1. REE ORES, TITANIUM AND TIN ORE
GROUP 2
Abdullah karaarslan
Burçin meral
Cemal demirkıran
Gürkan tamer

2. REEs are the strategic and indispensable elements of the century because they are used in stable, high temperature, abrasion, corrosion resistant, high technology products for different purposes in the defense sector.
Oxides are very difficult to reduce to metal and rarely found in nature, these elements are called "rare earth elements, REE".

3. REE minerals with economical prescription

4. Uses of rare earth elements

5. Rare Earth reserves
REE reserves in the world are concentrated in 8 countries and are around 140x10^6 tons.
China is in the first place in the world with 55x10^6 tons in terms of REE reserves.

6. REE minerals flotation
It contains several mineral REEs such as monazite and xenotime. As the particle size becomes smaller, enrichment of minerals by gravity method becomes very difficult and causes mineral losses. For this reason, it is beneficial to enrich the freed minerals from 100μ to 15μ with flotation.

7. In addition to REE from Bayan Obo's ore, magnetite, fluorite, hematite and niobium minerals are gained.75μ boyutu altına öğütülmektedir.
The pH is adjusted with Na2CO3.
For the suppression of other impurities Na2SiO3 and Na2SiF6.
Hydroxamic acid is used as the collector.
Calcite, fluorite and barite are depressed between pH 5-6.
After selective flotation, a concentrate containing about 45% REE is obtained with about 80% recovery containing monazite and bastnazite.
In this current flowsheet, magnetite is taken from the first stage and hematite is taken from the second stage.

9. Cationic collectors such as fatty acids are used in the flotation of monazite and bastnasite. Better results were obtained when these collectors were supplemented with alkyl sulphate or phosphate ester.
Since the behaviors of the cesium group or bastnasite and monazite float are similar to those of calcite, barite, apatite, tourmaline, pyrochlore and other impurities, enrichment of these minerals with selective flotation is difficult.
Monazite floats at pH 7-11 using cationic collectors such as oleic acid and sodium oleate.

10. As the pH value of the medium increases, the absorption of sodium oleate by the monazite also increases.
As the pH value of the medium decreases, the ability of the monazite to floatability decreases

11. Bastnazite is associated with the impurities involved in flotation activity. As the pulp temperature increases in flotation, the REE gain also increases.

12. In this ore example, synchisite, parasitic as well as bastnazite
In this ore example, synchisite, parasitic as well as bastnazite. And as monazite secondary REEs, calcite, barite, silicate and dolomite as impurities. Barite also contains strontium.
Hydroxamic acid is more effective than fatty acids.
3-4.5 kg / t soda Na2CO3
g / t sodium fluorosilicate
kg / t lignin sulphonate
g / t oil fatty acid
The graph shows the effect of the pH value of the medium on flotation when benzoic acid is used as a picker in the selective flotation of monazite and bastnasite.

14. Dong Pao REE reserves are located in the north-western region of Vietnam. The main minerals in the mineralization are bastnazite, florspat, parasitic. The reservoir of this bed is around 5x10 ^ 6 tons
The ore is then flotated with barite followed by fluorite and REE in the final flotation stage.
For barite flotation;
Depressant sodium silicate
Activator barium klorite
Collector Petroleum sulfonate, sodium alkyl sulphonate and succinamate mixture
For Flouride flotation;
Mixture of quebracho and lignin sulphonate
Collector Oleic acid and phosphoric ester mixture
For Bastnazite flotation;
Collector Tall oil fatty acid supplemented with three ethylene tetramines
Depressant High molecular weight lignin sulphonate

15. The flow chart of the plant used in the enrichment of this ore is given in Fig.

17. Titanium Minerals
Titanium is the most abundant metal in the earth crust, and is present in excess of 0.62%. It can be found as dioxy titanium and the salts of titanium acids. Titanium is capable of forming complex anions representing simple titanites. It can also be found in association with niobium, silicates, zircon and other minerals. A total of 70 titanium minerals are known, as mixtures with other minerals and also impurities. Only a few of these minerals are of any economic importance.

18. Out of the 70 known titanium minerals, only a few have any economic value.
The most important titanium minerals are ilmenite, rutile and perovskie. Loparite is a major mineral for production of niobium and REO.

19. FLOTATION PROPERTIES OF MAJOR TITANIUM MINERALS
Extensive research has been carried out mainly on ilmenite and, to a lesser degree, on flotation of rutile and perovskite. Flotation studies have been performed on titanium minerals from both hard rock and fine-grained sand deposits.

20. Practices in beneficiation of ilmenite ores using flotation
Titania A/S, Norway
This is one of the oldest operations in the world. The mine and plant are located in the southern part of Norway. This ore can be classified as an ilmenorutile, with ilmenite and magnetite as the valuable minerals. The gangue consists mainly of feldspar, hypersthene and biotite. The secondary minerals present in this ore include pyrite, olivine and pyrrhotite.

21. Over a period of years, the Titania A/S flowsheet has changed as the ore in the plant changed. The flowsheet that is currently being used is shown in Figure This flowsheet utilizes a two-stage flotation method, where in stage 1, pyrite and apatite are recovered, followed by ilmenite flotation in stage 2.

22. Before sulphide flotation, magnetite was removed using a low- intensity magnetic separation method. The reagent scheme used at the Titania A/S plant is shown in Table

23. The major problem associated with beneficiation of this ore was the fact that the apatite tended to float with the ilmenite concentrate. Two options were examined to control apatite flotation:
apatite flotation in the pyrite circuit using small amounts of tall oil, and use of NaF to depress the apatite during the ilmenite cleaning operation.
Both methods were capable of lowering the apatite content of the ilmenite concentrate, with an appreciable loss of ilmenite.

24. Rutile/ilmenite-zircon bulk flotation and separation
Several large deposits of fine mineral sands containing rutile, ilmenite and zircon exist in Australia (Wimmera mine) and in the Soviet Union. The rutile, ilmenite and zircon cannot be preconcentrated. In most cases, flotation was used which involved bulk flotation followed by titanium–zircon separation. Over the years, several effective processes have been developed for bulk flotation followed by titanium–zirconium separation. The type of method used is dependent on the type and mineralogy of the fine sand. The following section describes three major methods developed for bulk Ta/Zr flotation and separation.

25. Method 1
This method has been successfully used in the Soviet Union. The flowsheet with the type and levels of reagent additions is shown in Figure.

26. The bulk flotation can be accomplished with the addition of small doses of oleic acid plus oxidized emulsion of fuel oil. The fuel oil is treated with 10% solution of NaOH at a temperature of 60–80°C for 1 h. The following method was used for rutile–zircon separation; the concentrate was thickened, followed by heat conditioning to 60°C. After the heat treatment, the zircon was floated without the addition of collector. The zirconium tailing is the rutile concentrate. The zircon concentrate was thickened, followed by gravity cleaning. In some cases, the heat-treated pulp is washed before zircon flotation. The following metallurgical results were obtained:
Rutile product – 92.5% TiO2 at 90% recovery
Zircon concentrate – 0.2% TiO2, 63% ZrO2 at 94% ZrO2 recovery.

27. Method 2
It involves bulk flotation of rutile, ilmenite and zircon followed by selective flotation of rutile and ilmenite and depression of zircon. Figure shows the flowsheet with type of reagent additions used in selective flotation of titanium from zircon. Guadalajara (Mexico) rutile ilmenite ore

28. The collector used was a mixture of oleic acid and kerosene in a ratio of 1:1. The mixture was aerated with oxygen during a period of 2 h before using. The advantage of using the oxidized mixture is that it desorbs easily from the mineral surfaces during separation. The metallurgical results obtained using Method 2 are shown in Table.

29. Method 3
It involves bulk titanium/zircon flotation using succinamate collector followed by bulk concentrate pretreatment and selective zircon flotation. This method was developed for beneficiation of the Wimmera heavy mineral sand from Australia . The beneficiation flowsheet with type and level of reagents is shown in Figure.

30. The sand preparation method had a significant impact on both collector consumption, as well as quality of the bulk concentrate. It was found that the mixture of Na2SiO3/tall oil addition to the scrubbing stage before desliming improved the slime decoating from the heavy mineral surface resulting in a significant improvement in concentrate grade. In addition, collector consumption was reduced by 50%. The mixture consisted of 70% Na2SiO3 and 30% tall oil fatty acid. The effect of the levels of silicate tall oil additions and conditioning times are presented in Table.

31. the mixture of Na2SiO3/tall oil was added to the scrubber before desliming. Collector used in the bulk circuit was sulphosuccinate. In the rutile circuit, phosphoric acid ester was used. Silica was rejected in a bulk talking. The overall metallurgical results obtained in the continuous operation are shown in Table.

32. CASSITERITE FLOTATION(TIN OXIDE)
The nominal size range for cassiterite flotation is between 2 and 100 microns. The top size is variable depending upon the liberation of the cassiterite particles. Cassiterite grains coarser than 100 microns are difficult to float whilst grains finer than 2 microns give selectivity problems. Hence the feed for casssiterite flotation should be reduced to 95% microns and then deslimed at 2 microns to give a feed containing no more than 8% -2 microns.

33. When it comes to flotation of a Tin rich ore like cassiterite, collector is a most important reagent as it determines froth grade and recovery . The optimum addition is controlled by several factors;
Ore type
Head grade
Product grade and recovery
The collector used in cassiterite flotation often have an effect on the froth properties. Excessive collector additions can give froth properties. Excessive collector additions can give froth stability problems and hence selectivity problems. The types of collecto used in the flotation of cassiterite are varied. A number of factors control the choice of collectors used.

34. The following is a list of some of the collectors which are available:

35. Frother
A frother should be used with extra caution in oxide flotation as ezcessive amounts of frother will alter the foth composition, increasing the recovery of water and hence increase the recovery of the gangue minerals. The choice of frother for cassiterite flotation as recently become an important variable as the effects of various frother and concentrations have been investigated. The frother MIBC has historically been the frother used but recent limitations with this reagent have led to the use of alternatives such as Aerofroth 65, Senfroth 41G and Dowfroth 250.

36. Depressants
The reagent sodium silico fluoride (Na2SiF6) is the most commonly used depressant in cassiterite flotation, acting both as a slime dispersant and also reducing the floatability of certain minerals, especially fluorite, tourmaline and other silicates. It is also thought to activate cassiterita in some circumstances. This reagent is added prior to the collector addition varies depending on the ore source, but kg/tonnes of feed is a good starting point
Other depressant which are occasionally used are:
Sodium silicate: slime dispersant but will depress cassiterite if added in large quantities
Lignin sulphonate : depressant for gangue slimes
Cyquest: precipitation of heavy metal ions.

37. Modifiers
It is necessary for the PH of the flotation pulp to be at he correct value and held relatively constant, for maximum selectivity and recovery.
Cassiterite flotation is nearly always performed in an acid environment, the exact value depending on the ore source and collector to be used . Sulphuric acid is used for PH adjustment in most cases. Changes in PH can cause to the froth. A reduction in PH will give better selectivity but usually at a lower recovery. If the PH increased the opposite will occur as presistent froths are formed
Alkali(NaOH): The addition of NaOH is sometimes used to increase the PH in the cleaning stages. The higher PH helps in dispersing slime and improving the %Sn grade .

38. . The beneficiation flowsheet