Scholarly record

LANDFILL UTILIZATION WITH COPPER DEPO CLAY - 1

Milenko Jovanović

Abstract

Forecast of international experts shows that by the end of the first quarter of this century there will be about 20-30% less copper produced from natural resources in relation to consumption (needs) in the world. Therefore, it is planned to compensate for the lack of processing of raw materials with recycling of technogene waste, which contains copper. In this respect the planned implementation of this process (technological process) has a special significance, especially as the processi ng of these raw materials, in addition to solving the economic effects of (environmental) problems in the field of environmental protection which is of a great importance for the city of Bor (and its surroundings). Key words: clay, technogene waste, copper, landf ill, reserves of mineral raw materials (mineral resource) GE1ERAL I1FORMATIO1 The exploitation of copper ore in Bor area be gan at the beginning of the 20th century. Parallel to this, ore melting was also done t ogether with melting of copper concentrate and precious metals, after finishing constr uction of the flotation drive (in 1934). Smelting of ores and obtaining of concentr ates of the exploitation of Bor copper deposits was carried out in furnace processing pl ants by the 60s of the last century. In addition to concentrates obtained of the Bor mine and concentrates obtained of the slot: Lipe, Majdanpek, Bucim, Cerova (M. Krivel j) the import from abroad has been done after that period. As a by-product of the process technogene waste and slag were created. Estimated quantities amounted to over 15 million tons. Depending on the technologies that were used in exploitation, me tallurgical smelting process stages in which slag appeared as well as characteristics of ore, copper concentrate and smelter, technogene waste was created with different physical, mineralogical and chemical characteristics. All slag formed in different periods were delayed in several locations, and some locations have been carried out and moved because of mining works, opening and expanding of the open pit (the old open pit mine and open pit ore body, "H"). Most of the slag at the site between pit ore body, "H" and the former ablution old pit workshop, so this location for better conversation below represents a "slag Depot - 1. The existence of slag, with a significant c ontent of useful components, particularly copper and precious metals, clearly indica tes the need to study possibilities of processing slag to the valorization of all useful components. The first attempt of evaluation of copper and precious metals of the slag in industrial procedure was made during 2001. In the period from 2002 to 2006 flotation processed 11th International Multidisciplinary Scientific GeoConference SGEM2011 www.sgem.org International Multidisciplinary Scientific GeoConference SGEM 2011 162 about 900,000 tons of slag. Obtained substantial amounts of copper, gold and silver that the applied procedures make possible valu ation of useful components from these materials. Having regards researches of this area in the phase of exploitation, processing and flotation process a geological research at the request of the RTB was done in 2006, followed by the preparation of and certification of reserves furnace slag and useful components of the site "dirt Depot - 1. Forecast of international experts shows that by the end of the first quarter of this century there will be about 20-30% less copper produced (from natural resources) in relation to consumption (needs) in the world. Therefore, it is planned to compensate for the lack of processing of raw materials with recycling of technogene waste, which contains copper. In this respect the planned implementation of this process (technological process) has a special significance, especially as the processi ng of these raw materials, in addition to solving the economic effects and (envir onmental) problems in the field of environmental protection. GEOLOGICAL STRUCTURE OF THE FIELD The dominant part of the material, on which furnace clay was accumulated, has technogene origin as a by-product of intensive mining and processing ore in Bor. Base, on which slag was delayed, is made of tailing got from the open pit mine “ Čoka Dulkan“. In the southeast of the landfill furnace slag formed furnating barren (on the old surface mine "RT H), northeast side seems barre n pit (High plans) and the North West - waste water jacket furnace slag. All these formations are accumulated on the former paleo relief, which was built by the Bor conglomerate, andesite, hydrothermal altered volcanic and vulcanoclastite rocks unchanged vulcanoclastite rocks and alluvial sediment. DESCRIPTIO1 OF WASTE SLAG The terrain on which the furnace slag "Slag Depot - 1" was deposited is located in the southeastern part of the industrial zone TI R (smelting and refining). Landfill is located, in part, in the old river bed of Bor and in part on its western slopes. Over time deposition of slag thickness forms high plat eau of about 30 m. The long axis dimension (NW - SE) is about 650 m, and the short (SW - NE) - about 200 meters. Clay is characterized by a strong heterogeneity in terms of physical, mineralogical and chemical properties. The result is a variety of ores, concentrates and smelter used in the process of smelting, as well as technologies th at have been applied in a relatively long period (60 years). On the basis of qualitative mine ralogical analysis the followi ng mineral composition of slag was established: sulphide solid soluti on (Cu-Fe), halkozin, pyrite, copper, cuprite, magnetite and mineral waste. Non metallic minerals (mullock) presented the appearance of glass with different eutectics dendrites (fajalit, etc.). The most common ore mineral of the sulphide phase "solid” solution sulphide is Cu-Fe. In addition to the described furnace slag dum p there are three locations where clay was deposited: Depository slag - 2, depot slag - slag depot 3 and – 4. The second-largest landfill, where the clay has been deposited, "the depot slag - 2" (water jacket clay oven), is located north-w est of the previously described, the area 11th International Multidisciplinary Scientific GeoConference SGEM2011 www.sgem.org betw milli The oxid e is 0.4 In t h excav body As a with cont e slag In 19 depo Tech A ch and o conc the a show The coole found conc is tur granu flotat proce ween the ol d on tons an d results of c e is 26 %, t 4 g/t and sil he process t vated and m y, "H" - dep result of m the overbu ent of use fu - 3) is abou 997, the del ot - 4, where hnological R hronological other non-s entration w area within t wn. first docu m ed at diffe r d that in v a entrate with rned in gran uling clay. tion slag p r ess in the B d smelter a d its qualit y chemical tes the content ver content the ore bo d moved to a ot slag third moving the s urden from o ul compon e ut 700,000 to aying of t h e is currently Figure 1: Research l overview o standard cla will be given the framewo mented ext e rent conve r arious mode h a copper c nuling clay, Based on t h rocessing w Bor flotation and the old y is determ i sting are: o v of magnetit t is 8,8 g/t. dy landfill o site that i s d. slag and dep open pit m i ents was d i ons. he s l a g o n t y delayed. Subvertica of the activi ay in Bor C n in the follo ork of the In ensive rese a rter slag, w es of cooli n content of 2 , and slightl he results f was done as n. pit. Estim a ined at a s m verall Cu = te is 2.41, s opening " H s located s o position on ine (the or e iluted. Esti m the landfill al section slo ities related Copper Sme owing descr nstitute of c arch on thi s hich conta i ng the slag 20-25 % and ly lower tha from the re s well as se l ated quanti t mall numbe = 0.604 %; p sulfur conten H" part of t h outh of the n the present e body "H" ) mated cap a – 1 was mo opes at "Dep d to determin elter as flot ription. The copper in Bo s subject is ined about can be ex a d the use of an those per searching, t lection of e ty on this s er of sampl e participation nt is 0.5%, he slag fro m former ope t site, it ca m ), and for t h acity of thi s oved to the pot slag 1" ning the val ation and o e activities t or duting th sued in 19 7 4 % copp e amined in p f copper of rcents when the technolo equipment f Ge site is abo u es (ten sa m n in total c o the gold co m the Dep o en pit mine me to the m hese reason s location ( old open pi luation of co other metho that took pla he past perio 70. The sa m er. Researc h producing co 90-92 % wh n it is turned ogical schem for technolo eology 163 ut 1.9 mples). opper ontent ot - 1 - ore mixing s the depot it slag opper ods of ace in od are mples h has opper hen it d non meo f ogical 11th International Multidisciplinary Scientific GeoConference SGEM2011 www.sgem.org International Multidisciplinary Scientific GeoConference SGEM 2011 164 During the 1971 the investigation about possibilities of evaluation of copper in different samples was carried out, for which testing of physical and mechanical properties of clay has been done: - Samples from the old smelter slag, which contain below 0.4 % copper; - Samples furnace slag, which contain 0.20 to 0.83 % Cu; - Samples of converter slag, containing 1.0 to 3.5 % Cu. In mid-1972, the industrial flotation tes ting for copper valorization from slag was carried out. For this purpose a slag to the landfill "bed" has been specially cooled and after the necessary degree of fragmentation flotation it subjected to the treatment. During the probe a total of 5913 tons of slag processed, the main copper content was 4.80 %. Copper concentrate is produced with high copper content of 38.79%, copper usage of 83.83 %. If within this campaign, which was lasted 73 shifts, 14 shifts are separated, in which the content of copper in input slag was below 3.0%, then it is evident that in these shifts was made the content of copper in concentrate of 25.08 % and with utilization of 87.46 %. During the 1989 the sample was taken of furnace slag - Cork - which is formed on the container - cinder domes for transport to a landfill. The sample contained 1.0 % Cu, of which about 27 % are copper oxide, 1.2 g/t Au and 10 g/t Ag. The investigation determined that a concentrate containing about 14.5 % Cu with the use of about 72 % can be produced from this slag. Simultaneously with the formation of the previous sample, the second sample was formed that contained 5.63% Cu, of which about 15 % copper oxide, 2.98 g/t Au and 9.88 g/t Ag. The investigation concluded that the tested sample can produce a copper concentrate with about 22% Cu, 10.3 g/t Au and 38 g/t Ag, Cu with the use of about 94 %, 84 % gold and silver, about 94 %. Testing at the old smelter slag in1995 showed that sample contained about 5.3 % Cu of which there were about 20 % oxide copper. From the samples tested a concentrate containing about 16 % copper, 4 g/t Au and 28 g/t Ag, with utiliz ation of all three elements of 90-92 % was produced. The participation of magnetic fractions and distribution of copper and passed the appropr iate conclusions were examined in this sample . In the previous study examination of slag sa mples taken from the "bed" was performed. The sample contained 1.47% copper, in which the copper oxide relatively shares the amount to 19 %, with traces of gold and silver. Copper concentrate is produced of about 4% Cu and about 81 % are useful, which is rated as unsatisfactory. Additional analysis showed that the copper in the clay has been dispersed in the melted substratum (magnetit and silicate compound), which makes possible the achievement of a higher degree of concentration. In conclusion, we could say that the slag can be mixed in the ratio of 1:1 and flotation achieves a reasonable economic results. Based on the results of the tests defined by the technological scheme of processing slag from the Bor flotation hour processing capacity of 125 tons was specified as normative material and processing costs. At the end of 1996 the new tests were performed on the sample of slag "Dance" of pots with fiery furnace slag, outpouring the land fill near the railway, and the sample contained 2.22 % Cu, of which there were 28 % of copper oxide, 0.38 g/t Au and 7.0 g/t Ag. The samples made only basic flotation experiments and produced a concentrate 11th International Multidisciplinary Scientific GeoConference SGEM2011 www.sgem.org Geology 165 with 11 % Cu, 3.43 g/t Au and 28.64 g/t Ag. The efficiency of Cu 87.35%, to 96.75 Au and Ag 83.39% was realized. With the prev ious two samples it was also taken the sample who presents mixture of copper matte s and converter slag, which is, in fact, limpet from the pots that is used for conve rter slag transport – korku. The sample contained 21.18 % Cu, while the share of copper oxide was only about 12 %, 1.90 g/t Au and 7.40 g/t Ag. The copper concentrate containing about 36 % Cu, 7 g/t Au and 48 g/t Ag was produced from the examined samples. The efficiency of Cu of 98 % to 94 % Au and Ag 90 % was realized. Based on the previous results a conceptual design of the processing slag was done, where the mass amounted to about 5800 tons and 10,000 tons estimated at Hald. The solution is related to the processing of slag flotation plant in Bor. At the beginning of 1997 at the request of TIR and preliminary documentation - Outokumpu, slag processing of 400,000 per year is defined by the technological process and the verification of the selection of basic equipment in flotation Bor was carried out. During the 1997 the slag sample was taken from the converter hall, where it should be able to perform testing half-industrial valu ation Cu, Au and Ag. The samples are called "clay pots - large" copper content 16.5%, and “small clay pots” with copper content of 24.75 %. Due to the large presence of copper metal, which has size of bricks slag crushing in crushing plant couldn’t be done and, therefore, only laboratory tests were made. A low utilization of copper was achieve d at both samples, which is not higher than 80%, and there are a very high content of copper in concentrates. Additional data analysis have shown that in this case it was a converter clay, but probably the cold material with a high admixture of cuprous chloride and delafosit or copper oxide has led to the conclusion that the material comes from the anode furnace. In the late 1997 the slag sample was taken from the "bed", which contained less than 2% Cu, of which there were about 20 % Cu oxide, and the same is made of copper concentrate with 10 % Cu and Cu utilization of 80 %. At the same time the sample was taken from the slag heaps of agglomeration, which contained 5.18 % Cu, of which the part of Cu oxide were about 15 %, and copper concentrate with about 24 % Cu and the use of 80 % was produced from it. Based on the results of previous research, at the end of the nineties the preliminary variant solution of flotation slag processing means, for a capacity of 50,000 and 500,000 tons per year, has been done. In the same time the possibility of using the existing flotation plant in Bor was discussed, as well as the minimum required building new plants and equipment. At the end of the ni neties the preliminary design flotation flash furnace slag processing has done by the concept of Sober company, and a part of the reconstruction project in the Bor Copper Smelter, and also a study of opportunities of slag converter by flotation concept companies - Mitsui. During 2004 and 2005 laboratory tests have continued utilization of useful components from samples smelter slag which is then already processing, and within the industrial plant flotation tests in Bor. Considering th at the utilization of copper in concentrate ranging about 45-60 % there is an idea to ma ke testing the opportunities of leaching copper flotation from the island base (final tailings process) in order to further utilization of residual copper concentration after the flotation process. Swelling flotation sample contained a concentration of 0.32 % total copper, of which about 10 % of any oxide. The laboratory methods for the chemical department of PMS concentration of the Institute of copper were made considering leaching samples for di fferent experimental conditions. Drinking water was us ed as alkali solution and also the solution of sulfuric 11th International Multidisciplinary Scientific GeoConference SGEM2011 www.sgem.org International Multidisciplinary Scientific GeoConference SGEM 2011 166 acid was added for pH regulation. Relationship between solid and liquid phases in the experiments was a 1:2, or 33 % of the solid phase. During the research the influence of several parameters was examined. It was done at different solution pH values (pH = 1 and pH = 1.5). The influence of various oxidants on unleashing copper was also examined. For this purpose, the ferric chloride FeCl3, ferric sulfate Fe 2 (SO 4)3 and hydrogen peroxide H2O2 were added. It was also tested and achieved the level of copper in leaching at different time intervals (5min, 10min, 15min, 20min, 30min, 40min, 50min, 60min). With leaching swelling furn ace basic slag flota tion for different conditions achieved a small degree leaching copper, the highest value of only 20% with the addition of hydrogen peroxide as an oxidi zer. Consumption of sulfuric acid was great (the highest value 160 to 195kg / t). In the case of leaching plus ferric chloride as oxidizer, the consumption of sulfuric acid was considerably less than 30kg/t, but the degree of leached copper was lower. It is generally assumed that the swelling leaching copper slag flotation furnating can not expect additional valuation cost of copper, which is probably the result of a significant content of copper sulphide minerals in the island flotation concentration (over 50%), which is quite difficult to dissolve sulfuric acid. The report on this research was submitted to the Copper Mines Bor. Parallel to the research of leaching swelling furnace slag flotation, the research base slag flotation with the addition of lignite and anth racite with low mass pa rticipation in order to increase the efficiency of copper at this stage of the process was carried out. From the literature it is known that coals have mark ed absorption properties, and that the properties used mainly for precious metals processing technology - so-called process CIP (Carbon in Palp). Copper content in the sample was 0.85% with 20% oxide copper. Laboratory experiments were first dete rmined by technological parameters of production results from industrial processes. The trials were also formed to analyze differences in the actual technological la boratory results between different types of reagents to drive used (KEX; KAX; NaIPX) a nd also show the effectiveness of the use of various types of coal in the process of flotation furnace slag, and preliminary the establishment of prolonged flotation time. Two series of preliminary tests were done. After the first series is clearly visible increasing utilization of copper (up to 7%), adding lignite mass of 2%. In the second series of experiments it was determined "reference" state of utilization of copper in the labor atory and on industria l and technological parameters as the mean of three consecu tive experiments obtained utilization amounted to 52.23%. The degree of increasing in efficiency of copper with the use of coal flotation process depended on the type of coal used and the best is the use of lignite. Generally, in this series of e xperiments to increase the trend is not repeated in the first series and amounted to only 2-3%, and ranged up to 55.09%. In any case, the value achieved the best utilization of copper in both series of experiments is the use of coal flotation. In the same period a preliminary examination of the concentration of magnetic islands flotation furnate slag concentrations were made that is aimed at determining possibilities to extract other commercial products from these materials. In fact, chemical analysis showed that the fina l mullock furnating slag flotation process is significantly different from the final flotation tailings of primary ore. RDA analysis determined the significant occurrence of magnetite Fe3O4 an d fajalit Fe2SiO4 caused by "artificial" delay furnating slag and rapid cooling. C ontent of iron and iron compounds leads to the possibility of additional definitive treatment of overburden in order to prepare for use in black metallurgy, and steel mills. On the ot her hand a definite mullock furnace flotation slag contains compounds that would be mini mal technological interventions and could 11th International Multidisciplinary Scientific GeoConference SGEM2011 www.sgem.org be f puzz magn basel Dens The f M fra densi Fe - Fe3O Al2O SiO2 As s conc of ir o of m Figu CO1 Of al comp incre usefu thank can mate perfo class inves the i copp The possi ecolo comp focused in zuolana " M netic concen line sample sity - 3575 k following p action ity - 3660 k 37.98 % O4 - 11.42 % O3 - 4.81 % - 32.74 % seen from entration m on compoun odern equip ure 2: Samp 1CLUSIO1 ll mentione ponents fr o easing effici ul compon e ks to its c h find their erials, susp s ormed in the sical influe stigated, suc

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DOI resolver: doi.org/10.5593/sgem2011/s01.122

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