Philippine Associated Smelting and Refining Corporation

Isabel, Leyte

“A Feasibility Study for a Tellurium Recovery Facility of

PASAR’s Copper Refinery Plant”

Regina Zarahfe A. Cuizon

METP 7
February 2012

ABSTRACT
The paper studies the feasibility for a tellurium recovery facility in PASAR. The
tellurium (Te) metal will be recovered and purified from copper telluride (Cu2Te).
Through a careful evaluation and consideration of success-determinant factors
such as the cost, product conversion and production capacity, the design of the
facility has been considered as economically viable.

1
 TABLE OF CONTENTS
TITLE PAGE

I. Introduction --------------------- 1–4

A. Slimes Produced During Copper --------------------- 1-2

Refining
B. Current Process of PASAR --------------------- 2
C. Tellurium --------------------- 2–4
D. Design Objectives and --------------------- 4
Requirements

II. Proposed Plant Design --------------------- 5 – 14

A. Process Diagram --------------------- 5

B. Description of the Process --------------------- 5–8
C. Recycle Streams --------------------- 8
D. Overall Input – Output Diagram --------------------- 8
E. Basic Assumptions --------------------- 9 – 11
F. Process and Equipment Design --------------------- 12 - 14

III. Costing --------------------- 14

IV. Economic Feasibility Evaluation --------------------- 14 – 15

V. Conclusion and Recommendation --------------------- 16

VI. References -------------------- 17 – 19

VII. Appendices -------------------- 19

A. Mass Balance Calculations -------------------- A-1 – A-11

B. Heat Balance Calculations -------------------- B-1 – B-5
C. Mechanical Equipment Design -------------------- C-1 – C-49
D. Miscellaneous Design Calculations -------------------- D-1 – D-22
E. Economy -------------------- E-1 – E-14
F. Flow Process Chart -------------------- F-1 – F-4
G. Plant Lay-out -------------------- G-1

2
I. INTRODUCTION

The Philippine Associated Smelting and Refining Corporation (PASAR) is the only copper smelting and
refining plant in the Philippines. PASAR primarily produces electrolytic copper cathodes used in the
manufacture of various kinds of electric cables, telecommunication wires, copper shapes and copper-
based products. It also produces granulated slag used as a low-cost abrasive in sandblasting, iron
concentrates used as an additive in cement production, selenium powder used mainly for making
components of electrical equipment like photocopiers, lasers, and voltage regulators, sulfuric acid for
fertilizer production and the manufacture of industrial chemicals, doré metal and copper telluride
solids.

A. SLIMES PRODUCED DURING COPPER REFINING

During the electrolytic refining of copper, insoluble components, known as anode mud or
slimes, are produced. These anode slimes accumulate at the bottom of the electrolytic cells.
Despite being only a by-product in the production of copper, these slimes contain substantial
amounts of precious metals [1, 2, 3]. Table 1 shows the most probable forms in which these metals
are present in the slimes.

[5, 6, 7]
Table 1. Chemical Composition of Slimes
Gold Au, (Ag, Au)Te2
Silver Ag2Se, Ag2Te, CuAgSe, (Ag, Au)Te2AgCl, Ag
Pt-metal Metals
Copper Cu2S, Cu2Se, Cu2Te, CuAgSe, Cu2Cl2, Cu
Selenium Ag2Se, Cu2Se, CuAgSe, Se
Tellurium Ag2Te, Cu2Te, (Ag, Au)Te2, Te
Bismuth Bi2O3, BiAsO4
Ni NiO

The estimated amount of slimes produced in the Refinery, containing the precious metals, is
usually around 1% of the copper production. Thus, it is highly imperative that a slimes treatment
facility be installed in an electrolytic copper plant. Aside from recovering the precious metals
such as gold and silver, the extraction of selenium and tellurium from these slimes are also
given importance as the demand for these metals for modern technological applications has
increased.

B. CURRENT PROCESS OF PASAR

In PASAR, tellurium is recovered from the anode slimes in the form of copper telluride (Cu2Te).
The recovery of tellurium in the By-Products Plant is done after the slime decopperization or the
removal of copper from the slime through the addition of the purified electrolyte solution. The
decopperized slime, which contains CuSO4 and other elements such as the precious metals and
Se, and the filtrate are separated by means of a centrifuge. The tellurium compounds comes out
in the filtrate and passes through a plate and frame filter press for removal of the remaining
decopperized slime prior entering a reaction tank where it is added with copper grains to
cement out tellurium as copper telluride [18].

3
C. TELLURIUM
Tellurium (Te) is a brittle, silver-white, lustrous metalloid that looks similar to tin. It was
discovered in 1782 by the Hungarian mineralogist Franz-Joseph Muller von Reichenstein, but
was isolated and named in 1798 by the German chemist Martin Heinrich Klaproth after the Latin
word for earth, “Tellus” [8, 9]. Tellurium belongs to the Chalcogens, the 16th group in the periodic
table of elements. It possesses properties similar to that of sulphur and selenium. However, it is
less reactive, more basic, more metallic and shows strongly amphoteric behavior [6]. The
properties of tellurium are indicated in Table 2.

Table 2. Properties of Tellurium [8, 10, 11, 12]

Atomic Number 52
Atomic Weight 127.6
Atomic Volume (cm3/mol) 20.5
Oxidation States -2, +4, +6
Melting Point (°C) 449.5
Boiling Point (°C) 989.8
Electronic Configuration (Kr)4d105s25p4
Density @ 293K (g/cm3) 6.24
Color Silvery
Specific Heat Capacity (J/g-K) 0.20
Heat of Fusion (kJ/mol) 17.49
Heat of Vaporization (kJ/mol) 114.1
Heat of Atomization (kJ/mol) 197
Thermal Conductivity (W/m-K) 3.0
Electrical Conductivity (S/cm) 0.02 x 106

Tellurium is rarely found in its pure state. It is usually found as a compound in the ores of
bismuth, copper, gold, lead, mercury, nickel, silver and zinc [9]. The metal itself is even found to
be one of the rarest in the earth’s crust amounting to only 10 parts per billion, hence, mining
solely for its content is not justifiable. Nearly all of the tellurium produced today is a by-product
of the metals processing lines. Tellurium is chiefly produced from the anode slimes formed
during the electrolytic refining of copper [8, 13, 14, 15, 16, 17]. It is also formed during the refining of
other primary metals such as lead and zinc [6]. The major world producers of refined tellurium
are Canada, Japan, Peru, China and Russia [9, 13]. Among the industrial applications of this refined
tellurium are illustrated in Figure 1.
Free machining additives
5%
10% Catalysts, chemical uses

10% Nonferrous alloys

50%

25% Photoreceptors, thermoelectric

devices
Other uses

[12]
Figure 1. Uses of Tellurium

4
 D. DESIGN OBJECTIVES AND REQUIREMENTS
The objective of this study is to come up with an economic feasibility and a process design in the
recovery and purification of tellurium from copper telluride. It is required that the facility be
able to process 38,700 kg Cu2Te per year. The specific requirements needed to be able to carry
out this task are as follows:
• the process concepts including the types of materials, the operating conditions and the
mode of operation
• the type of reactors to be used with its mechanical design and the flowrates of the
incoming and outgoing streams of the system
• the desired product properties and the economics of the project

II. PROPOSED PLANT DESIGN

A. PROCESS DIAGRAM
The proposed flow diagram for the production of tellurium from copper telluride is shown in
Figure 2 below.

Copper telluride (Cu2Te)

Alkaline
Sodium hydroxide (NaOH) Leaching
O2 Figure 2.
Process Flow Diagram for the Production
of Tellurium from Copper Telluride and
Settling Processing of By-product

Filtration

Sulphuric acid (H2SO4) Acidification

Na2SO4 soln Evaporation-

Settling
Crystallization

Centrifugation Centrifugation

Re-dissolution Drying

Sodium hydroxide (NaOH) Electrowinning Na2SO4

solids

Te metal of
99.5% purity
5
B. DESCRIPTION OF THE PROCESS
As mentioned above, tellurium is recovered in the By-Products Plant as copper telluride. The
recovery and purification of tellurium from this compound mainly involves different processes
which will be further explained below. Considering that only 38,700 kg of copper telluride is to
be processed per year, a batch mode of operation will be adapted as this is the most suitable for
small scale operation and the pieces of equipment used are quite simple. Mass and energy
balances will be performed in order to define all the incoming and outgoing streams in the
plant.

B.1 Alkaline Leaching of Cu2Te Solids

Copper telluride (Cu2Te) solids, frequently referred to as cementation solids, produced from
the treatment of copper anode slimes is used as the raw material in the production of
tellurium (Te) metal. It is leached with 250 grams/liter or approximately 20% sodium
hydroxide (NaOH) solution [19] for about 2 hours under aerated conditions to selectively
dissolve tellurium according to the reaction:

2Cu2Te(s) + 4NaOH + 3O2
2Na2TeO3(aq) + 2Cu2O(s) + 2H2O

The process is done under 85°C and pH 11.5. The solids is approximately 15% of the entire
feed. It is assumed that 80% of the tellurium is extracted in order to give sodium tellurite
(Na2TeO3) in the solution [20].

B.2 Settling and Filtration

The copper (II) oxide (Cu2O) precipitate formed and the undissolved solids is then allowed to
settle for approximately 6-7 hours to separate it from the leach solution. It is assumed that
98% of the Cu2O precipitate and undissolved solids will settle at the bottom of the tank, and
this constitutes 90-95% of the total leach slurry.

On the other hand, filtration is being done to the solution in order to further remove the
precipitate and undissolved solids that have not settled and go with it. The filter cake is
assumed to contain about 10% leach solution. These separation techniques are employed in
order to ensure that only the sodium tellurite solution is processed with sulfuric acid (H2SO4)
during acidification. Both techniques are done at 25°C and 1 atm. The separation efficiency
of both techniques is based on the performance of the same techniques done during the
decopperization of copper anode slimes at the By-Products Plant.

B.3 Acidification
[20] [8]
The purified sodium tellurite solution from above is then acidified at 80°C to pH 5.6
according to this reaction:
Na2TeO3(aq) + H2SO4
TeO2(s) + Na2SO4 + H2O

Acidification is done to precipitate essentially 98% of the Te in Na2TeO3 as tellurium dioxide

(TeO2), thus, leaving a barren liquor [21].

6
 B.4 Settling and Centrifugation

The TeO2 precipitate is then recovered via settling and centrifugation. The TeO2 precipitate is
allowed to settle for about 6-7 hours at 25°C and 1 atm. The slurry is to contain about 90-95%
precipitate. It is assumed that this amount already represents 98% of the precipitate that is
formed. In order to recover all of the TeO2 precipitate, centrifugation is employed. During
centrifugation, the recovery is about 90% with the TeO2 cake containing about 10% liquor. The
rotational speed that is set is 1,100 revolutions per minute. All of the assumptions for these
techniques are based on the design and performance of the same techniques done and/or
equipment used during the decopperization of copper anode slimes at the By-Products Plant.

B.5 Re-dissolution

The TeO2 precipitate that is recovered is then re-dissolve in 250 grams/liter or approximately
20% sodium hydroxide (NaOH) solution [19] to produce the electrolyte solution according to
the reaction:
TeO2(s) + 2NaOH
Na2TeO3(aq) + H2O

In this process, it is assumed that all of the TeO2 precipitate is dissolved in caustic solution to
give the Na2TeO3 solution. This reaction is set to occur at 85°C [22].

B.6 Electrowinning

Tellurium is electrowon from such electrolyte, which is at 45°C, using stainless steel
electrodes. The cathodic current density and cell voltage set are 160 A/m2 and 2.5 V,
respectively. The expected current efficiency is 90% according to the process done by PRM
Refinery. The electrowinning process follows the reaction:

Na2TeO3(aq) + H2O
Te + 2NaOH + O2

According to the study of Sany, 2009, the Te metal that is expected to be produced in
this process is of 99.5% purity.

C. RECYCLE STREAMS AND BY-PRODUCT

In order to recover the unextracted Te from the leach slurry, filter cake and centrifuge filtrate,
recycle streams are also designed. The leach slurry and filter cake is fed back to the leaching
tank to get the approximately 20% Te that was not extracted in the previous batch. On the
other hand, the centrifuge filtrate of the 1st pass, which contains some TeO2 precipitate, is fed
back to the centrifuge, and the spent electrolyte solution is recirculated to extract some Te
metal in it. Meanwhile, the Na2SO4 solution is processed to obtain Na2SO4 solids, which can be
sold to the market like the paper, detergent, textile and glass manufacturing companies,
hence, giving an additional income to the company.

7
 D. OVERALL INPUT – OUTPUT DIAGRAM (MASS BALANCE)

The overall input-output diagram is given in Figure 3.

300 kg Cu2Te solids 75.23 kg Te metal

74.85 kg Te
40% Te = 120 kg Te
0.38 kg impurities
18% H2O = 54 kg H2O
13% Cu = 39 kg Cu
29% other metals = 111 kg other metals
(71.35 ppm Au, 629.9 ppm Ag)
Tellurium 76.18 kg Na2SO4 solids
Refining - 75.42 kg Na2SO4
- 0.76 kg H2O
1,746.93 kg NaOH Process
solution 1,632.92 kg H2O vapor

58.19 kg H2SO4
85.55 kg Na2SO4 filtrate
solution 8.39 kg Na2SO4 precipitate
77.16 kg H2O

1.15 kg Centrifuge Filtrate

1.13 kg TeO2 precipitate
0.02 kg Na2SO4 soln (liquor)
- 0.019 kg Na2SO4
154.74 kg Leach Slurry -0.001 kg H2O
7.74 kg Na2TeO3 soln
- 0.70 kg Na2TeO3
MASS IN: 2,105.12 kg - 7.04 kg H2O
147 kg Cu2O precipitate and
MASS OUT: 2,105.12 kg undissolved solids

3.63 kg Filter Cake

0.36 kg Na2TeO3 soln
- 0.03 kg Na2TeO3
- 0.33 kg H2O
3.27 kg Cu2O precipitate and undissolved solids

75.73 kg Spent Electrolyte Solution

14.45 kg Na2TeO3
61.28 kg H2O

Figure 3. Overall Input-Output Diagram for the Production of Tellurium from Copper Telluride and Processing of By-product (per Batch)

8
E. BASIC ASSUMPTIONS

E.1 Battery Limit

The battery limit for this plant is tabulated below.

Inside Battery Limit Outside Battery Limit

Leaching of Cu2Te solids, Acidification of Design of Washing Equipment of the Te Metal

Leach Solution, Re-dissolution of TeO2
precipitate and Electrowinning Design of Acid Mist Capture System

Separation and purification processes: Specification of crane and conveyor system

Settling, Filtration and Centrifugation
Wastewater treatment facility
Processing of Na2SO4 solution to obtain the
solids Product packaging and shipment

Design of the equipments: Specifications and design of bus bars, heat

• Leaching Tank exchangers, pumps, piping and specifications
• Acidification Tank of controllers, jackets, gaskets, flanges,
• Re-dissolution Tank compressor and insulations
• Electrowinning Cell
• Settling Tanks Identification of sampling points and design
• Nutsche Filter of inspection of methods
• Centrifuges
• Evaporator-Crystallizer
• Tray Dryer
• Storage Tanks of Raw and In-
process Materials

Table 3. Battery Limit of the Process of Tellurium Production

E.2 Plant Location

The best location for the plant would be at the back of the Refinery Building as it is accessible
to trucks for transportation of raw material, Cu2Te solids, from the By-Products plant.

9
E.3 Block Scheme Diagram

Figure
gure 4. Block Scheme Diagram for the Production of Tellurium from Copper Telluride and Processing of By
By-product
product (per batch)

10
E.4 Process Flow Sheet

Figure 5. Process Flow Sheet for the Production of Tellurium from Copper Telluride and Processing of By-product
By

11
F. PROCESS AND EQUIPMENT DESIGN
In the production of Te metal, it is not only the process that will be considered, but also
the materials of construction as well as the sizing and design of the equipment.

F.1 Equipment Selection and Design

Manual calculation is used in the process of the designing and sizing the
equipment. Mass balance calculations were manually done to come up with the
necessary specification needed in the production process. Calculations for the
dimension of the tanks, as well as the necessary impellers are shown in Appendix C.

F.2 Auxiliaries and Miscellaneous Design

Pipes.
The optimum pipe diameter,Di,opt, that is used for the pipings were based on the
size of the pipes at the By-Products Plant. The volumetric flowrate, as well as the
time for transfer of material from tank to tank were determined. The detailed
calculations and data on the nominal pipe size, outside diameter, schedule number
and wall thickness are shown in Appendix D.

Inlet and Outlet Openings.

The diameter for the inlet and opening will be the same for the optimum pipe
diameter which is the same to the inner diameter of the pipe. It will be connected
using a double-welded butt joint with a joint efficiency equal to 0.75.

Pumps.
There are two major types of pumps: Dynamic and Positive Displacement.
Centrifugal pumps are used in this design. This pump is a type of a dynamic pump.
Centrifugal pumps are widely used in chemical processing plants and refineries [23].
The advantages in using a centrifugal pump are: its simplicity, it has low first cost,
uniform flow, small floor space, low maintenance expense, quiet operation, and
adaptability for use with a motor or turbine drive [24].

Joints and Fittings.

The joints and fittings for the pipe connections will be the 90° elbow joints for the
bending in pipe connections during the transfer of fluids from one reactor to
another [25].

Connectors.
The connectors used in the pipes are the flanges, gaskets and bolts. Flanges are
usually utilized in order to give adequate strength in the pipe connections. Class #
150 is the best flange type to be used since it minimizes bending stresses [24].
Gaskets, on the other hand, are used in order to seal those spaces that are in
between the objects connected. The use of gaskets is advantageous since it has the

12
ability to withstand high compressive loads. The type of gasket chosen is the spiral
wound gasket since its bolt forces are high due to the alternating seal of filler and
metal materials [26]. On the other hand, truss head bolts are chosen because it can
cover large diameter clearance holes in metal sheets.

Valves.
Ball valves will be utilized as the control valves in this design as the operation
requires an on/off valve service. Ball valves are versatile and have a good on/off or
throttling capability. They have a straight-through flow passage that reduces
pressure drop in the wide-open state and provides tight shutoff capability when
closed. In addition, the segmented ball valve provides for shearing action between
the ball and the ball seat that promotes closure in slurry service [24].

Flow Meters.
To be able to monitor and regulate the rate of flow, a flow meter is needed in the
set up. A rotameter is used in this design. A rotameter consists of a vertical
oriented glass tube with a larger end at the top, and a metering float which is free
to move within the tube. Fluid flow causes the float to rise in the tube as the
upward pressure differential and buoyancy of the fluid overcome the effect of
gravity. The height of the float is an indication of the flow rate. The tube can be
calibrated and graduated in appropriate flow units. Rotameter are cheap and easy
to operate [24].

Thermocouples and pH controllers.

To measure temperatures accurately, thermocouples will be utilized.
Thermocouples are needed to monitor the desired temperature of the pieces of
equipment. They are positioned not far from the openings in the outlet stream in
order to determine the temperature of the fluid that exits from the equipment.
The pH of the substances is monitored using pH controllers which are placed near
the openings in the inlet stream of the equipment.

13
III. COSTING

The overall cost and revenue for the production of tellurium from copper telluride is shown
in Table 4. Note that are already rounded up to the nearest thousands. The exact values and
detailed calculation can be found in Appendix E.

EXPENSES AMOUNT
A. TOTAL INVESTMENT COST (CAPEX) Php 95,576,000
 Total Direct Cost 66,784,000
 Total Indirect Cost 16,325,000
 Others 12,467,000
B. ANNUAL OPERATING EXPENDITURES (OPEX) Php 122,406,000
 Variable Cost
Raw Materials 98,994,000
Miscellaneous Materials 149,000
Utilities 1,731,000
Recycling Cost 903,000
Operating Labor (Operator) 372,000
Taxes on Sales Stocks 12,322,000
 Fixed Cost 7,935,000
REVENUE AMOUNT
ANNUAL REVENUE Php 246,439,000
Table 4. Overall Cost and Revenue for the Production of Tellurium from Copper Telluride

IV. ECONOMIC FEASIBILITY EVALUATION

One of the main considerations for designing a plant is its economic aspect. In this section,
the total investment costs, annual production costs, annual net profit, and other economic
criteria are considered and measured, which are shown in Table 5. Values for the different
economic criteria are given to determine the feasibility of the plant from its economic point
of view.

CRITERIA FORMULA AMOUNT

Total Investment
Cost (CAPEX) Php 95,576,000
Annual Gross Income – Annual
Annual Net Profit Php 124,037,000
Production Cost
price of products cost of raw materials
Economic Margin 59.83%
price of products
Return on Investment Annual Net Profit
 100% 129.78%
(ROI) Total Investment Cost
Annual Net Profit
Rate of Return (ROR)  100% 259.56%
Average Investment
Total Investment Cost
Payback Period 10 months
Annual Net Profit
Table 5. Economic Criteria

14
 From the table above, it can be seen that the economic margin, ROI and the ROR are high,
and the payback period is short. However, these factors are not only the bases if the design
is feasible as there is also a need to consider the net profit from the sales of Te metal and
by-product. This net profit should be greater than the income that the company would get if
Cu2Te solids is sold as is. A financial comparison between these products is given in Table 6.

Cu2Te solids Te metal and by-products

Expenses
• Capital Expenditures
None Php 95,576,000
• Annual Operating
None Php 122,406,000
Expenditures
Annual Revenue Php 98,705,000 Php 246,439,000
Annual Net Profit Php 98,705,000 Php 124,037,000
Economic Margin None 59.83%
Return on Investment (ROI) None 129.78%
Rate of Return (ROR) None 259.56%
Payback Period None 10 months
Table 6. Financial Comparison

The annual net profit from the sales of Te metal and by-product is higher by Php 25M
compared to the annual income from the sales of Cu2Te solids.

Note: All the values are already rounded up to the nearest Php 1,000. The exact values and
detailed calculation can be found in Appendix E.

V. CONCLUSION AND RECOMMENDATION

 An integrated process for the recovery and purification of Te metal from Cu2Te solids
was successfully designed through a careful evaluation and consideration of success-
determinant factors such as the cost, product conversion and production capacity.

 The design is definitely promising, attractive and reliable since it meets the objectives
and is economically sound. The resulting design has an economic margin of 59.83%, a
return on investment of 129.78%, a rate of return of 259.56% and a payback period of
10 months. These values can still be further improved if proper optimization
techniques will be applied such that it would increase productivity or lessen the cost.

 Considering the economic viability of the design, it is highly recommended that this
tellurium recovery facility be pursued as this would give the company an additional
profit of Php 25M from the processing of Cu2Te to produce and sell pure Tellurium as
compared to the annual income from currently selling Cu2Te solids only.

15
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43. Zhejiang Dafeng Light Machinery Co. Limited
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45. SHIHISA ENGINEERING PVT LTD
46. Zhangjiagang Gaohong Centrifugal Machinery Manufacture Co., Ltd.
47. Changzhou Chemical Science Equipment Co., Ltd.
48. Zhengzhou Shenlong Pump Co., Ltd.
49. ASM Handbook. 2006. Corrosion: Environment and Industries (ASM International). Volume
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50. www.ird.gov.hk Date accessed: January 30, 2012
51. Anticorrosivos Industriales Ltda. (ANCOR) and TECMIN S.A., www.ancortecmin.com
52. OnlineMetals.com Date accessed: February 2, 2012
53. Hangzhou Semya Machinery Co., Ltd
54. Jiangyin Longchang Machinery Manufacturing Co., Ltd
55. FG Orduna, L Ybanez and W Perez
56. C Ledesma, A Reyes, G Nepumuceno, E Tan, A Matiga and N Gelig
56. JL Pohino, J Lacbayen, MJ Talaban, J Morao, SA Lacaba and JC Viguilla
57. JC Bentoy

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