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#2008 The Japan Institute of Metals EXPRESS REGULAR ARTICLE
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
In manufacturing tungsten lament coils at lamp indus- 2.1 Reactor and raw materials
tries, a very ne tungsten wire is coiled around molybdenum A schematic of Mo recovery process from spent acid are
mandrel wire/rods to form so-called a coiled coil. The shown in Fig. 2. The 10 L capacity reactor was provided with
formed coiled coil is then heat-treated and cut to a size, and a cooling-heating jacket which is connected to a cooling or
immersed in a solution of mixed nitric acid and sulfuric acid heating water system, a motor driven impeller, the ammonia
which dissolves the molybdenum mandrel leaving the coiled gas inlet valve, and a drain system connected to a centrifuge
coil tungsten as shown in Fig. 1. Such operation results in the hydroextractor. The ammonia gas was supplied from a 50 kg
generation of large volumes of spent acid containing H2 SO4 , capacity tank of liquid anhydrous ammonia with an evapo-
HNO3 and dissolved molybdenum. Molybdenum is usually rator. The o-gas outlet valve was connected to a water
dissolved in amount of 8090 g/L of spent acid solution. The scrubber.
volume of spent acid generated from a typical coil manu- A local lamp industry uses the mixed nitric acid-sulfuric
facturing company in Korea ranges from 300 to 600 liters acid aqueous solution (HNO3 : H2 SO4 : H2 O 1 : 0:6 : 0:8)
(containing 25 to 50 kg molybdenum) per day. to dissolve molybdenum mandrels from coiled tungsten
In the past, it was a common practice in these companies to laments as following reactions;
neutralize the spent acid with sodium hydroxide and 2HNO3 Mo(s) MoO3 (s) 2NO(g) H2 O 1
discharge it into waste water system. The loss of molybde-
num in this manner is economically signicant, and the MoO3 (s) 2H2 SO4 MoO2 (HSO4 )2 H2 O 2
discharge of nitrate and sulfate ions and heavy metals like The spent acid thus obtained contains about 19 mass%
molybdenum into the nations rivers is undesirable from the HNO3 and 32 mass% H2 SO4 and 100 g/L Mo. The specic
environmental view. Furthermore, this disposal method gravity of spent acid is about 1.4.
became illegal by the environmental protection law enforced
in Korea since 2003. 2.2 Ammonia neutralization
In the present work, the molybdenum recovery process Figure 3 shows the procedure of molybdenum recovery
using ammonia gas neutralization1,2) was implemented and from the spent acid by ammonia neutralization. The spent
improved by pursuing a way of utilizing the mother liquor as acid/water volume ratio in a 6 L mixed solution was varied
a chemical fertilizer. The new process used a high acid/water from 1/3 to 1/0. After predetermined volumes of water and
ratio for high eciency of molybdenum recovery, and also acid were mixed in the reactor, anhydrous ammonia was
for high total nitrogen content as ammonium and nitrate ions introduced into the solution at a rate of 10 NL/min via
in neutralized acid solution. The ammonium molybdate was nozzles immersed near the bottom of the reactor. The
roasted to produce molybdic oxide, MoO3 , and it was impeller was turned on at a rate of 300 rpm to insure
reduced by hydrogen to produce a commercial grade homogeneous mixing. The reaction was strongly exothermic
molybdenum metal powder. The mother liquor was analyzed and the solution temperature increased to above 90 C in the
and tested for chemical fertilizers after mixing with some middle of neutralization process. As the acid/water volume
additives to meet the specications.3) 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
Recovery of Molybdenum from Spent Acid by Ammonia Gas Neutralization 203
(a) (b)
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 MoO3 powder. The ammonia o-gas from the roasting
process was treated in a water scrubber.
Fig. 6 Ammonium molybdate crystals precipitated in partially neutralized solutions of dierent pH values.
2.6 Analysis of Mo products soluble elements were mixed with mother liquor to meet the
The molybdenum products obtained by the preceding specication for chemical fertilizers.
processes were analyzed by X-ray diraction (XRD) analysis
for the phase identication, scanning electron microscopy 3. Results and Discussion
(SEM) for the particle sizes and morphologies and a laser
granulometer (Malvern Co., Master Sizer) for the particle Figure 4 shows the variation of pH of spent acid/water
size distribution. Thermo-gravimetric (TG) analyses were mixed solutions during the course of ammonia neutralization
also carried out to check the conditions of roasting of as a function of dilute ratio. During the process, the solution
ammonium molybdate and hydrogen reduction of MoO3 to samples were taken for the pH measurement of partially
produce Mo powder. neutralized acid solution. After the pH measurements, the
sample solutions were held for 24 hours at room temperature
2.7 Mother liquor for the precipitation of ammonium molybdate. The ammo-
The mother liquor, the residual solution after the ltration nium molybdate precipitates can have dierent chemical
of crystallized ammonium molybdate, was analyzed for total formulas depending on pH values of partially neutralized
nitrogen as ammonia and nitrate ions, water-soluble metallic acid solution.4,5) Therefore, the Mo recovery ratio was
elements (Mo, Fe) and harmful elements (Arsenic, Thiocya- determined from the residual Mo content in the mother
nate, Nitrous acid, Buret-N, Sulfamic acid). Some water- liquor of each solution sample after the ltration of
Recovery of Molybdenum from Spent Acid by Ammonia Gas Neutralization 205
100 (a)
Run 4 90C
600
60
400
25C
Run 1
Intensity
40 300
200
20
40 (a)
35 7000
30 Mo
Mo 6000
Weight loss (%)
25
weight loss : 37% 5000
20
15 4000
Intensity
10 MoO3 3000
5
2000
0