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A COMPLETELY RECYCLING OF METALS FROM SPENT Co/Mo/Al2O3 CATALYST

Meng Yun a, Wang Ben b, Li Zengxin a


Chemistry Department of Normal College, Qingdao University, Qingdao 266071, China School of chemical engineering, Qingdao University of Science and Technology, Qingdao 266042, China
a

Abstract: A completely metals recovery process has been developed for spent Co/Mo/Al2O3 catalyst used in industry. The process started with a regeneration of the catalyst to eliminate carbon and sulfur. After a caustic roasting, the material was leached by concentrated ammonia to obtain a solution containing mainly molybdenum, and a solid containing essentially alumina, cobalt. The solution was treated with nitric acid and concentrated ammonia to obtain high purity Ammonium molybdate. The solid was continually dissolved by sulphuric acid. Aluminium was recovered by directly crystallized with ammonium sulfate to form ammonium alum. Cobalt was converted into complex ion by excess ammonia and then recovered as high purity metal cobalt powder by replaced with zinc powder. The yield recovery for molybdenum, aluminum and alcobalt are over 90%, 85% and 90%, respectively. The process is simple and feasible and can yield good economic returns. Keywords: Spent Co/Mo/Al2O3 catalyst; Recycle; Molybdenum; Cobalt; Aluminium

1.

Introduction The hazardous nature of the spent catalysts is attracting the attention of environmental authorities in many countries and the refiners are experiencing pressures from environmental authorities for safe handling of spent catalysts. Several alternative methods such as disposal in landfills, reclamation of metals, regeneration/rejuvenation and reuse, and utilization as raw materials to produce other useful products are available to the refiners to deal with the spent catalyst problem[1-2]. The choice between these options depends on technical feasibility and economic considerations. This present study is exploring the possibilities for recovering metals completely from spent Co/Mo/ Al2O3 catalysts. The process started with a regeneration of the catalyst to eliminate hydrocarbons, carbon and sulfur. After a caustic roasting, the material was leached by concentrated ammonia to obtain a solution containing mainly molybdenum, and a solid containing essentially alumina, cobalt. The solution was treated with nitric acid and concentrated ammonia to obtain high purity Ammonium molybdate. The solid was continually dissolved by sulphuric acid. Aluminium was recovered by directly crystallized with ammonium sulfate to form ammonium alum. Cobalt was converted into complex ion by excess ammonia and then recovered as high purity metal cobalt powder by replaced with zinc powder. 2. Experimental procedure

2.1 Materials and Apparatus The spent Co/Mo/Al2O3 catalysts (B301) was obtained from the atmospheric residue hydrodesulfurization working procedure of Qilu Petroleum Company. For consistency, the spent catalyst for all the experimentation was collected from one batch. The sample was in the form of a black dust coated pellet. The chemical analysis of the catalyst is shown in Table 1.
Table 1 Chemical analysis of contaminants from Co/Mo/Al2O3 catalyst Contaminant properties Carbon (wt.%) Sulfur (wt.%) Vanadium (wt.%) Cobalt (wt.%) Molybdenum (wt.%) Aluminum (wt.%) Iron (wt.%) Fresh 2.90 9.35 Spent 18.00 6.8 4.80 3.35 9.20 34.50 0.25 After roasting 0.35 0.25 3.86 9.95 35.00 0.23

All other chemicals were of analytical grade. The major equipments were high temperature box electric stove and SO2 absorption tower. 2.2 Experimental process The recycling process described in Fig.1 has been designed for a complete recycling of metals.
Spent catalyst Roasting Crushing and screening Concentrated ammonia leaching Filtering Replacing Dissolving SO2 absorption tower

Zn powder

Filter liquor Filtering

Filter cake Filtering

Sulfuric acid

Filter liquor Nitric acid MoO3 Ammonia

Co powder

Filter liquor Ammonia+ Sulfuric acid Crystallizing Filtering

Residue

Ammonium molybdate

Ammonium Alum Filter liquor Filtering

Neutralizing

Ammonia

Removing Fe,Al

Ammonia Complex Replacing Co powder

Zn powder

Fig. 1. Flow scheme of the recycling process of spent catalysts.

3.

Results and discussion

3.1 Roasting experiment Powder XRD analysis of the spent Co/Mo/Al2O3 catalyst after roasting is shown in Fig.2. From the results, one can see that the main phase of this spent catalyst after roasting was well crystallized Al2O3. CoMoO3 compound was also detected. This high level of carbon and sulfur could be effectively removed by roasting at 500 for 4~12h with opening to atmosphere to provide mixed oxides formation. After the roasting experiment, the presence of vanadium was found to be negligible. This result may be due to the low melting point of vanadium oxide[3]. The chemical reaction during roasting of spent sulfided Co/Mo/Al2O3 catalyst can be summarized as follows:
1 MoS 2 ( s ) + 3 O2 ( g ) MoO3 ( s ) + 2 SO2 ( g ) 2
1 CoS 2 ( s ) + 2 O2 ( g ) CoO ( s ) + 2 SO2 ( g ) 2

(1) (2)

At atmospheric pressure, MoO3 starts volatilizing at 893K[4]. So the roasting temperature must be maintained below 893K in order to avoid the volatilization of Mo. 3.2 Effect of spent catalyst particle size The influence of spent catalyst particle size was studied using the particle size range (as received, >2000m, 850m ~2000m, <500 m). Fig.3 represents the effect of the particle size of the spent catalyst on the percentage conversion of molybdenum. The data show that as the particle size decreases to <500m, maximum conversions of molybdenum were obtained.
100 80

% conversion of Mo

60

40

20

received

>2000

850-2000

<500

Particle size of spent catalyst in micron

Fig. 2. Powder X-ray diffraction analysis results of spent Co/Mo/Al2O3 catalyst after roasting.

Fig. 3. Effect of particle size on the percentage of Mo conversion.

3.3 The recovery of Mo Molybdenum may be dissolved in an alkaline solution, but the oxide of cobalt can hardly dissolved in an alkaline solution[5].Based on this information and a leaching process can be employed to recovery molybdenum from spent catalyst. After leaching with concentrated ammonia, Ammonium molybdate can be obtained. Then adjust the pH value to be about 1.5~2.0 by adding HNO3, molybdic acid can be obtained. The reaction formula is as follows:
MoO3 + 2 NH 3 H 2 O ( NH 4 ) 2 MoO4 + H 2 O

(3)

( NH 4 ) 2 MoO 4 + 2 HNO3 + H 2 O H 2 MoO 4 + H 2 O + 2 NH 4 NO3

(4)

The effect of 18% ammonia: Mo% in spent catalyst ratio and leaching time on percentage recovery of molybdenum was studied at the temperature of 50 ~60 . The 18% ammonia: Mo% in spent catalyst ratio varied from 1 to 26 and the leaching time varied from 0 to 6 hours and the results obtained are illustrated in Fig.4 and Fig.5.
100
100 80

% conversion of Mo

80

% conversion of Mo

60

60

40

40

20

20 2 4 6 8 10 12 14 16 18 20 22 24

Time / h

18% Ammonia:Mo% in spent catalyst

Fig.4. The effects of concentrated ammonia: catalyst ratio on Mo recovery

Fig.5. The effect of leaching time on the recovery of molybdenum

Fig.4 reveals that at 18%ammonia: Mo% in spent catalyst ratio 20: 1, molybdenum recovery reaches 92%. Further increase in 18% ammonia content produces on appreciable variation in molybdenum recovery. Thus, Mo% in spent catalys: concentrated ammonia ratio 1:20 is considered to be the optimum. Fig. 5 illustrates the significant effect of leaching time on the recovery of molybdenum. Prolonging the contact time is accompanied by a noticreable increase in the metal removal which means that molybdenum recovery is a rate process depending on the time of the reaction. For more than 5h, 91% conversion was achieved. 3.4 The treatment of filter cake After extracting Mo, the filter cake mainly contains Al2O3 and CoO. In order to extract Al and Co, 98% H2SO4 was added into filter cake, and the reaction is very intense, the temperature will elevate quickly. The main reactions are as follows: The main reactions during this process are:
Al2 O3 + 3H 2 SO4 Al2 ( SO4 ) 3 + 3H 2 O
CoO + H 2 SO4 CoSO4 + H 2 O

(5) (6)

The filter cake contains a small quantity of Fe. The reaction is as follow:
Fe2 O3 + 3H 2 SO4 Fe2 ( SO4 ) 3 + 3H 2 O

(7)

3.4.1 The recovery of metal Al The solution after dissolving H2SO4l is diluted until the content of Al2(SO4)3 is about 30%.

Because Al2(SO4)3 can react with (NH4)2SO4 to Ammonia alum crystal and CoSO4 still remain in the solution, most Al can be removed. The reaction is as follow:
Al 2 ( SO4 ) 3 + ( NH 4 ) 2 SO4 + 24 H 2 O ( NH 4 ) 2 SO4 Al 2 ( SO4 ) 3 24 H 2 O

(8)

Adds ammonia and (NH4)2SO4 quantificationally in the certain proportion to the solution, warm up temperature to 80 ~90 , then each 30min stirs for 1~2min, until it is refrigerated to room temperature, then there has a great deal of colorless transparent Ammonia alum crystal. Usually for spent Co/Mo/Al2O3catalyst recycling only Co, Mo were recycled, but Al was processes as residue. Al was recycled as Ammonia alum in this process ,which can greatly enhances the economic efficiency. 3.4.2 The recovery of Co powder Because in the solution a great deal of Al2(SO4)3 is recycled as Ammonia alum, a Ammonia alum molecule has 24 crystal water, which causes CoSO4 solution volume reduce greatly, and plays the role to concentrate Co, thus greatly enhanced the Co recycling ratio. Adds 18% ammonia water to the concentrated solution, with unceasingly stir adjusts the pH value to 6.0~6.5, removes a little residual Al and Fe impurity in the solution by filtering. Continues to add excess 18% ammonia until it produces the red cobalt ammonia complex. Then at room temperature, with unceasingly stir, scatters Zn powder(200 meshes) to the solution until the solution color vanish to make Co replace completely. After filtering and drying, Co powder is obtained. The main equations of this process are:
2+ Co 2+ + 6 NH 3 Co( NH 3 ) 6 2+ + 2Co( NH 3 ) 6 + Zn 2Co + 3Zn( NH 3 ) 2 4

(9) (10)

Analysis of economic and environment efficiency The waste liquid produced by the process contains NH4NO3 (NH4)2SO4 and some trace element, for example Mo, Zn, Al, etal. The waste liquid can be used as fertilizer in the agricultural production, which does not produce contamination. Only SO2 which produces in the oxidizing roasting spent catalyst can pollute the environment if it does not be disposed. We use NaCO3 to reversion absorption in the absorption tower to produce NaHSO3, so eliminated the pollution. Dispose 1000 tons spent catalyst, economic efficiency was shown at table 2:
Table 2 Economic efficiency analysis of the complete recycling metals method from Spend Co/Mo/Al2O3 catalyst substance amounts(t) price(ten thousand RMB/t) recovery Co powder Ammonium molybdate 2.6 17 30~40 6 78~104 102 226.5~252.5 income(ten thousand RMB) expand(ten thousand RMB) total(ten thousand RMB)

4.

Ammonia alum cost Spent catalyst 18% Ammonia Nitric acid Zn powder Sulfuric acid Other net profit

465 100 500 150 3 60

0.1 0.1 0.08 0.2 2 0.12

46.5 10 40 30 6 7.2 50 83.3~109.3 143.2

Conclusions A completely metals recovery process has been developed for spent Co/Mo/ Al2O3 catalyst used in industry for hydrodesulfurization. The yield recovery for molybdenum, ammonium and alcobalt are over 90%, 85% and 90%, respectively. The strength of the process lies in the sensible combination of conventional regeneration, roasting, pyrometallurgical, hydrometallurgical techniques and innovative metal replacement and crystallizaion technology. Reference
[1] [2] [3] [4] [5] [6] Chang T., 1998. J. Oil Gas 9, 7984. Trimm D.L., 2001. Appl. Catal. A: Gen 212, 153160. Trimm T.L., Akashah S., Absi-Halabi M., Bishara A. (Eds.), 1989. Proceedings of the Conference on Catalysts in Petroleum Refining, Kuwait, 58 March Elsevier, Amsterdam, pp. 4160. Sutulov A., 1976. Molybdenum and Rhenium: 17781977. Conception Pub., Chile. Cotton F.A., Wilkinson G., 1972. Advanced Inorganic Chemistry, 3rd Edition, Wiley, NY. Sun D. D., Tay J. H., Cheong H. K., Leung D. L. K., G.R. Qian, 2001. Recovery of heavy metals and stabilization of spent hydrotreating catalyst using a glassceramic matrix, Journal of Hazardous Materials B87, 213223.

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