Upgrading mining waste to develop added value final products

V. Aggelatou and E.I.P. Drosos

Department of Mineral Processing, Institute of Geology and Mineral Exploration

Th. Zampetakis and A. Meidani

Grecian Magnesite Research & Development Centre

S. Dambitzias and N. Arvanitidis

Peripheral branch of Central Macedonia, nstitute of Geology and Mineral Exploration

ABSTRACT The mean mineralogical composition of all dunite/harzburgites in the western Chalkidiki ophiolite complex is 55-60% olivine, 30-35% serpentine and 9-12% pyroxenes. Dunite/harzburgite formation in Yerakini area is the waste material produced from the beneficiation process of magnesite (MgCO3). It has been proven that after beneficiation of this waste material by appropriate methods, a material rich in olivine (75%) with a low serpentine content (below 10%) and a correspondingly low LOI value (1.5-2.0%) could be provided. Thus, in the frame of an ongoing EU program (ProMine), process routes such as dense media separation, shaking table and magnetic separation have been tested. The final product will be evaluated for the production of nano-silica for cement and paper applications. 1. INTRODUCTION The targets of EU-funded ProMine project (ProMine website) are the development and marketing of new, high added value products from waste raw materials produced by the extractive industry and the development of better exploitation and production practices on sites using a holistic approach, which includes all possible resources, and a more environmentally friendly responsible management. Under this scope, Grecian Magnesite (GM) with the aid of Institute of Geological and Mineral Exploration (IGME), have directed their efforts towards alternative

management of GMs dunite/harzburgite waste stream, promoting its valorisation as raw material for nanosilica production. In the southernmost part of the ophiolite complex in western Chalkidiki Peninsula, the Gerakini area, magnesite (MgCO3) deposits are exploited by GM producing magnesia (MgO) as final product. The mineable depth of the deposits exceeds 70 m. Dunites and harzburgites, which are serpentinized to different degrees, are the hosts to the magnesite veins. Ore is extracted in open pits and the process to transform the extracted RoM to final products, consists of four different stages: i) pre-beneficiation, ii) main beneficiation, iii) calcination/sintering and iv) end-processing. The capacity of the main processing line is 4500 tonnes of RoM per 8-hour shift. In 2008, the annual gangue material produced by this process was around one million tonnes. The beneficiation process produces waste types that are inert, non-hazardous and nonleachable under normal environmental conditions. Waste rocks are used to rehabilitate exhausted pits, as gravel and construction materials. It has been reported by several studies (Dambitzias et al. 2003 & 2009, IGME 2005) that a considerable amount of this waste contains a rather high percentage of olivine. From this material, using appropriate beneficiation methods, it is possible to produce a product with a content of ~75% in olivine, which is tested for various possible uses including the production of nano-silica using sulphuric acid (Lazaro 2010, Jonckbloedt 1998), that can be used as an additive in the production

of high performance concrete (Qing et al. 2007, Brouwers 2006) or in paper coating applications using acids and CO2 (Koljonen et al. 2004, US patent No.2004/0213705). Research has been undertaken in order to establish a flow-sheet of removing undesired constituents and developing an appropriate processing scheme for the olivine enrichment taking in consideration the economics of the processes. Towards this direction the mineralogy of the ore needs to be considered as this dictates the grade of liberation required and the process that can facilitate this. In order to fulfil the nanosilica production process demands and the final products properties, certain specifications are required as far as the feed material is concerned; i.e. low loss of ignition (a low serpentine content ), absence of carbonates, and high olivine content (>70%). The objective of this preliminary study is to investigate and develop the procedures which can be employed so as to increase the olivine content in waste material coming from mining and processing of magnesite ores by removing minerals containing water of crystallisation such as serpentine and eliminating, in the highest possible degree, associated pyroxenes. 2. MATERIALS AND METHODS 2.1 Samples preparation procedure quality characterization At first, three types of waste materials that could be supplied by the quarry were identified. Representative sampling and sample preparation together with grain size analysis, mineralogical study and chemical analysis were performed for the three indicative Gerakini dunite waste rocks and their size fractions. These materials were then stockpiled for further use. Each feed material (initial grain size of <100mm) was prepared in order to receive an adequate quantity for the tests that would be carried out, and then it was crushed (jaw crusher) at a size of <25 mm. In Table 1 the results of the chemical analysis of the three selected samples are presented. The results of semi-quantitaive analysis (X-RD) of the three samples are shown in Table 2. The samples were chemically analysed by ICP-MS and Atomic Adsorption Spectrophotometer methods.

In Figures 1-2 olivine ((Mg,Fe)2SiO4) and pyroxene (mainly enstatite, ((Mg,Fe)SiO3) crystals are depicted in contrast to weathered (serpentine, (Mg,Fe)3Si2O5(OH)4) material.
Table 1. Chemical analysis of the test samples

GM1 SiO2 Al2O3 Fe2O3 CaO MgO (K,Na)2O LOI Ni Cr Co 42.5 0.65 8.30 0.75 40.00 0.03 6.75 2150 740 105

GM2
% in dry weight

GM3 43.70 1.35 7.25 1.80 31.90 0.25 12.20 1730 520 90

46.10 0.95 6.00 7.50 19.50 0.15 18.85

mg/Kg in dry weight

1310 560 73

Table 2. Mineralogical analysis of the test samples

GM1 Olivine Pyroxenes Serpentine Quartz Dolomite Magnesite Talc Other 50 13 21 3 3 6 2 3-5

GM2
% mineral phase

GM3 23 15 17 13 5 13 3 11

2 8 14 29 21 9 6 11

50m

50m

Figure 1: Thin section of sample GM1: olivine

The evaluation results show that sample GM1 has the highest olivine content and does not. 50m 50m

Table 3a. Grain size distribution of GM1 size fractions

Sample GM1/1 GM1/2 GM1/3 GM1/4 GM1/5 GM1/6 TOTAL

Grain size (mm) -1.70+0.212 -0.212+0.180 -0.180+0.125 -0.125+0.075 -0.075+0.0380 -0.038

%Mass Distribution 65.8 2.53 7.16 7.70 6.57 10.3 100.0

Table 3b. Chemical nalysis of GM1 size fractions

Figure 2: Thin section of sample GM1: serpentine

contain high amounts of calcium carbonate minerals (calcite or dolomite) or free silica. Thus, sample GM1 was selected as the most appropriate to be further tested by various beneficiation methods. 2.2 Grain size analysis The entire quantity of feed sample marked as GM1 having a grain size of 5-100 mm was initially crushed by means of a jaw-crusher (Bronto Jaw Crusher) to a grain size of +1.70 mm. After that, the products were further processed by a role crusher having cylinders of 250 mm diameter and 150 mm length in order to produce a product with grain size of -1.70 mm. 2827.49 gr of sample GM1 were screened into six different size fractions named GM1/1 to GM1/6 and submitted to chemical analysis. The results of these analyses are presented in Tables 3a-b. As it is noted from the abovementioned results there is no differentiation in elemental distribution in all size fractions except for the finest size fraction. In GM1/6, the percentage of SiO2 and MgO are reduced and the LOI is almost doubled due to higher serpentine content.iefly sample GM1 consists mainly of olivine (55-60 %), pyroxenes (~12 %) and 20% serpentine. Other constituents include talc, actinolite, chlorite, magnesite and dolimite (each less than 3%).

Sample GM1 GM1/1 GM1/2 GM1/3 GM1/4 GM1/5 GM1/6 TOTAL

SiO2 44.15 43.70 44.15 43.80 44.15 43.80 42.50 43.63

Fe2O3 8.50 8.35 8.50 8.40 8.35 8.25 8.30 8.35

MgO 37.5 37.6 38.5 38.5 38.0 37.3 34.0 37.4

LOI 6.8 5.50 4.25 4.60 4.70 5.85 10.0 5.84

2.3 Olivine beneficiation testwork Beneficiation tests towards the enhancement of the compositional quality of the rocks in terms of enriching the olivine content were carried out in laboratory scale. Several series of tests were carried out involving various processing techniques such as DMS, Wilfley shaking table and magnetic separation. Quality and recovery results of products are based on chemical and mineralogical analyses of the initial material and the resulting products. Loss of ignition (LOI) itself, is a quite clear indication of the efficiency and the success of the process followed. 2.3.1. Magnetic separation In our study a Frantz dry magnetic separator of CHAS.W.COOK was used. Two individual size fractions of the selected sample (GM1) were processed namely GM1/1 and GM1/2 having a grain size of -1.70 mm and -0.212+0.180 mm, respectively, at two different field intensities (0.4 and 0.6 A) keeping other parameters stable (slope 200). In Tables 4a-4b the data from the conducted experiments are summarised.

Table 4a. Results of magnetic separation process (Intensity 0,4 A)

Size Product fraction <1,70mm Magnetic Non-magnetic TOTAL 0,180Magnetic 0,212mm Non-magnetic TOTAL

% w/w 77,35 22,65 100,0 65,95 34,05 100,0

% Olivine 52,0 60,0

parameters of GM pre-beneficiation process. A suitable quantity of the sample (about 100 - 150 g) was added into the liquid solution and stirred with a glass rod for about 1 min, after which it was left to settle.
Table 5. Heavy liquids used in DMS tests

Substance Diiodomethane Triethyl phosphate

Bulk Density (g/ml) 3.180-3.325 1.069

Table 4b. Results of magnetic separation process (Intensi-ty 0,6 A)

Size fraction <1,70mm 0,1800,212mm

Product Magnetic Non-magnetic TOTAL Magnetic Non-magnetic TOTAL

% w/w 99,3 0,7 100,0 93,4 6,96 100,0

% Olivine 65,0 70,0

At higher liquid BD the separation to sinkfloat fractions was almost instant (1-2 s), whereas in lower liquid B.D. (e.g.BD=2.90 g/ml), a little more time was needed (~5-10 s) for the separation to take place. The two fractions were then carefully collected using a special strainer, washed with acetone and dried at 200oC to decompose the remaining DIM. TG-DT and X-RD analyses were performed on 63 m comminuted samples. The recognised phases according to X-RD results for the sinks fraction were olivine (main phase) and serpentine and enstatite (secondary phases), with no indication of magnesite. In the floats fraction olivine remains the main phase with serpentine, enstatite and magnesite constituting the secondary phases. The tests were conducted on two grain sizes of feed material; 2-16 mm and 2-5,6 mm. The percentage of olivine content was calculated by difference based on geological studies of the area (Dambitzias, 2005) which have reported a maximum pyroxene level around 12%, while the various impurities (other than serpentine and carbonates) do not exceed 4%. The results show that the enrichment in olivine content is not affected by the decrease in grain size tested in the present study; however, it is affected by the BD of the media used. More specifically, it raises from 69.9% on sinks of 2.90 g/ml bulk density to 75% for media having a bulk density of 3.10 g/ml. At this BD the recovery of the separation tests is relatively low (in average 34%), possibly due to poor liberation of olivine grains.

The results from the magnetic separation show that the magnetic separation enhances the content of the waste material in olivine. The most effective intensity of the magnetic field tested, was that of 0.6 A, that achieved to recover a product of 70% olivine in a grain size between 0.212 mm and 0.180 mm. As far as the coarser grain size of 1.70 mm is concerned, the magnetic separation process resulted in an olivine content of approximately 65%. 2.3.2. Dense Media Separation Given that the BD range for olivine is 3.3-3.4 g/ml, 2.5-2.6 g/ml for serpentine and ~2.9 g/ml for magnesite, the selected BD value of the heavy liquid would be best set between 2.8 to 3.3 g/ml. Having that in mind, the beneficiation tests were conducted at three different bulk density values: 2.90, 3.00 and 3.10 g/ml. The heavy liquid and solvent used are depicted on Table 5. After the necessary quartering, crushing and sieving procedures two size fractions of sample GM1 were produced: 2-16 mm and 2-5.6 mm, both representative of the starting material. The fraction <2 mm was removed in an effort to resemble the actual industrial production

Table 7a. Results of dense media separation tests for sample GM1 for 2-16 mm grain size

Table 7b. Results of dense media separation tests for sample GM1 for 2-5,6 mm grain size

BD=3,10 g/cm3

BD=3,10 g/cm3

%LOI %Recovery1 %Serpentine %Carbonates % Olivine2 %LOI %Recovery %Serpentine %Carbonates % Olivine %LOI %Recovery %Serpentine %Carbonates % Olivine

SINKS 2,15 37,1 7,6 1,7 74,7 SINKS 3,25 61,0 10,0 3,0 71,0 SINKS 3,50 73,9 11,0 3,3 69,7

FLOATS 8,23 62,9 18,6 8,4 57,0 FLOATS 7,95 39,0 19,0 7,3 57,7 FLOATS 10,22 23,0 21,9 7,0 55,1

%LOI %Recovery1 %Serpentine %Carbonates % Olivine2 %LOI %Recovery1 %Serpentine %Carbonates % Olivine2 %LOI %Recovery1 %Serpentine %Carbonates % Olivine2

SINKS 2,01 30,6 7,0 2,0 75,0 SINKS 2,96 57,4 9,5 2,6 71,9 SINKS 4,14 78,3 10,1 4,0 69,9

FLOATS 7,43 69,3 19,0 6,0 59,0 FLOATS 9,53 42,6 21,4 8,3 54,3 FLOATS 10,58 21,7 23,1 8,7 52,2

BD=3,00 g/cm3

BD=3,00 g/cm3

BD=2,90 g/cm3

BD=2,90 g/cm3

1. mass recovery, 2 .minimum value

The total results of this study are presented in Table 7a-b. 2.3.3 Wilfley shaking table The experimental study of the dunite waste material (GM1) was conducted in lab scale using Wilfley shaking table. The size fraction 1.70 mm was fed to the table and the analyses of the concentrates (No1, No2) and tailings (No3 to No6) are presented in Table 8. According to the results, an enrichment in olivine content is achieved in the first fractions-products. The olivine content increases up to ~61% but at 33% w/w of the feed material. In any case it should be noted that these results are referred to grain sizes below 1.70 mm. 3. CONCLUSIONS This study represents only a preliminary experimental work on the possibility of using different mineral beneficiation methods for enriching waste dunite material in olivine. The results from the tests outlined here are encouraging and support the conclusion that waste material can be reclaimed effectively.

Table 8. Results of shaking table process

Products %R %LOI %Ol. %S. No1 9,32 3,05 60 12 No2 24,01 4,55 62 12 No3 10,71 5,90 54 21 No4 10,40 6,05 53 27 No5 38,82 6,3 52 16 No6 6,74 7,25 51 16 TOTAL 100,00 R: recovery, Ol: olivine, S: serpentine The metallurgical results show that it is possible by using a feed-waste material with just 55% olivine content, to obtain a product with a higher percentage of olivine (~75%), by means of economical and environmentally friendly methods. Depending on the required quality of olivine product for each specific application (grain size, purity, etc) and in relation to the beneficiation process cost-benefit analysis, an assemblage of proper processing routes can be applied to achieve the desired result.

REFERENCES
Brouwers, H.J.H. (2006). The role of nanotechnology for the development of sustainable concrete, Proceedings of ACI Session Nanotechnology of concrete: recent developments and future perspectives, (Eds. K. Sobolev and S.P. Shah, American Concrete Institute, Michigan), 7 November, Denver, U.S., 69-90. Dambitzias, S., Maltzari, F., Kaklamaki, N., Iliadi, A. (2003). Innovative technologies- Recording & exploitation techniques of mining, metallourgy industry & abandoned public mines wastes, Report on pilot applications: Magnesite, 3rd Community Support Framework, Operational Program Competitiveness, IGME. Dambitzias, S. (2005). Structure characteristics of stockwerk magnesite deposits in Chalkidiki Perfecture, Deposition of magnesite, 2nd Conference of Economic Geology, Mineralogy and Geochemistry committee, p.291-296. Dambitzias, S. (2009). Industrial minerals, innovative technologies, new products, 2009: Evaluation of olivine in environmental applications, 3rd Community Support Framework, Operational Program Competitiveness, final technical report.

IGME (1995). Olivine/Dunite for Industrial & Environmental Applications, Final technical report (GR-OLIV), Brite/Euram II Research action programme. Jonckbloedt, R.C.L. (1998). Olivine dissolution in sulphuric acid at elevated temperaturesimplications for the olivine process, an alternative waste acid neutralizing process, Journal of Geochemical Exploration 62 , pp 337346. Koljonen, T., Siikavirta, H., Zevenhoven, R. Savolainen, I., 2004. CO2 capture , storage and reuse potential in Finland, Energy 29, p.1521-1527. Lazaro, A. (2010). Nano-silica production by a sustainable process; application in building materials, 8th fib PhD Symposium in Kgs. Lyngby, Denmark, pp 1-6. promine.gtk.fi Qing, Y., Zenan, Z., Deyu, K., Rongshen, Ch. (2007). Influence of nano-SiO2 addition on properties of hardened cement paste as compared with silica fume, Construction and Building Materials 21, pp 539545. US patent No.2004/0213705, Carbonation of metal silicates for long -term CO2 sequestration.