Professional Documents
Culture Documents
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Lech Bolinski
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ACDfOWLBDGBKBHTS
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ABSTRACT
..
.
'l'ABLB OP COH'l'BIt'1'S
paq.
~'
CHAPT ER 2: PREVIOUS WORK 17
~' 2.1. Hydrometallurgical methods. 17
!l 2.2. Oxidants. 18
~
,~ 2.3. problems with excessive alumina
i
'"
~l dissolution. .......... .. 19
....
~
i'
~ 2.4. Leaching reactors. • . . • . . • 20
~, 2.5. Rate of P~M dissolution. . . . . 21
>,
"
~
;'
1
2.6. Industrial applications. ... 22
2.7. Process 1: Catalyst substrate dissolution by
r:f
a sulphuric acid digestion. . . . • . • • • . 22
~
r
~ 2.8. Process 2: PGM extraction from honeycombs by
i ~
~
"t support by chloride leaching: CRO-Redox
process. . . . . . . . . . . . . . . . . . . 28
~
~
.,
,
·· ····
2.11. Pyrometallurgical processes. 32
2.12. Process 5: primary Copper or Nickel
Smelters. ·
·..··· ········
· 33
······
2.13. Process 6: Plasma Fusion. · 34
· ··
2.14. ether methods of PGM recovery. 36
········
2.15. Chemistry of aqua regia.
2.16. Spontaneous decomposition of aqua regia.
36
37
2.17. Basic chemistry of platinum and rhodium. 39
2.18. Redox reactions in aqua regia.
···· , 40
2.19. PGM cxidation in aqua regia.
· ····
·
2.20. PGM extraction from pregnant solution by
41
solution.
·· ············ 93
4.9. Washing.
· · • · · 93
ft
3.3M HCl 1 O. IBM A1Cl] 1 3. SM HNO] for 3 hO\lrs. . . 60
Figure 16: Catalyst leaching in stirred reactor using
1.66M HCl / 0.29M AlCl) / 3.SM HNO, for 3 hours.. ~3
(
,
TABLES
.'
- - l
CBAP~.R 1: IMTRODUCTIOM
1.1. Introduction
POLLUTANT [g/km]
YEAR
Carbon Hydrocarbons Nitrogen
monoxide oxides
USA:
1975 9.3 0.93 1.9
1983 4.4 0.25 1.2
1993 2.1 0.25 0.6
California:
1970 5.6 0.25 0.93
1977 4.4 0.25 0.44
1983 2.1 0.16 0.25
European Community:
Over 2 1 1988: 5.3 2.0 0.7
1.4 - 2 1 1991: 6.2 1.7
Under 1.4 1 1990: 9.3 3.1 1.2
1992: 3.9 1.1
,« Japan:
....
1 1975: 9.3 0.93 1.9
1983: 3.1 0.25 1.2
Australia:
1987: 9.3 0.93 1.9
Brazil:
1992: 9.3 0.93 1.9
1997: 2.1 0.25 0.6
Mexico:
1991: 9.3 0.93 1.9
1993: 2.1 0.25 0.6
1. catalyst support
2. washcoat
3. catalyst material.
': ''''l~
.~
1
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7
.
i
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o
•
,
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•
l
•
1
PBLLETS 1I0.0LITRS
CORDIER/TE SUPPORT
.,
'.
PREPARED CATALYST
, 11
\
DUAIID
SDPPLY
(
Total Mine Russian Reeyclinq other
Supply Prod. Sales Autocat. Reeyelinq
[t/y] [t/y] [%] [t/y] [%] [t/y] [%] [t/y] [%]
Tot. 228.0 140.1 61.4% 70.2 30.8% 8.6 3.8% 9.1 4.0%
1.9. Contaminations.
1.11. oil.
"
,
r
18
2.2. oxi4anta.
PrLLeTS
o L -_ _-.,._ _ _- '
Alum/num (Scrap)
PG" a";';~~/o~l@
o '-------,.---=---'---'
Soflds
Of fuslcn
HONCYCOMBS
Alummum (Scrap)
r-_~_II_,r_a_,._ _ [®
~~----~------~ ~-------r------~
HCI/CI>f.-1
HCI
27
L.achlng Agen /
(Ch/orld.s Mlx/ur.)
8) ~------,-------~
@
~------,,------~
@
r---~----~--------~
Sollds
Solld.
Fllirai.
Sollds
Impurlly M.lals
HydroAId••
AliSo. )1
10 .vaporallon
ct alum producllon
{
mirai.
R.cycl.
HCI9aS
Al,O.
10 alum producllan
32
rejected. Essentially, during leaching step 1, complete
removal of impurities is achievable, leaving a purified
residue that is suitable for conversion to alum. Pregnant
solution from step 2 is allowed to cool, and PbCl 2 is
crystallized. Next, the solution is filtered and PbC1 2 is
removed, step 3. A system of PGM recovery from the leaching
solution consists of neutralization, by NaOH, step 4, so
removing impurity metal hydroxides, step 5, sorption and
reduction-to-metal on an anion exchange resin, Amborane 345
(step 6), and then cementation with aluminum, step 7.
Excessively high resin consumption was experienced and the
step was replaced by PGM precipitation directly from non-
neutralized leach solution by hydrogen reduction. PGM
concentrates from filtration steps 6 and 7 are sent to
further refining, while the filtrate is treated to allow
AICl) crystallization, step 8, and filtration, step 9. The
filtrate is recycled to leaching step 1, while residue
(AlCl)o6H20) is readily decomposed to HCl and alumina at over
200°C, step 10. The HCl~~ generated during the decomposition
is absorbed in the spent leach solution, step 11, and
recycled to the leaching stage.
HONcrCOM8S or PCLLHS
Sla~
1
1
i
1
1
Fiqure 8: Flowsheet of Process 6 - PGM recovery by plasma
fusion technique.
i
(
r
36
Despite the fact that aqua reqia has been known and
used for centuries, a composition of the mixture was never
defined. In 1916, Hoke and Moore reported that chemists and
chemical textbooks described aqua reqia as a mixture of HCl
and HNO] but did not specify the acids ratio [30]. Some
other sources defined aqua reqia as three parts of HCl and
one part of HNO] taken as ordinary concentrated commercial
acids [31] [32] [33]. In those days, the molality of
concentrated HCl was the same as now, equal to 10.1 M, but
HNO] was only 11.1 M (-16 M today). The acid ratio and
molalities rouqhly corresponded to a widely accepted
assumption that HCl and HNO] reacted in the ratio 3HCl/ 1HN03 •
[
Nowadays handbooks define aqua reqia as a mixture of 1
part of concentrated HCl and 3 parts of concentrated HNO] or
1 part of concentratad HCl, 3 parts of concentrated RNO] and
1 part of water [16]. The abc/ve definition is imprecise, and
also does not mean the same as in 1916, because while
molality of concentrated HCl has remained unchanqed since
1916, the term "concentrated RNO]" now means -16 M acid.
39
(
NOCl ;t NO(a> + Cl- (11)
"'.UR OuT
TH(RHO~UT
/
TH R T R IIATEP BATH
[lECTRaDE
075 fil
.
48
'oIATER OUT
STIRRER
lliERMoMETER
ELECTRODE
"'" 'oIATER IN
065M
CLAMP
HEATING
JACKET
LEACHANT
RESERVOIR
1 ...
% Pt, Rh leached
100 ~---------------------------------------------.
90
80
70
60
50
40
30
20
10 o Platinum
o Rhodium
o ~--~----~----~----~--~----~----~____~__~
20 30 40 50 60 70 80 90 100 110
Temperature [deg C]
% Pt, Rh leached
100.-----------------------------
90 -
80
70
60
50
40
30
20
10 o Platinum
o Rhodium
o ~--_+----4-----+_--~----_+----~----+_--~----~
20 30 40 50 60 70 80 90 100 110
Temperature [deg C]
% Pt, Rh leached
100 . - - - - - - - - -_ _ _ _ _ _ _ _ _ _ ~
~J ~I C) 1
90
80
70
60
50
40
30
--
20
---------J-
10
o ~--~----~----1-----~--~-----+----1---~
20
Q C'
o
Platinum
Rhodium
30 40 50 60 70 80 90 100 110
Temperature [deg C]
61
(
solution. ~GM extractions very quickly increase with an
increase of temperature, and are from 5% to 8% better than
for HCI-HNO] solutions (Figures 13 and 14), however hiqher
temperatures are still necessary to achieve good recoveries.
A temperature of 900C was considered to be the approximate
optimum for leaching, because recoveries are only 2-3% lower
than at the boiling point of 107°C.
% Pt, Rh leached
100 ~---------------------------------------------,
90
80
70
60
50
40
30
20
10 o Platinum
o Rhodium
o ~---+----~--~~--~----+----4----~-----+---~
20 30 40 50 60 70 80 90 100 110
Temperature [deg cl
t
64
% Pt, Rh leoched
100 r - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ------
90
80
70
60
50
40
30
20
10
I-~~-~-Ietinu~-]
~ Rhodium
o f------+-----+------j----- --+-------
a 2 3 4 5
Time [heurs]
% Pt. Rh leoched
100~--------------------------------------------'
o E)
90
------~OA-----~D
80
70
60
50
40
30
20
10
[~ Platinum
Rhodium
0
0 2 3 4 5
lime [hours]
% Pt, Rh leached
100 ~----------------------------------------------,
90
80
70
60
50
( 40
30
20
10 Platinum
Rhodium
O~------~---------+--------~-- ______~________~
o 2 3 4 5
Time [hours]
% Pt. Rh leached
100 r - - - - - - - - - - - -
__A----_+:~
90
80
70
60
50
40
30
20
r--~- ----------
1 1
10 Plaltnum
i
1 [J Rhodium
L ______________ _
% Pt, Rh leoched
100 ~--------------------------------------'------,
90
80
70
60
50
40
30
20
10 10- Plotinum ]
~ Rhodium
O~------~------~------~-------+I ______~
o 2 3 4 5
lime [hours]
.
70
% Pt, Rh leoched
100 ~---------------------_._-_.-
90
BO
70
60
50
40
30
20
10 ü
Plotin;u]
o Rhodium
L--_ _ __
o ~----t----+----+-----+------
o 2 3 4 5
Time [hours]
~ Pt. Rh leached
100 ,-------------------------- ------
95
90
85
~ _--+:::t----+J
80
75
70
,'f
. 65
60
55
50
45
0 Plct;n~
0 Rhodium
---
o 2 3 4 5 6 7 8 9 10
Concentration of HCI [M)
% Pt. Rh leached
100 ~----------------------------------------------,
95
90
85
~-~D~----~D~______8
80
75
70
65
o Plotinum
D Rhodium
60 L -_ _ _ _ _ _L -_ _ _ _ _ _L -_ _ _ _ _ _~_ _ _ _ _ _~ _ _ _ _ _ _ _~_ _ _ _ _ _~
o 2 3 4 5 6
Concentration of HCI (M]
,
74
~ Pt, Rh leoched
100 , - - - - - - - - - - - - - - - --~- -- -- - -- ~~- ~
95
90
85
80
75
70
65
o Plotinum]
o Rhodium
60~-----L-----L----L-----~----~-----
o 2 3 4 5 6
% Pt leached
100
95
90
85
80
75
70
--l
Cl AICI 3 :O M
65
0 AICI .0.18 M
3
(> AICI :0.29 M
3
60
0 2 3 4 5 6 7 8 9 10
% Rh leached
100
95
90
85 -.
80
~-tr--BO-_-'8 __ _
75
70
65
60
55
50 0 AICI 3 : DM
0 AICI3 : O.18M
45
0 AICI : O.29M
3
40
0 2 3 4 5 6 7 8 9 10
.
78
..
~ Pt, Rh leached
1 00 ~------------------------ -------- -
90 ___J
80
70
60
50
l ,~,
o
PloHnum
Rhodium
------~. -
40
30
20
10
o 2 3 4 5
% Pt, Rh leoched
100~----------------------------------·------------,
o Plotinum
D Rhodium
40
30
20
10
o 2 3 4 5
Concentration of HNO [M]
a
.
82
The above considerations are less applicable to
honeycombs, because the structures of pellets and honeycombs
are very different. Honeycomb catalyst has narrow internal
channels difficult to penetrate by the leaching solution,
and this suggests that, to increase PGM recoveries,
honeycombs, unlike pellets, may require grinding to expose
PGM trapped inside the channels. Excessive A1 20) dissolution
is not a problem, because honeycombs are mostly made of acid
resistant cordierite.
Form of
catalyst
, Pt
leached
,Rh
leached
Form of % Pt ,Rh
catalyst leached leached
,
87
% Pt. Rh 1eached
100 ~----------------------------------
90
---~
80
70
50
40
30
20
--
10 0 Platinum
0 Rhodium
0
0 2 3 4 5
Time [hours]
% Pt, Rh leached
100~----------------------------------------
70
60
50
40
30
20
10 0 Platinum
0 Rhodium
0
0 2 3 4 5
Time [hours]
.
89
~ PI Rh leached
100 - - - - - - - - . - - - - - - - - . _ - -
90
80
70
60
50
40
30
20
10 Platinum
Rhodium
0 -1
0 2 3 4 5
Tlme [hours]
% Pt, Rh lee_ned
100~---------------------------------------------~
90
~ _ _---EJ
80
70
co
50
..
,, 40
30
20
10 0 Pletinum
0 Rhodium
0
0 2 3 4 5
Time [hours]
% Pt. Rh leached
100 , . . - - - - - - - - - - - - - - - - - - - - - - - - - - -
90
80
70
60
50
40
30
% Pt. Rh leached
100 , - - - - - - - - - - - - - - - - - - - - - - - - - -
90
8Q
70
60
50
40
30
20
10 0 Plotinum
0 Rhodium
0
0 2 3 4 5
Time [hours]
% Pt, Rh leached
100
90
80
ô7
>
V
70
60 ~
Stirred Reactor
50
0 Pt
• V Rh
40
Tubular Reactor
30
0 Pt
20
0 Rh
10
o 1-----+----+----+-----l-------1
o 2 3 4 5
Time [heurs]
autocatalyst autocatalyst
placed placed
"horizontally" "ve.ctically"
Pt concentration
before leaching 1070 [ppm] 1070 [ppm]
Rh concentration
before leaching 51 [ppm] 51 [ppm]
Pt concentration
after l\:!aching 150 [ppm] 140 [ppm]
;r
.. Rh concentration
after leaching 14 [ppm] 15 [ppm]
-
0 Platinum
98
Rhodium
96
94
92
90
88
86
"'"
84
82
80
78
76
3 hrs AICI3+~O 4 hrs jet
leaching washing leaching washing
CF) ® @ ®
~igur. 37: Effect of washinq followinq leachinq into 8.0M HCI
1 3.5M HNO] at 94-97°C.
99
98
D Platinum
_ Rhodium
96
94
92
90
88
86
84
82
80
78
76
3 hrs AICI 3 +HlO 4 hrs jet
leaching woshing leaching woshing
o ®
Jli9'U'e 38: Effect of washinq followinq leachinq into 1. 66M HCl
-, 1 O.29M Alel] / 3.5M HNO] at 94-97°C.
.'
100
102
~iqur. 391 HCl mean activity (aHQ) in HCl-3.sM RNO, and HC1-
0.29M A1C1 3-3. SM HN03 in differant HCl concentrations and at
lOO·C.
103
14
13
12
11
10
" 7
HONEYCOMBS
sonds
• SOl/d'!0
PbCI;ïL.\\:::J-=
_ _-.-_ _ _-'
Sol/ds
.,osl. disposai
(
Slrlpplng
og.nl ...--_ _----'L-_ _- - - ,
,..cycl.
CBAPTD 51 CO_CLU.IO_.
...,1
q(25) q(lOO)
( Where
rOt - the reduced activity coefficient of a cation-
.. 115
l
anion pair in a solution contains only 1 pair of ions.
(29)
PUblication 1988.
1
122
.
125
Chemistry, Vol. 42(1970), No. 8, pp. 867-871.