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De-oiling: Acetone wash was given to catalyst for oil removal. 50gm of catalyst was washed with
80ml acetone and dried in room temperature. From the de-oiling oil and soft coke is removed from
the catalyst surface.
Crushing and Screening: Extrudates of catalyst were taken in motor pestal for crushing. After
crushing, it was passed through the sieve with mesh no 40 (420 m) to get uniform particle size.
Figure 4.1 shows the powder form of catalyst.
These are two TGA (Thermo gravimetric analysis) curves. These curves show the weight loss with
temperature. (Figure 4.2)
During the decoking carbon and sulphur content were removed, so that weight of catalyst was
decreases with time. Table 4.2 shows the weight loss of catalyst (extrudate and powder form)
during the different temperature for 3hr and 5hr.Table 4.2 shows the weight loss of extrudate and
powder form of catalyst when the temperature range 500C to 800C.
In leaching process take 1gm catalyst powder was contacted 100ml acid solution (10%
concentration) of HCl, H2SO4 and HNO3. Leaching experiments were conducted in a 250 ml flask
fitted with a seal to avoid evaporation loss. The contents were stirred with a magnetic stirrer at 30
C. Take samples regular time interval for to determine concentration of metals in leachate with
time for 4 hr.
The different acidic leaching is shows below. (Figure 4.4)
In leaching process. After the leaching process leachate and insoluble residue were separated. The
insoluble from the 1st stage of leaching dried and weight and again contacted with fresh acid
solution for the 2nd leaching process. Table 4.4 shows the concentration of W, Si and Al in HCl,
H2SO4 and HNO3 in 1st stage leaching.
Acids W Si Al Ni
(ppm) (ppm) (ppm) (ppm)
HCl 68.04 10.69 627.24 23.70
H2SO4 210.84 9.49 365.59 64
HNO3 385.37 10.71 429.49 42
Figure 4.5 shows the metal concentration of W, Si and Al in various acids in leachate.
Metal composition in leachate(1st stage)
HCl H2SO4 HNO3
627.235
429.488
385.373 365.585
210.837
68.043 64 23.7 42
10.6899.48810.706
W Si Al Ni
Fig. 4.5: Metal composition in acidic leachate (1st stage)
Table 4.5 shows the weight of insoluble residue in different acids after 1st stage leaching.
Table 4.5 Insoluble residue of acidic leaching (1st stage)
Table 4.6 shows the concentration of W, Si and Al in acids during the 2nd stage leaching.
Table 4.6 Metal composition in acidic leaching (2nd stage)
Acids W Si Al
(ppm) (ppm) (ppm)
HCl 3 6 105
H2SO4 11 10 510.6
HNO3 22 14 187.59
Figure 4.6 shows the metal concentration in acidic leachate in 2nd stage.
510.6
187.59
105
3 11 22 6 10 14
W Si Al
Figure 4.7 shows the weight of insoluble residue after the 1st and 2nd stage acidic leaching.
Insoluble Residue
0.8
0.679
0.7
0.573 HCl
0.6 0.524
0.5 0.447
0.4 0.336 H2SO4
0.3
0.2 0.15
HNO3
0.1
0
1st stage 2nd stage
Figure 4.8 shows the insoluble residue of HCl, H2SO4 and HNO3 after acidic leaching.
HCl Residue H2SO4 Residue HNO3 Residue
Na2CO3 FUSION
Catalyst powder was fusion with Na2CO3 the ratio of catalyst to Na2CO3 was 1:1.35 at 750 C
for 4hrs in the crucible. The fusion was occur only on surface. When the mixture was taken in the
ceramic boat, it was fused and forms hard solid. The mixture was fused on boat surface because
of silica which is present in it. (Figure 0.9)
Fig. 4.2: Fusion with Na2CO3
NaOH FUSION
The mass ratio of NaOH to catalyst powder was taken as 1.83:1. The mixture was placed in a
ceramic boat and heated in a furnace at 650 C (under access of air) for 2-4 h in muffle furnace.
Insoluble Residue
Alumina pH adjustment Ni
Recover by 2N HCl (9 pH) Si
y
Evaporation Nickel
Recovery
Tungsten recovery
Here 1gm of catalyst powder was taken and roasted with alkali for 2hr. Roasted powder was
contact with fresh 10ml water. Three water leaching stages were followed.
Table 4.8 shows the metal concentration in three stages of water leaching.
Figure 4.13 shows the metal concentration in water leachate in three stages.
Metal recovery
8000 7578
7000 6322.56
6000
5000
4000
3000 Tungsten
22512230
2000 Alumina
1000 595
170.94 70 90
0
1st 2nd 3rd Mixed leachate
Stage
Here 1gm of catalyst powder was taken and roasted with alkali for 4hr. Roasted powder was
contact with 10ml fresh water. Three water leaching stages were followed.
Table 4.10 shows the concentration of metal in three water leaching stages.
Table 4.4 Metal concentration in water leachate
Stage W Al
(ppm) (ppm)
1st 4890 2752
2nd 796 103
3rd 156 66
Figure 4.14 shows the metal concentration in three water leaching stages
Metal recovery
5000 4590
4500
4000
3500
2820
3000
2500
2000 Tungsten
1500 Alumina
1000 796
500 103 156 66
0
1st 2nd 3rd
Stage
Figure 4.15 shows the insoluble residue after three water leaching stages
Insoluble residue after water leaching
0.6
0.4
0.2
0
1st 2nd 3rd
2 hr 4 hr
When 2 gm of catalyst is roasted with alkali for 2 hr. Roasting powder was contact with 50ml
fresh water. Three water stages were applied.
Table 4.12 shows the metal concentration in water leachate in three water leaching stages.
Table 4.6 Metal concentration in water leachate
Metal concentration
8000
6000
4000
2000
0
1st 2nd 3rd Mixed leachate
W Al
Figure 4.17 shows the insoluble residue after three water leaching.
Insoluble Residue
3.5
3
2.5
2
1.5
1
0.5
0
1st 2nd 3rd
Insoluble Residue
Alumina pH adjustment
Recovery by 2N HCl (9 pH),
5M NH4OH add at 70 C
Evaporation
Tungsten recovery
After the three stages of water leaching, mix the all leachate for the extraction. For the alumina
recovery pH was maintained up to 9. The pH of water leachate was 11.98 (basic solution). So that
pH is adjust by adding 2N HCl solution. After the pH adjusted up to 9, leachate was heated up to
70 C. Then NH4OH was added to the leachate solution for alumina precipitation.
Figure 4.19 show the alumina precipitation during the pH adjustment in leachate.
Fig. 4.12: Alumina precipitations
Precipitation of alumina was removed by filtration or centrifuge. Precipitate was collected, dried
and weight. From the EDS analysis determine the concentration of alumina in precipitation.
Table 4.14 shows the metal concentration in leachate after precipitation. (Adding NH4OH)
pH W Al
(ppm) (ppm)
8 1599 4
9 1685 35
10 2107 256
2 1334 24
Figure 4.20 shows the W and Al concentration in leachate after precipitation
Metal concentration
3000
2000
1000
0
8 9 10 2
W Al
EXTRACTION
In extraction process 10% Aliquat 336 in kerosene was used as an extractant (Figure 4.23)
Table 4.16 shows the metal concentration during the 1st stage of extraction.
Extraction
30
28 28
26 26
25 Tungsten (1st satge)
24
22
1 2 3
For the 2nd stage of extraction, take an aqueous phase from the 1st stage leaching and aqueous phase
contact with the fresh extractant. Here the ratio of organic phase to aqueous phase was 1. Both
phases were contacted and shaking for the 20-30 min on shaker. Phases were separated by
separating funnel. Table 4.15 shows the metal concentration in 2nd stage of extraction.
Table 4.17 shows the metal concentration in aqueous phase after 2nd stage extraction.
Table 4.11 Metal concentration in extraction
STRIPPING
Organic phase and aqueous phase were separated from the extraction process. Organic phase was
contacted with 2M NH4OH, shake for 20 min on shaker. After stripping organic phase and aqueous
phase were separated by separating funnel.
Figure 4.26 shows the aqueous phase after the stripping process.
After the stripping, aqueous phase separated. When the solution is slowly evaporated, crystals form
in the solution. (Figure 4.27)
Time ppm
30 min 115
1 hr 107
2 hr 125
3 hr 118
4 hr 98
Figure 4.28 shows the Ni concentration in leachate with time.
Ni concentration in leachate
150
100
50
0
30 min 1 hr 2 hr 3 hr 4 hr
ppm
The total recycling process demonstrated its ability to reduce hazardous waste disposal to the zero
limit and save natural resources with economic benefits. The recovered metals such as Mo. V, Ni
and Co could be used in steel manufacture and the alumina could be used for the manufacture of
refractories, ceramics and abrasives.
Cemented tungsten carbides are currently used extensively in various industries, especially in
manufacturing industries where WC is used to make a variety of hard metals. Cemented tungsten
carbides are commonly used in the production of cutting tools for machining processes, wear
resistant parts, and similar industrial uses.
APT can be calcined under reducing conditions to form tungsten blue oxide, which is a mixture of
tungsten oxides and other constituents; calcined under oxidizing conditions to form tungsten
trioxide; decomposed by hydrochloric acid to form tungstic acid; or subjected to partial thermal
decomposition to form ammonium metatungstate. Tungsten blue oxide is the most commonly used
starting material to make tungsten metal powder which is used to make tungsten alloys, carbide
powder, and metal. Tungsten trioxide can be used to make tungsten metal powder and is also used
as a yellow pigment. Tungstic acid is used to make tungsten chemicals and ultrafine tungsten metal
and tungsten carbide powders. Ammonium metatungstate is used to make tungsten chemicals and
catalysts (Lassner and Schubert, 1999, p. 208-215).
CHAPTER 6
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