Recovery of Molybdenum from Spent Acid by Ammonia Gas Neutralization

Jong-Jin Pak
1;
*
, Jong-Oh Jo
2
, Chul-Hwan Park
2
, Jin-Goo Kang
2
and Dong-Hyuk Shin
1
Department of Metallurgical and Materials Eng., Hanyang University, Ansan 426-791, Korea
1
Professor, Department of Metallurgical and Materials Eng., Hanyang University, Ansan 426-791, Korea
2
Graduate Student, Department of Metallurgical and Materials Eng., Hanyang University, Ansan 426-791, Korea
The present work reports the commercialization of a recycling process of spent acid to recover molybdenum. The process consists of
ammonia gas neutralization of spent acid containing molybdenum, crystallization and ltration of ammonium molybdate, roasting and hydrogen
reduction of molybdic oxide to produce a commercial grade molybdenum metal powder. The mother liquor, highly nitrogeneous residual
solution after the ltration of ammonium molybdate, can be utilized to produce chemical fertilizers.
[doi:10.2320/matertrans.MER2007193]
(Received August 7, 2007; Accepted November 7, 2007; Published December 12, 2007)
Keywords: spent acid, molybdenum, ammonia neutralization, ammonium molybdate, chemical fertilizer
1. Introduction
In manufacturing tungsten lament coils at lamp indus-
tries, a very ne tungsten wire is coiled around molybdenum
mandrel wire/rods to form so-called a coiled coil. The
formed coiled coil is then heat-treated and cut to a size, and
immersed in a solution of mixed nitric acid and sulfuric acid
which dissolves the molybdenum mandrel leaving the coiled
coil tungsten as shown in Fig. 1. Such operation results in the
generation of large volumes of spent acid containing H
2
SO
4
,
HNO
3
and dissolved molybdenum. Molybdenum is usually
dissolved in amount of 8090 g/L of spent acid solution. The
volume of spent acid generated from a typical coil manu-
facturing company in Korea ranges from 300 to 600 liters
(containing 25 to 50 kg molybdenum) per day.
In the past, it was a common practice in these companies to
neutralize the spent acid with sodium hydroxide and
discharge it into waste water system. The loss of molybde-
num in this manner is economically signicant, and the
discharge of nitrate and sulfate ions and heavy metals like
molybdenum into the nations rivers is undesirable from the
environmental view. Furthermore, this disposal method
became illegal by the environmental protection law enforced
in Korea since 2003.
In the present work, the molybdenum recovery process
using ammonia gas neutralization
1,2)
was implemented and
improved by pursuing a way of utilizing the mother liquor as
a chemical fertilizer. The new process used a high acid/water
ratio for high eciency of molybdenum recovery, and also
for high total nitrogen content as ammonium and nitrate ions
in neutralized acid solution. The ammonium molybdate was
roasted to produce molybdic oxide, MoO
3
, and it was
reduced by hydrogen to produce a commercial grade
molybdenum metal powder. The mother liquor was analyzed
and tested for chemical fertilizers after mixing with some
additives to meet the specications.
3)
2. Experimental Procedures
2.1 Reactor and raw materials
A schematic of Mo recovery process from spent acid are
shown in Fig. 2. The 10 L capacity reactor was provided with
a cooling-heating jacket which is connected to a cooling or
heating water system, a motor driven impeller, the ammonia
gas inlet valve, and a drain system connected to a centrifuge
hydroextractor. The ammonia gas was supplied from a 50 kg
capacity tank of liquid anhydrous ammonia with an evapo-
rator. The o-gas outlet valve was connected to a water
scrubber.
A local lamp industry uses the mixed nitric acid-sulfuric
acid aqueous solution (HNO
3
: H
2
SO
4
: H
2
O = 1 : 0:6 : 0:8)
to dissolve molybdenum mandrels from coiled tungsten
laments as following reactions;
2HNO
3
() Mo(s) = MoO
3
(s) 2NO(g) H
2
O() (1)
MoO
3
(s) 2H
2
SO
4
() = MoO
2
(HSO
4
)
2
() H
2
O() (2)
The spent acid thus obtained contains about 19 mass%
HNO
3
and 32 mass% H
2
SO
4
and 100 g/L Mo. The specic
gravity of spent acid is about 1.4.
2.2 Ammonia neutralization
Figure 3 shows the procedure of molybdenum recovery
from the spent acid by ammonia neutralization. The spent
acid/water volume ratio in a 6 L mixed solution was varied
from 1/3 to 1/0. After predetermined volumes of water and
acid were mixed in the reactor, anhydrous ammonia was
introduced into the solution at a rate of 10 NL/min via
nozzles immersed near the bottom of the reactor. The
impeller was turned on at a rate of 300 rpm to insure
homogeneous mixing. The reaction was strongly exothermic
and the solution temperature increased to above 90

C in the
middle of neutralization process. As the acid/water volume
ratio increased, the time to reach the temperature above 90

C
decreased and the circulation of the cooling water through the
reactor jacket was required to avoid solution boiling. The
aimed solution pH was in the range of 2:53:0 in the present
work.
*
Corresponding author, E-mail: jjpark@hanyang.ac.kr
Materials Transactions, Vol. 49, No. 1 (2008) pp. 202 to 207
#2008 The Japan Institute of Metals EXPRESS REGULAR ARTICLE
2.3 Precipitation
After the partial neutralization, the ammonia supply was
shut o and the solution temperature was maintained at
above 90

C at least for 2 hours by circulating hot water

through the reactor jacket. During this precipitation process,
the agitation of the solution was continued with the impeller
at a rate of 300 rpm. After precipitation, the solution was
drained to a centrifuge hydroextractor to collect all ammo-
nium molybdate crystals precipitated. The mother liquor after
the ltration of ammonium molybdate precipitates was stored
in a separate tank for other use.
2.4 Roasting
The ammonium molybdate separated from the neutralized
solution was dried at 120

C and roasted in the air at 500

C to
obtain MoO
3
powder. The ammonia o-gas from the roasting
process was treated in a water scrubber.
2.5 Hydrogen reduction
Two stages of hydrogen reduction of MoO
3
to Mo were
carried out in a batch-type reduction furnace. The rst stage
reduction of MoO
3
to MoO
2
was carried out at 600

C in
hydrogen atmosphere for 2 hours. The second stage reduction
of MoO
2
to Mo was carried out at 9301000

C for 8 to 14
hours depending on Mo powder sizes to be obtained.
Fig. 2 Mo recovery process from spent acid.
Fig. 3 A ow sheet for Mo recovery from spent acid.
(a) (b)
Fig. 1 Tungsten coil on Mo mandrels. a) Before Mo dissolution b) After Mo dissolution
Recovery of Molybdenum from Spent Acid by Ammonia Gas Neutralization 203
2.6 Analysis of Mo products
The molybdenum products obtained by the preceding
processes were analyzed by X-ray diraction (XRD) analysis
for the phase identication, scanning electron microscopy
(SEM) for the particle sizes and morphologies and a laser
granulometer (Malvern Co., Master Sizer) for the particle
size distribution. Thermo-gravimetric (TG) analyses were
also carried out to check the conditions of roasting of
ammonium molybdate and hydrogen reduction of MoO
3
to
produce Mo powder.
2.7 Mother liquor
The mother liquor, the residual solution after the ltration
of crystallized ammonium molybdate, was analyzed for total
nitrogen as ammonia and nitrate ions, water-soluble metallic
elements (Mo, Fe) and harmful elements (Arsenic, Thiocya-
nate, Nitrous acid, Buret-N, Sulfamic acid). Some water-
soluble elements were mixed with mother liquor to meet the
specication for chemical fertilizers.
3. Results and Discussion
Figure 4 shows the variation of pH of spent acid/water
mixed solutions during the course of ammonia neutralization
as a function of dilute ratio. During the process, the solution
samples were taken for the pH measurement of partially
neutralized acid solution. After the pH measurements, the
sample solutions were held for 24 hours at room temperature
for the precipitation of ammonium molybdate. The ammo-
nium molybdate precipitates can have dierent chemical
formulas depending on pH values of partially neutralized
acid solution.
4,5)
Therefore, the Mo recovery ratio was
determined from the residual Mo content in the mother
liquor of each solution sample after the ltration of
Fig. 4 Variations of the pH of spent acid during NH
3
injection.
Fig. 5 Variation of Mo recovery with pH values of partially neutralized
acid solution.
Fig. 6 Ammonium molybdate crystals precipitated in partially neutralized solutions of dierent pH values.
204 J.-J. Pak, J.-O. Jo, C.-H. Park, J.-G. Kang and D.-H. Shin
ammonium molybdate precipitates. The Mo recovery ra-
tio(R) was calculated by following equation.
R(%) = ([Mo]
o
[Mo]
f
)=[Mo]
o
100 (3)
where [Mo]
o
is the initial Mo content in a spent acid/water
mixed solution and [Mo]
f
is the Mo content in the mother
liquor after the ltration of ammonium molybdate precip-
itates.
Figure 5 shows the variation of Mo recovery ratio with pH
values of partially neutralized acid solution by ammonia. The
highest Mo recovery ratio of above 99% was obtained at the
pH values of 2:53:0. In Fig. 6, it can be seen that
ammonium molybdate crystals precipitated at this pH range
are highly crystalline. However, at the higher pH values, the
crystals looked like dissolved again in the solution.
After the neutralization of spent acid by ammonia to the
pH value of 2:53:0, the ammonia supply was shut o, and
the solution was agitated with the impeller at a rate of
300 rpm. Figure 7 shows the eect of temperature on the Mo
recovery ratio during the precipitation process. At a solution
temperature of 90

C, the precipitation of ammonium mo-

lybdate was completed over 99% within an hour. However, at
room temperature, the Mo recovery ratio reached only about
60% after 2 hours. Therefore, the optimum precipitation
condition was determined as; the solution temperature of
above 90

C and the agitation by an impeller for 2 hours. The

solution temperature can be maintained above 90

C by
circulating hot water through the reactor jacket. After
precipitation, the solution was drained to a centrifuge
hydroextractor to collect all ammonium molybdate crystals
precipitated. Figure 8 shows XRD data and SEM image of
ammonium molybdate crystals. The crystals were identied
as ammonium tetramolybdate (4MoO
3
2NH
3
H
2
O) by XRD
analysis. Figure 9 shows the particle size distributions of
ammonium molybdates obtained at dierent dilute ratios of
acid/water mixed solutions. The acid/water ratio of 1/1
showed the most uniform size distribution. The average
particle size was about 100 mm.
The TG analysis indicated that ammonium tetramolyb-
date decomposed NH
3
and H
2
O to form MoO
3
at above
450

C. The weight change corresponded to the decompo-

sition of NH
3
and H
2
O from 4MoO
3
2NH
3
H
2
O. The
powder obtained in the TG analysis was conrmed as MoO
3
by XRD analysis. Figure 10 shows a change of the weight
loss of MoO
3
during the TG analysis under H
2
atmosphere.
About 50 mg of MoO
3
powder was heated up to 1000

C
with a heating rate of 10

C/min under a hydrogen ow

0 20 40 60 80 100 120
0
20
40
60
80
100
Run 1
Run 4
1:1 dilute, 10L stainless reactor
90C
25C
R
e
c
o
v
r
y

(
%
)
Time(min)
Fig. 7 The eect of temperature on Mo recovery during the precipitation
period.
10 20 30 40 50 60
0
100
200
300
400
500
600
. .
H
2
O 2NH
3
4MoO
3
I
n
t
e
n
s
i
t
y
2
(a)
(b)
Fig. 8 Identication of ammonium molybdate. a) XRD data b) SEM image
Fig. 9 Particle size distribution of ammonium molybdate product.
Recovery of Molybdenum from Spent Acid by Ammonia Gas Neutralization 205
rate of 100 mL/min. The weight loss was increased rapidly
at temperatures above 500

C, and it reached to a constant

value of 37% at above 750

C. The theoretical weight loss of

oxygen due to the reduction of MoO
3
to Mo is 33.3%.
Some extra weight loss of 3% may be attributed to the
initial water content and vaporization of MoO
3
during
heating.
In commercial processes for the reduction of MoO
3
to
Mo,
6,7)
two stage reduction method of MoO
3
MoO
2

Mo is generally used because MoO
3
shows a relatively high
vapor pressure at a temperature above 650

C. The reaction
between Mo oxides with hydrogen may be expressed by
following reactions;
8)
MoO
3
(s) H
2
(g) = MoO
2
(s) H
2
O(g) (4)
Log K
(4)
= 4469:7=T 1:27
MoO
2
(s) 2H
2
(g) = Mo(s) 2H
2
O(g) (5)
Log K
(5)
= 4363:9=T 2:87
where Ks are the equilibrium constants of above reactions
and T is the temperature in Kelvin.
The reaction (4) is exothermic and thermodynamically
favorable at the temperature range of 550600

C. The
reaction (5) is endothermic, and relatively a high temperature
and H
2
/H
2
O ratio greater that 2 are required to proceed the
hydrogen reduction of MoO
2
. The temperature for second
stage reduction was varied from 930 to 1000

C depending on
the Mo powder size to be obtained. As the reduction
temperature decreased, the size of reduced Mo powder
decreased. However, at a lower reduction temperature, a
longer reduction time was required for the completion of Mo
reduction. Figure 11 shows XRD data and SEM image for the
morphology Mo powder obtained by hydrogen reduction at
950

C. The reduced Mo grains had the spherical shape and

uniform particle size range under 5 mm.
The residual solution after the ltration of crystallized
ammonium molybdate contained high total nitrogen. Typi-
cally, it contained about 8.1 mass% of total nitrogen when the
acid/water ratio of 1/1 was used in the ammonia neutraliza-
tion process. About 0.016 mass% of water-soluble Mo was
also present in mother liquor. According to the bulletin of the
Rural Development Administration of the Korean Ministry of
Agriculture and Forestry,
3)
chemical fertilizers can be
synthesized by adding about 2 mass% of water-soluble
phosphoric acid and/or water-soluble potassium in this
solution as shown in Table 1. Other useful water-soluble
elements such as Cu, B, Zn and Fe can be added depending
on the specications. Harmful elements such as Arsenic,
Thiocyanate, Nitrous acid, Biuret-N and Sulfamic acid were
not present in the mother liquor obtained in the present work.
4. Conclusions
In the present work, the molybdenum recovery process
using ammonia gas neutralization of spent acid was tested
and successfully implemented by producing a commercial
grade molybdenum metal powder and utilizing the mother
liquor as a fertilizer. The new process used a high acid/water
ratio for a high eciency of molybdenum recovery and also
for high total nitrogen content in mother liquor. The
ammonium molybdate obtained from the spent acid was
roasted, and reduced by hydrogen to produce molybdenum
metal powder of spherical shape and uniform sizes under
5 mm. The mother liquor after the ltration of ammonium
molybdate contained high total nitrogen, and it was utilized
to produce chemical fertilizers.
0 200 400 600 800 1000
0
5
10
15
20
25
30
35
40
weight loss : 37%
MoO
3
Mo
W
e
i
g
h
t

l
o
s
s

(
%
)
Temperature (C)
Fig. 10 Weight loss of MoO
3
during TG analysis under H
2
atmosphere.
20 30 40 50 60 70 80 90
0
1000
2000
3000
4000
5000
6000
7000
Mo
I
n
t
e
n
s
i
t
y
2
(a)
(b)
Fig. 11 Mo powder obtained by H
2
reduction of MoO
2
. a) XRD data b)
SEM image of Mo powder
206 J.-J. Pak, J.-O. Jo, C.-H. Park, J.-G. Kang and D.-H. Shin
Acknowledgement
This work was nancially supported by the Resource
Recycling R&D Center (Grant No.: 2C-B-2-1).
REFERENCES
1) A. D. Kulkarni: Molybdenum Recovery from Spent Acid Solution
(U.S. Patent 3,963,823, 15 June 1976).
2) H. R. Heytmeijer: Rapid and Ecient Recovery of Molybdenum from
Spent Mandrel Dissolving Acid Solution (U.S. Patent 4,307,065, 22
December 1981).
3) The bulletin of the Rural Development Administration, Notication
No. 1996-6, The Korean Ministry of Agriculture and Forestry,
December 1996, 146147.
4) G. P. Haight and D. R. Boston: Journal of Less-Common Metals 36
(1974) 95102.
5) C. J. Hallada: Journal of Less-Common Metals 36 (1974) 10310.
6) W. V. Schulmeyer and H. M. Ortner: Journal of Refractory Metals &
Hard Materials, 20 (2002) 261269.
7) R. F. Rennie: Continuous Reduction of Molybdenum Compounds,
(U.S. Patent 2,402,084, 11 June 1946).
8) E. T. Turkdogan: Physical Chemistry of High Temperature Technology,
(New York, Academic Press 1980).
Table 1 Specication of chemical fertilizers and analysis of mother liquor.
Items Specication Mother Liquor
Basic Components
Total N, water-soluble phosphoric acid and
(Minimum 2)
water-soluble potassium totals more than Total N: 8.1%
10%
Water-soluble Elements Mo: 0.0005%, Fe: 0.1%, Ca: 1.0%,
Mo: 0.016%
(Minimum 2) Mg: 1.0%, Zn: 0.05%, B: 0.05%
Harmful Elements Thiocyanate: 0.005%, Arsenic: 0.004%,
(Per 1% Basic Nitrous acid: 0.02%, Biuret-N: 0.01%, Not present
Components) Sulfamic acid: 0.005%
Recovery of Molybdenum from Spent Acid by Ammonia Gas Neutralization 207