.5 M
0.01 g humic acid + Mg/Al
hydrotalcite
Desorption
minute
5, 15, 30, 60, 120
Shaker bath separation
Desorption (continued)
filtrate UV-Vis 400 nm
% Elution Vs t
Characterization of Functional Group of Humic Acid
Table Distribution of oxygen containing functional groups (meq/100 g) in humic acids isolated from widely different climatic zones
Climatic zone Tropical
Indonesia Kalimantan
Acidity Artic@ Subtropical@
South1) Central2) East3) North
Sumatera4) Central Java5)
Others@
COOH 320 420 - 520 341 424 353 322 343 380 - 450 Phenolic OH 240 210 - 250 332 288 330 298 300 210 - 570
Alcoholic OH 490 290 6 29 6 10 n.d. 20 - 490
Total 560 630 - 770 673 712 683 619 643 560 - 890 @ Stevenson, 1982 1) Gambut district 2) Barembeng village 3) Sambutan village 4) Labuhan Batu village 5) Rawa Pening n.d.: not determined
0 3 6 9 12 14
pH
Stab
ility
of
Mg/
Al h
ydot
alci
te
(%)
20
80
60
40
100
0
0.25
0.5
0.75
1
0 5 10 15
pH
Frac
tion
of a
dorb
ed a
nion
SO42-HAFA
Effect of Medium Acidity on the Adsorption of Anions on Mg/Al Hydrotalcite
The Change of Medium Acidity after the Adsorption of Anions
pH pH pH Anion
Awal Akhir Anion
Awal Akhir Anion
Awal Akhir
3.0 5.1 3.0 4.2 2.9 4.6
5.0 5.7 5.0 5.1 5.0 5.3 7.0 6.2 7.0 5.6 7.3 5.9
9.0 8.1 9.0 8.4 9.3 8.4
11.0 8.9 11.0 9.2
Fulvat-
11.3 9.0
SO42-
13.0 9.3
Humat-
13.0 9.7
Interpretation of the Adsorption Process
OH- H O2 CO32- HCO3
-
OH-
H O2
CO32-
HCO3-
M , M2+ 3+
M , M2+ 3+
OH
OH
OH
OH
+ +
Hydrotalcite Anionic sorbate (A )n- Hydrotalcite containing sorbate
Effect of Interaction Time on the Adsorption of Anions
0
20
40
60
80
100
0 30 60 90 120 150 180
t (min)
Ani
on re
mai
ned
(%)
HASO42-FA
Adsorption Capacity of Mg/Al Hydrotalcite for Humic Acid
0
40
80
120
Ads
orpt
ion
capa
city
(mg/
g)
Kaolin
clay
Fisher
PAC Darc
o G-60
ALDRICH Grap
hite p
owder
Cabot V
ulcan xc
72
Cabot M
onarc
h 1400
Cabot P
earls
2000
Carbon
Chitin
Chitosan
Mg/Al H
ydrotalci
te
Zn/A
l Hyd
rotalcit
e
0
25
50
75
100
0 60 120 180
Adsorption time (min)
%
HAFA
0 60 120 180
Desorption time (min)
HAFA
Regeneration of Mg/Al Hydrotalcite from Humic Acid
Mg/Al hydrotalcite is a very potential adsorbent for the remediation of acid mine since:
1. Easy to be synthesized2. Highly stable at wide range of medium acidity3. Highly adsorb anions occurring in acid mine4. Increasing the pH of medium to close to neutral5. Easy to be regenerated
Implication:1. Dissolution of metals from soil and minerals in acid mine may be minimized2. The desorption product may be used to ameliorant