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Hydrochloric Acid from Aqueous
Solutions by Tri-n-dodecylamine
60(2), pp. 130-135, 2016 and Tri-n-octylamine / diluents
DOI: 10.3311/PPch.8355
Creative Commons Attribution b
Jamal Stas1*, Hala Alsawaf 1
research article Received 13 July 2015; accepted after revision 16 September 2015
Abstract 1 Introduction
The extraction of HCl from aqueous solutions using two types Hydrochloric acid is an important chemical and widely used in
of long-chain tertiary amines tri-n- dodecylamine/ kerosene a variety of industries and chemical processes and in some cases
and tri-n-octylamine/ kerosene in the presence of octanol-1 or as a very successful substitute in processes that otherwise use sul-
tributyl phosphate as modifier has been studied. The effect of phuric acid. The largest applications of HCl are: Steel pickling,
mixing time, HCl concentration in the aqueous phase, amine oil well acidizing, food manufacturing, plastics, pharmaceuticals,
concentration, organic to aqueous phase ratio, modifier per- organic chemical synthesis, and ore processing [1-4].
centage in the organic phase, NaCl concentration in the aque- A large amount of acidic waste water which is listed as a
ous phase and temperature were studied. The effect of some hazardous waste will be generated from hydrometallurgical
diluents such as: toluene, benzene and xylene on HCl extrac- and acid pickling industrial units. So, the recovery of HCl from
tion was also investigated and found to follow the order: its aqueous streams is crucial and needed to prevent environ-
Benzene > toluene > kerosene + 10% octanol-1 ≈ xylene mental pollution and to recycle the recovered acid.
Tri-n-dodecylamine and tri-n-octylamine showed a great Tertiary amines such as: Tri-n- dodecyl amine, tri-n-octy-
affinity towards HCl in all tested diluents. Both amines (TDA lamine, Alamine 308 (tri-isooctylamine), TEHA (tri-2-ethyl
and TOA) can be successfully used for HCl recovery from hexyl amine), Alamine 336 (a mixture of triocty/decyl amine)
aqueous acidic solutions. have been proven to be effective extractant to recover HCl and
Water was found to be effective to strip HCl from the acid H2SO4 from aqueous solutions [5-8]. The extraction reaction of
loaded organic phase and more than 95% of HCl can be recov- HCl by tertiary amines can be written as follows:
ered in three stripping stages at Vaq/Vorg = 20/1 and 75 °C.
R 3 N (org) + HCl (aq) R 3 NHCl (org) (1)
Liquid – Liquid Extraction of Hydrochloric Acid by TDA and TOA 2016 60 2 131
1.2 0.25
1.0 0.20
0.8 0.15
[HCl]org
0.6 0.10
Kd
0.4 0.05
0.2 0.00
3.2 Effect of HCl concentration in the aqueous phase diluents and there is no need to add a modifier to the organic
The extraction of hydrochloric acid in the range of phase, but it is not recommended to use aromatic diluents in
(0.01-8 M) by 0.1 M tri-n-dodecylamine /kerosene containing an industrial scale because they are known to be carcinogenic
10% octanol-1 as modifier at an organic to aqueous phase ratio and can produce environmental problems. Consequently using
(Vorg/ Vaq = 1), and at 25 °C was examined. The results are shown kerosene containing octanol-1 as modifier is advisable for its
in Fig. 2. It is obvious that the concentration of hydrochloric advantages, lower operation cost and lower toxicity.
acid in the organic phase [HCl]org was increasing in accordance
with Le Chatelier’s principle with the increase of hydrochloric 140
TDA/kerosene + 10% octanol-1
acid in the aqueous phase [HCl]aq, until [HCl]org reaches the 120 TDA/benzene
TDA/toluene
value of 0.1 M, then no changes of [HCl]org was observed in the 100 TDA/xylene
range of acidity ([HCl]aq = 0.2−3.5M) and the molar ratio of the TOA/kerosene + 10% octanol-1
80 TOA/benzene
extracted HCl concentration to the initial tri-n-dodecylamine TOA/toluene
TOA/xylene
Kd
60
concentration was equal to 1 ([HC]org/[TDA]i ≈1). So it can be
concluded that the nature of extracted species within this range 40
of acidity will be in the form of R3N.HCl. Afterwards, [HCl] 20
org
restarted to increase again with the increase of [HCl]aq from 0
3.5−8 M, which means that other species like R3N.(HCl)2 and 0.0 0.2 0.4 0.6 0.8 1.0
R3N. (HCl)3 will be formed (1<[HCl]org/ [TDA]i <3). [R3N]i (M)
YHCl %
0.5M TDA + TBP 50
0.2
40
30
0.1
20
10
0.0
0 5 10 15 20 25 30 35 40 0
0.5 1.0 1.5 2.0 2.5 3.0
Modifier (%)
Vorg/Vaq
Fig. 4 Variation of [HCl]org vs. octanol-1 and TBP percentage Fig. 5 Variation of YHCl% vs.Vorg/Vaq.
in the organic phase. □ [TDA]i = 0.1 M /kerosene + 10 (v/v)% octanol-1.
● [TDA]i = 0.1 M/kerosene + (5−35% v/v octanol−1). ■ [TDA]i = 0.5 M /kerosene + 10 (v/v)% octanol-1.
○ [TDA]i = 0.5 M/kerosene + (5−35% v/v octanol−1). [HCl]i = 0.5 M , Vorg/Vaq = 0.5−3, t = 40 °C.
▲ [TDA]i = 0.1 M/kerosene + (5−35% v/v TBP).
∆ [TDA]i = 0.5 M/kerosene + (5−35% v/v TBP).
[HCl]i = 0.5 M , Vorg/Vaq = 1, t = 40 °C. T (K)
300 305 310 315 320 325
-0.58 100
90
-0.59
(Vorg/ Vaq = 1, t = 40 C). The results were represented in Fig. 4.
o LogKd = 214.44 (1/T) - 1.3095 80
-0.60 r= 0.9939
In the form of [HCl]org against modifier percentage in the organic 70
phase. It can be seen from Fig. 4 that octanol-1 and TBP have a -0.61 60
YHCl (%)
50
Log Kd
very small positive effect on HCl extraction and TBP has a little -0.62
40
bit greater effect than octanol-1, especially at high amine con- -0.63
30
centration 0.5M TDA/kerosene. Thus, 10% (v/v) of octanol-1 or
-0.64 20
TBP is mandatory to be added to tri-n- dodecylamine to prevent
10
third phase formation and accelerate phase separation. -0.65
0
0.00306 0.00312 0.00318 0.00324 0.00330 0.00336
3.5 Effect of phase ratio on HCl extraction 1/T
The effect of phase ratio on the extraction of HCl by Fig. 6 Effect of temperature on HCl extraction.
TDA/ kerosene was done by mixing an aqueous solution of 0.5 [TDA]i = 0.1 M/kerosene + 10% (v/v) octanol-1,
M HCl with 0.1 M TDA/kerosene containing 10%(v/v) octanol-1 [HCl]iaq = 0.5 M. Vorg/Vaq = 1 , T = (300−325 K).
Liquid – Liquid Extraction of Hydrochloric Acid by TDA and TOA 2016 60 2 133
100
70
90
80 60 75 oC
65 oC
70 50 55 oC
60 0.5 M TDA
0.1 M TDA 45 oC
40
50
YHCl %
Ystrip (%)
40 30
30 20
20
10
10
0 0
0.0 0.2 0.4 0.6 0.8 1.0 0 5 10 15 20
[NaCl]i (M) Vaq / Vorg
Fig. 7 Effect of NaCl concentration in the aqueous phase on HCl extraction. Fig. 8 Effect of Vaq/Vorg ratio and temperature on HCl stripping from0.5 M
■ [TDA]i = 0.5 M/kerosene + 10 % (v/v) octanol-1, TDA/kerosene + 10 % (v/v) octanol-1.
□ [TDA]i = 0.1 M/kerosene + 10 % (v/v) octanol-1, [HCl]i org = 0.465 M, mixing time = 20 min,
[HCl]i = 0.5 M, [NaCl]i = 0.2 – 1 mol/L, Vorg/Vaq = 1, t = 40 °C Vaq/Vorg = 0.5−20. t = ♦ 45 °C, □ 55 °C, ▲ 65 °C, ● 75 °C.
3.8 Stripping of HCl from the loaded TDA/kerosene No effect of NaCl was observed on HCl extraction and the
+10%(v/v) octanol-1 temperature has a small negative effect on HCl extraction, the
To investigate the ability of stripping hydrochloric acid from ∆Ho for the extraction reaction was found to be −4.1 kJ/mol.
the loaded organic phase of 0.5 M TDA/kerosene + 10% (v/v) Temperature and aqueous to organic phase ratio Vaq/Vorg have
octanol-1 and regenerate the extractant, many stripping experi- a great effect on HCl stripping from the acid loaded TDA/kero-
ments were carried out by mixing the acid loaded organic phase sene + 10% (v/v) octanol-1 when water was used as a stripping
with double distilled water at different organic to aqueous phase agent. The optimum operation conditions for HCl stripping are:
ratios ranging from 0.5 to 20 and at four different temperatures VH2O/Vorg = 20/1, t = 75 °C, and 3 stripping stages.
(45, 55, 65 and 75 °C). The results presented in Fig. 8. Show
that the yield of HCl stripping is increasing with the increase Nomenclature
of Vaq/Vorg ratio and temperature. The best operating conditions M Concentration in mol L−1
to recover about 64% of HCl from the loaded organic phase [HCl]i Initial hydrochloric acid concentration in the
in just one contact were found to be (Vaq/ Vorg = 20, t = 75 °C) aqueous phase (M)
and in three successive contacts, more than 95% of HCl will be [HCl]aq Equilibrium hydrochloric acid concentration
recovered from the loaded organic phase. in the aqueous phase (M)
[HCl]org Equilibrium hydrochloric acid concentration
4 Conclusion in the organic phase (M)
The equilibrium studies of two immiscible phases: water [HCl] org
i
Initial hydrochloric acid concentration in the
and tertiary amines (TDA and TOA) showed that: organic phase (M)
TDA/kerosene and TOA/kerosene have high affinity [TDA]i Initial tri-n-dodecylamine concentration in
towards HCl. Although the yield of HCl extraction by TOA the organic phase (M)
is a little bit higher than that of TDA, both amines regard- [TBP]i Initial tri-n-butyl phosphate concentration in
less their price are advisable to be used for HCl recovery from the organic phase (M)
aqueous acidic solutions. [TOPO]i Initial tri-n-octyl phosphine oxide
Benzene showed a positive effect on HCl extraction when it concentration in the organic phase (M)
was used as diluents, but it is preferable to use kerosene +10 % Kd Distribution ratio = [HCl]org/[HCl]aq
(v/v) octanol-1 to have lower operation cost and lower toxicity. ∆Hº Enthalpy change of the extraction reaction
The concentration of tertiary amines (TDA and TOA) and (Jmol−1)
organic to aqueous phase ratio Vorg/Vaq have a positive effect R gas constant (8.314 J K−1 mol−1)
on HCl extraction. The best operating conditions for HCl T Thermodynamic temperature (K)
extraction are: Vorg/Vaq = 1.5, [Amine] = 0.5M + 10% (v/v) t Celsius temperature (°C)
octanol-1, t = 40 °C. Vaq Volume of the aqueous phase
Liquid – Liquid Extraction of Hydrochloric Acid by TDA and TOA 2016 60 2 135