CA1326571C - Recovery of metal values from oil sands tailings slurry - Google Patents
Recovery of metal values from oil sands tailings slurryInfo
- Publication number
- CA1326571C CA1326571C CA000527560A CA527560A CA1326571C CA 1326571 C CA1326571 C CA 1326571C CA 000527560 A CA000527560 A CA 000527560A CA 527560 A CA527560 A CA 527560A CA 1326571 C CA1326571 C CA 1326571C
- Authority
- CA
- Canada
- Prior art keywords
- slurry
- solids
- bitumen
- metal values
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002002 slurry Substances 0.000 title claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 23
- 239000002184 metal Substances 0.000 title claims abstract description 23
- 238000011084 recovery Methods 0.000 title description 13
- 239000007787 solid Substances 0.000 claims abstract description 34
- 238000005188 flotation Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000010936 titanium Substances 0.000 claims abstract description 22
- 239000010426 asphalt Substances 0.000 claims abstract description 19
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 16
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004576 sand Substances 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 6
- 238000003809 water extraction Methods 0.000 claims abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 23
- 239000010665 pine oil Substances 0.000 claims description 9
- -1 alkyl aryl sulphonate Chemical compound 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000007885 magnetic separation Methods 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 22
- 229910052500 inorganic mineral Inorganic materials 0.000 description 21
- 239000011707 mineral Substances 0.000 description 21
- 235000010755 mineral Nutrition 0.000 description 21
- 239000012141 concentrate Substances 0.000 description 15
- 235000008504 concentrate Nutrition 0.000 description 14
- 238000000926 separation method Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910052779 Neodymium Inorganic materials 0.000 description 5
- 229910052746 lanthanum Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 229910052776 Thorium Inorganic materials 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- 229910052688 Gadolinium Inorganic materials 0.000 description 3
- 229910052772 Samarium Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- IXQWNVPHFNLUGD-UHFFFAOYSA-N iron titanium Chemical compound [Ti].[Fe] IXQWNVPHFNLUGD-UHFFFAOYSA-N 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- GRYSXUXXBDSYRT-WOUKDFQISA-N (2r,3r,4r,5r)-2-(hydroxymethyl)-4-methoxy-5-[6-(methylamino)purin-9-yl]oxolan-3-ol Chemical compound C1=NC=2C(NC)=NC=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1OC GRYSXUXXBDSYRT-WOUKDFQISA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 206010044565 Tremor Diseases 0.000 description 1
- LENJPRSQISBMDN-UHFFFAOYSA-N [Y].[Ce] Chemical compound [Y].[Ce] LENJPRSQISBMDN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 239000000727 fraction Substances 0.000 description 1
- 238000009291 froth flotation Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229910001608 iron mineral Inorganic materials 0.000 description 1
- 239000001034 iron oxide pigment Substances 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000006148 magnetic separator Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052590 monazite Inorganic materials 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 239000003027 oil sand Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- BULVZWIRKLYCBC-UHFFFAOYSA-N phorate Chemical compound CCOP(=S)(OCC)SCSCC BULVZWIRKLYCBC-UHFFFAOYSA-N 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000011275 tar sand Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/02—Froth-flotation processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B9/00—General arrangement of separating plant, e.g. flow sheets
- B03B9/02—General arrangement of separating plant, e.g. flow sheets specially adapted for oil-sand, oil-chalk, oil-shales, ozokerite, bitumen, or the like
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Geology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A process is disclosed for recovering metal values from aqueous tailings slurry obtained from a hot water extraction process in which bitumen is recovered from bituminous sand, the slurry containing solids com-prising by weight from about 5 to about 9% titanium, from about 2 to about 5% zirconium, from about 8 to about 12%
iron, from about 2 to about 5% residual bitumen and from about 50 to about 70% siliceous material, the pulp density of the tailings slurry being from about 8 to about 20%
by weight solids. The process comprises ensuring that the pH of the tailings slurry is in the range of from about 8 to about 11.5, subjecting the slurry to a flotation step in a flotation vessel comprising injecting air to cause flotation of a substantial amount of said metal values in a froth above the siliceous and other unwanted material, and removing the floating froth containing the substantial amount of metal values from the remainder of the slurry.
A process is disclosed for recovering metal values from aqueous tailings slurry obtained from a hot water extraction process in which bitumen is recovered from bituminous sand, the slurry containing solids com-prising by weight from about 5 to about 9% titanium, from about 2 to about 5% zirconium, from about 8 to about 12%
iron, from about 2 to about 5% residual bitumen and from about 50 to about 70% siliceous material, the pulp density of the tailings slurry being from about 8 to about 20%
by weight solids. The process comprises ensuring that the pH of the tailings slurry is in the range of from about 8 to about 11.5, subjecting the slurry to a flotation step in a flotation vessel comprising injecting air to cause flotation of a substantial amount of said metal values in a froth above the siliceous and other unwanted material, and removing the floating froth containing the substantial amount of metal values from the remainder of the slurry.
Description
This invention relates to the recovery of titanium, iron and zirconium values from aqueous tailings slurry obtained from a hot water extraction process in which bitumen is recovered from bituminous sand, commonly known as oil sand or tar sand, such as is found for example in the AthabasCa region of Alberta.
The hot water e~traction process is of course well known. The bituminous sand is treated with steam or water to produce a pulp which is then circulated with water at about 1~0F through a separation cell in which entrained air causes oil to rise to the top as a bitumen-rich froth which is removed. Such froth typically contains about 10% solids and 30~ water by weight. Sand settles to the bottom of the separation cell and is removed therefrom.
Bitumen is recovered from the froth, for example by dilu-tion with naphtha, and subjecting the diluted froth to a two-stage centrifugal separation~ ;
In a typical first stage, the diluted froth is treated in a scroll-type separator to remove the coarse and/or dense solids. In a typical second stage, the first stage product is passed through a disc-type centrifugal separator to remove fine solids and water from bitumen/
naphtha mixture. At present, the tailings streams from the two stages are combined and disposed o~ in tailings ponds. In addition to silica sand and clay and residual bitumen, the solids fraction of such tailings contains metal values typically comprising by weight from about 5 to about 10% titanium, from about 2 to about 5% zirconium, and from about 8 to about 12% iron. It appears that the residual bitumen binds the mineral grains togethex.
Various proposals have been made for recovering these metal values from such tailings solids. For example, Canadian Patent No. 1,076,504, issued April 29, 1980, and Canadian Patent No. 1,088,883, issued November 4, 1980, describe processes in which the residual bitumen is burned off before separation of the metal values. However, such processes have now been recognized as uneconomical. It has also been proposed to effect separation of the metal values by agglomeration, for example as described in Canadian Patent No. 1,200,788 issued February 18, 1986. However, such a process is only effective for small mineral par-ticles, for example less than about 37 microns, and also requires the presence of an oil phase.
The tailings solids also contain from about 0.3 to about 0.4~ by weight rare earth elements such as lan-thanum, thorium, samarium, praseodymium, gadolinium, yttrium cerium and neodymium. The prior art of which applicants are aware has not been concerned with the recovery of such rar earth element valuesO
It is therefore an object of the present invention to provide an improved process for the recovery of metal values from tailings solids of the kind referred to above.
The present invention is based on the discovery that it is possible to separate titanium, zirconium and iron values from such tailings solids by subjecting aqueous tailings slurry to froth flotation which causes the metal values to float in a froth, and furthermore that rare earth element values are also recovered with the metal values in the froth.
The present invention accordingly provides a pro-cess for recovering metal values from aqueous tailings slurry obtained from a hot water extraction process in which bitumen is recovered from bituminous sand, said slurry containing solids comprising by weight from about 5 to about 9~ titanium, from about 2 to about 5% zirconium, from about 8 to about 12% iron, from about 2 to about 5~ residual bitumen and from about 50 to about 70~
siliceous material, the pulp density of said tailings slurry being from about 8 to about 20% by weight solids.
The process of the present invention comprises ensuring that the pH of said tailings slurry is in the range of from about 8 to about 11.5, subjecting the slurry to a flotation step in a flotation vessel comprising in-jecting air to cause flotation of a substantial amount of said metal values in a froth above the siliceous and other unwanted material, and removing the floating froth con-taining said substantial amount of metal values from the remainder of the slurry. The floating froth also contains rare earth element values when these are present in the original tailings slurry.
A frothing agent comprising pine oil may be added in the flotation step, the pine oil preferably being in an amount up to about 0.2 parts per 100 parts by volume of the slurry. AlternativeIy, a frothing agent may comprise an alkyl aryl sulphonate in the flotation step, the alkyl aryl sulphonate being present in an amount up to about 0.05 parts per 100 parts by volume of the slurry. The alkyl aryl sulphonate may advantageously be Tretolite F-46 (trade mark).
The removed froth solids are preferably heated to burn off residual bitumen and produce bitumen-free solids. The different metal values in the bitumen-free t 326571 solids are preferably separated by means of magnetic separation or mechanical screening.
In practice of the invention, it is first ensured that the aqueous tailings slurry has a pulp density in the range of from about 8 to about 20~ by weight solids and a pH in the range of from about 8 to about 11.5. The pulp density may be lowered or increased if necessary by addi-tion of water or by thickening, and the pH may be lowered or increased if necessary by addition of an acid such as hydrochloric acid or by the addition of an alkali such as caustic soda. After pH adjustment, the slurry should be allowed to be conditioned for a short period of timet for example from about 1 to about S minutes.
In some instances, it may be beneficial to add a frothing agent in the flotation step, and in this case a further conditioning period should be allowed after such addition, for example from about 0.25 to about 2 minutes.
The flotation agent may comprise cresylic acid, pine oil, alcohols, methyl isobutyl carbinol or alkyl aryl sulphonates.
It has been found that pine oil and the frothing agent com-prising alkyl aryl sulphonate sold under the trade mark TRETOLITE F-46 is especially useful in the present invention.
The concentrations are up to about 0.2 parts per 100 parts by volume of the slurry in the case of pine oil, and up to about 0.05 parts per 100 parts by volume of the slurry in the case of TRETOLITE F-46.
The slurry is then transferred to a flotation ves-sel in which air is blown at an appropriate rate to cause frothing and flotation of the froth, and the froth is collected as overflow. Con~entional flotation cells or columns may be used.
"~ I 32657 1 Examples of the process as so far described above will now be given.
Approximately 1.1 litre aliquots of aqueous dilu-tion centrifuge tailings slurry containing approximately 2-3~ bitumen and 12-14% inorganic sollds were treated in a flotation column. Froth samples were collected and analyzed for Ti, Zr, Si, Fe and rare earth elements (REE). Table 1 shows the elemental analysis of the feed solids and the flotation concentrate.
Element Feed Concentrate ~ Overall grade % grade ~ Recovery Ti 6-8 16-20 80-85 Zr 2-3 5-8 85-90 Si 23-26 10-14 13-18 Fe 7-12 12-18 40-45 ;`:
REE* 0.3-0.4 0.8-l.I 85-90 *REE include La, Th, Sm, Pr, Gd, Y, Ce, Nd.
It will be noted that the Ti, Zr and Ree were enriched about three-fold with better than 80~ recovery.
Approximately 2.3 litre aliquots of the slurry used in Example 1 were treated in a DENVER (trade mark) laboratory flotation cell. The froths produced were re-covered and analyzed for Ti, Zr, Si, Fe and REE. The results are shown in Table 2.
. .
Element Feed Concentrate % Overall grade ~ grade % Recovery Ti 6-8 15-20 75-85 Zr 2-3 S~7 85-90 Si 23-26 10-16 20-25 Fe 7-12 14-18 45-55 REE 0.3-0.4 0.7-1.0 80-85 The results obtained show that conventional flotation , cells also can be employed to effect the separation o:E
: -10 these heavy minerals from the gangue.
The acidity of the aqueous dilution centrifuge slurry aliquots used in Examp1e 1 was varied, after which the slurries were treated in a flotation column for fixed flotation time (10 minutes~ to determine the effect of pH
on mineral recoveries. The results are shown in Table 3.
~: pH Feed Concentrate Heavy Mineral Overall Heavy Gradet Gradet Recovery (%)* Minerals to Gangue Selec-tivity Index 203.3 17 38 33 1.95 4.2 17 40 42 2.22 5.3 19 39 33 1.87 7.6 16 42 56 2.63 8.0 17 39 60 2.49 8.3 16 39 70 3-00 : ~3.8 16 39 77 3.30 9.6 16 42 77 3.54 10.1 16 39 74 3.11 11.7 16 40 72 3.18 3011.9 16 42 51 2.46 , Total of Ti, Zr, and REE minerals (Ti expressed as TiO2, Zr as ZrO2-SiO2 and REE as monazite (Ce, La, Th, Y, Nd)P04.
* These recovery values do not represent e~uilibrium re-coveries but reflect relative rates of recovery.
These results show that the best recoveries as well as maximum selectivities ~measure of effecti.veness of gangue mineral rejection) were obtained in the pH range 8.3 to 11.7.
Aliquots of the aqueous dilution centrifuge tailings used in Example 1 were treated with varying amounts of pine oil and the flotation tests of Example 1 were repeated. The results are shown in Table 4.
Pine Oil Feed Gradet Concentrate Heavy Mineral Concentration (%) Gradet (%) Recovery (%) (% v/v) 0 ~17 45 60 0.025 18 ~4 81 0.05 18 43 75 0.10 18 42 85 0.15 17 43 95 0.20 18 43 go 0.30 15 45 55 0.50 18 47 38 t Total of Ti, Zr and REE minerals assuming all the titanium present as T102, Zr as ZrO2~SiO2 and Ree as ~Ce, La, Th, Y, Nd)P04.
After the froth from the flotation step has been collected, it is desirable to burn off residual bitumen present with the metal and rare earth elemental values to provide a free-flowing solid particle stream before further separation steps are carried out. The froth is preferably heated in a muffle furnace to a temperature in the range of from about 340 to about 550C. Even though the froth typi-cally contains from about 40 to about 50% moisture, it -has been found that predrying is not desirable since this may result in the temperature in the burn-off equipment exceeding about 760C and causing sintering of the solids.
As an alternative to a muffle furnace, a Herreshof or other open hearth furnace or a fluidized bed combustion unit may be used if desired.
A significant portion of the mineral particles in the bitumen-free solids from the burn-off step will be of a size less than about 75 microns, which is in con-trast to beach sand where the opposite is the case. Typi-cally, the bitumen-free solids may contain by weight from 20 about 14 to about 18~ lron, from about 15 to about 20%
titanium, from about 5 to about 7~ zircQnium and from about .8 to about 1.1% rare earth elements.
Embodiments and examples of the invention for ~ -separating different metal values from the bitumen-free solids will now be described with reference to Figures 1 and 2 which show flow sheets of two different embodiments.
According to one embodiment of the invention, as shown in Figure 1, the bitumen-free solids from the burn-off step are slurried with water and passed to a gravity concentration circuit to remove fine gangue par-ticles with for example a particle size from about ~5 - . . , .~
-' 1 32657 1 microns and density of about 2.65 g/cm3. It has been found that a simple sedimentation vessel such as a cone classifier can be used for this purpose, the preferred value of the solid settling velocity being about 6 m/hr.
The underflow from the gravity sedimentation is subjected to dense medium separation to separate silica sand and clay from the heavy minerals. It has been found that use of dense medium with a density of about 2.95 g/cm was sufficient to effect such separation. As an alternative, a spiral circuit may be employed to effect the separation - o~ the silica sand and any residual clays from the minerals.
The heavy mineral concentrate is then subjected to low intensity magnetic separation to remove the strongly magnetic materials such as magnetite ~Fe304) and limonite.
This step is advantageously carried out with the solids in a wet state to minimize the loss of heavy minerals of rela-tively small size, for example less than about 75 microns.
The overflow from the sedimentation vessel contains the fine iron mineral which can further be processed to produce market grade iron oxide pigment.
The non-magnetic fraction is then subjected to dry high intensity magnetic separation. An induced roll magnetic separator is useful for this purpose and enables the solids to be separated into various fractions based on differences in their magnetic attractability. For example, by varying the armature current through a Frantz Isodynamic separator model L-l, it has been possible to separate the heavy mineral concentrate into five ~ractions, namely an iron-titanium slag, an iron-titanium slag with significantly enriched yttrium concentration, a rare earth mineral concentrate with significant amounts of an iron-_ g _ ~
1 32657 ~
titanium slag, a rutile concentrate with zircon contamina-tion, and a zircon concentrate with rutile contamination.
These fractions can be upgraded accordin~ to size and/or high tension separation to yield pure heavy mineral concen-trate.
Examples of this embodiment of the invention will now be described:
EXAMPLE 5 .
100 gm of hydrocarbon-free flotation concentrate was subjected to the upgrading procedure outlined in Figure 1. The results of the stream analysis are shown in Table 5.
Elemental Analysis (~ by weight) Stream # 1 2 3 4 5 6 7 8 9 Mbss (gm) 100 35 g.7 2.9 6.5 7.1 12.912.3 13.3 Ti 17 8.4 2.44.8 40 32 19 38 9.6 Zr 6.0 1.0 1.01.0 <1 ~1 1.0 9.0 29 Si 15 13 37 12 6.1 7.0 5.6 10 17 Fe 18 40 5.618 14 13 7.7 <1 <1 REE* 0.94 0.15 0.1 0 0.21 0.74 6.0 0.40 0.25 *Rare earth elements (Ce, La, m, Nd, Gd, Sm, Pr, Y) Another flotation concentrate sample (100 gm) after burn-off of bitumen was subjected to the upgrading procedure of Example 1 except that no dense medium was employed. The stream analyses are shown in Table 6.
-- 10 ~
Wt. Fraction Element in Stream (%) Stream # } ~ 3 4 5 6 7 8 9 Wt (gm)10037 - 4.8 8.57.5 13.615.011.6 Ti 18 9.0 - 9.6 38 31 22 3~ 5.4 Zr 6~01.0 ~1.0 <1 <1 1.5 13 30 Si 14 14 _18 9.8 8.4 9.8 14 26 Fe 18 36 - 30 14 12 7.5 <1 <1 REE* 0.95 0.18 - 0.45 0.15 0.694.6 0.92 0.~3 These results reveal the beneficial effect of using the dense medium to effect gangue (silica sandr rejection.
Contamination of the product streams by the silica sand is considerably reduced.
In accordance with another embodiment of the in-vention, as shown in Figure 2, it is posisble to effect reasonable separation of minerals in the bitumen-free solids from the burn-off stage by mechanical dry screening ~;
into four fractions, namely a coarse fraction, (-60 ~ 00 mesh), ~ ~
two intermediate fractions (-100 +200 mesh and -200 ~325 mesh) ~ -and a fines fraction t-326 mesh).
An example of this embodiment will now be des-cribed.
Flotation concentrate of the centrifuge tailings ~ (100 g) after burn-off to remove the residual bitumen ; separated into fractions when shaken on a mechanical shak-ing device in the process illustrated in Figure 2. The elemental analysis of this fraction is shown in Table 7A
and the distribution of the elements is shown in Table 7B.
Elemental Analysis (wt% in stream) Stream* #1 2 3 4 5 Wt of sample 100 6.7 39.5 21.3 32.5 (gm) Ti 18 13 27 19 804 Zr 5.3 1.5 4.0 15 2.0 Si 14 26 16 14 11 Fe 15 9.8 7.7 7.7 29 Ree0.88 0.13 0.682.7 0.10 *See Figure 2 for stream description Grain Size Element Distribution as Eraction of Total Can. Std.
Sieve Ti Zr Fe Si REE
-60 +1004.9 1.8 4.512.0 1.0 -100 +20058.429.5 20.243.0 30.4 -200 +32521.856.6 10.720.0 65.0 -325 14.9 12.1 64.725.0 3.7 -These results show that flotation and dry screening offer a simple process for the concentration of titanium, zirconium and rare earth heavy minerals in the intermediate size fractions (-100 + 200 mesh and -200 +325 mesh3 while con-centrating the iron in the -325 mesh fraction. These frac-tions can be thereafter advanced to further beneficiation steps to concentrate titanium-based, zirconium-based, rare earth element-based and iron-based minerals therefrom.
Other embodiments and examples of the in~ention will be readily apparent to a person ~killed in the art from the foregoing description, the scope of the invention being defined in the appended claims.
The hot water e~traction process is of course well known. The bituminous sand is treated with steam or water to produce a pulp which is then circulated with water at about 1~0F through a separation cell in which entrained air causes oil to rise to the top as a bitumen-rich froth which is removed. Such froth typically contains about 10% solids and 30~ water by weight. Sand settles to the bottom of the separation cell and is removed therefrom.
Bitumen is recovered from the froth, for example by dilu-tion with naphtha, and subjecting the diluted froth to a two-stage centrifugal separation~ ;
In a typical first stage, the diluted froth is treated in a scroll-type separator to remove the coarse and/or dense solids. In a typical second stage, the first stage product is passed through a disc-type centrifugal separator to remove fine solids and water from bitumen/
naphtha mixture. At present, the tailings streams from the two stages are combined and disposed o~ in tailings ponds. In addition to silica sand and clay and residual bitumen, the solids fraction of such tailings contains metal values typically comprising by weight from about 5 to about 10% titanium, from about 2 to about 5% zirconium, and from about 8 to about 12% iron. It appears that the residual bitumen binds the mineral grains togethex.
Various proposals have been made for recovering these metal values from such tailings solids. For example, Canadian Patent No. 1,076,504, issued April 29, 1980, and Canadian Patent No. 1,088,883, issued November 4, 1980, describe processes in which the residual bitumen is burned off before separation of the metal values. However, such processes have now been recognized as uneconomical. It has also been proposed to effect separation of the metal values by agglomeration, for example as described in Canadian Patent No. 1,200,788 issued February 18, 1986. However, such a process is only effective for small mineral par-ticles, for example less than about 37 microns, and also requires the presence of an oil phase.
The tailings solids also contain from about 0.3 to about 0.4~ by weight rare earth elements such as lan-thanum, thorium, samarium, praseodymium, gadolinium, yttrium cerium and neodymium. The prior art of which applicants are aware has not been concerned with the recovery of such rar earth element valuesO
It is therefore an object of the present invention to provide an improved process for the recovery of metal values from tailings solids of the kind referred to above.
The present invention is based on the discovery that it is possible to separate titanium, zirconium and iron values from such tailings solids by subjecting aqueous tailings slurry to froth flotation which causes the metal values to float in a froth, and furthermore that rare earth element values are also recovered with the metal values in the froth.
The present invention accordingly provides a pro-cess for recovering metal values from aqueous tailings slurry obtained from a hot water extraction process in which bitumen is recovered from bituminous sand, said slurry containing solids comprising by weight from about 5 to about 9~ titanium, from about 2 to about 5% zirconium, from about 8 to about 12% iron, from about 2 to about 5~ residual bitumen and from about 50 to about 70~
siliceous material, the pulp density of said tailings slurry being from about 8 to about 20% by weight solids.
The process of the present invention comprises ensuring that the pH of said tailings slurry is in the range of from about 8 to about 11.5, subjecting the slurry to a flotation step in a flotation vessel comprising in-jecting air to cause flotation of a substantial amount of said metal values in a froth above the siliceous and other unwanted material, and removing the floating froth con-taining said substantial amount of metal values from the remainder of the slurry. The floating froth also contains rare earth element values when these are present in the original tailings slurry.
A frothing agent comprising pine oil may be added in the flotation step, the pine oil preferably being in an amount up to about 0.2 parts per 100 parts by volume of the slurry. AlternativeIy, a frothing agent may comprise an alkyl aryl sulphonate in the flotation step, the alkyl aryl sulphonate being present in an amount up to about 0.05 parts per 100 parts by volume of the slurry. The alkyl aryl sulphonate may advantageously be Tretolite F-46 (trade mark).
The removed froth solids are preferably heated to burn off residual bitumen and produce bitumen-free solids. The different metal values in the bitumen-free t 326571 solids are preferably separated by means of magnetic separation or mechanical screening.
In practice of the invention, it is first ensured that the aqueous tailings slurry has a pulp density in the range of from about 8 to about 20~ by weight solids and a pH in the range of from about 8 to about 11.5. The pulp density may be lowered or increased if necessary by addi-tion of water or by thickening, and the pH may be lowered or increased if necessary by addition of an acid such as hydrochloric acid or by the addition of an alkali such as caustic soda. After pH adjustment, the slurry should be allowed to be conditioned for a short period of timet for example from about 1 to about S minutes.
In some instances, it may be beneficial to add a frothing agent in the flotation step, and in this case a further conditioning period should be allowed after such addition, for example from about 0.25 to about 2 minutes.
The flotation agent may comprise cresylic acid, pine oil, alcohols, methyl isobutyl carbinol or alkyl aryl sulphonates.
It has been found that pine oil and the frothing agent com-prising alkyl aryl sulphonate sold under the trade mark TRETOLITE F-46 is especially useful in the present invention.
The concentrations are up to about 0.2 parts per 100 parts by volume of the slurry in the case of pine oil, and up to about 0.05 parts per 100 parts by volume of the slurry in the case of TRETOLITE F-46.
The slurry is then transferred to a flotation ves-sel in which air is blown at an appropriate rate to cause frothing and flotation of the froth, and the froth is collected as overflow. Con~entional flotation cells or columns may be used.
"~ I 32657 1 Examples of the process as so far described above will now be given.
Approximately 1.1 litre aliquots of aqueous dilu-tion centrifuge tailings slurry containing approximately 2-3~ bitumen and 12-14% inorganic sollds were treated in a flotation column. Froth samples were collected and analyzed for Ti, Zr, Si, Fe and rare earth elements (REE). Table 1 shows the elemental analysis of the feed solids and the flotation concentrate.
Element Feed Concentrate ~ Overall grade % grade ~ Recovery Ti 6-8 16-20 80-85 Zr 2-3 5-8 85-90 Si 23-26 10-14 13-18 Fe 7-12 12-18 40-45 ;`:
REE* 0.3-0.4 0.8-l.I 85-90 *REE include La, Th, Sm, Pr, Gd, Y, Ce, Nd.
It will be noted that the Ti, Zr and Ree were enriched about three-fold with better than 80~ recovery.
Approximately 2.3 litre aliquots of the slurry used in Example 1 were treated in a DENVER (trade mark) laboratory flotation cell. The froths produced were re-covered and analyzed for Ti, Zr, Si, Fe and REE. The results are shown in Table 2.
. .
Element Feed Concentrate % Overall grade ~ grade % Recovery Ti 6-8 15-20 75-85 Zr 2-3 S~7 85-90 Si 23-26 10-16 20-25 Fe 7-12 14-18 45-55 REE 0.3-0.4 0.7-1.0 80-85 The results obtained show that conventional flotation , cells also can be employed to effect the separation o:E
: -10 these heavy minerals from the gangue.
The acidity of the aqueous dilution centrifuge slurry aliquots used in Examp1e 1 was varied, after which the slurries were treated in a flotation column for fixed flotation time (10 minutes~ to determine the effect of pH
on mineral recoveries. The results are shown in Table 3.
~: pH Feed Concentrate Heavy Mineral Overall Heavy Gradet Gradet Recovery (%)* Minerals to Gangue Selec-tivity Index 203.3 17 38 33 1.95 4.2 17 40 42 2.22 5.3 19 39 33 1.87 7.6 16 42 56 2.63 8.0 17 39 60 2.49 8.3 16 39 70 3-00 : ~3.8 16 39 77 3.30 9.6 16 42 77 3.54 10.1 16 39 74 3.11 11.7 16 40 72 3.18 3011.9 16 42 51 2.46 , Total of Ti, Zr, and REE minerals (Ti expressed as TiO2, Zr as ZrO2-SiO2 and REE as monazite (Ce, La, Th, Y, Nd)P04.
* These recovery values do not represent e~uilibrium re-coveries but reflect relative rates of recovery.
These results show that the best recoveries as well as maximum selectivities ~measure of effecti.veness of gangue mineral rejection) were obtained in the pH range 8.3 to 11.7.
Aliquots of the aqueous dilution centrifuge tailings used in Example 1 were treated with varying amounts of pine oil and the flotation tests of Example 1 were repeated. The results are shown in Table 4.
Pine Oil Feed Gradet Concentrate Heavy Mineral Concentration (%) Gradet (%) Recovery (%) (% v/v) 0 ~17 45 60 0.025 18 ~4 81 0.05 18 43 75 0.10 18 42 85 0.15 17 43 95 0.20 18 43 go 0.30 15 45 55 0.50 18 47 38 t Total of Ti, Zr and REE minerals assuming all the titanium present as T102, Zr as ZrO2~SiO2 and Ree as ~Ce, La, Th, Y, Nd)P04.
After the froth from the flotation step has been collected, it is desirable to burn off residual bitumen present with the metal and rare earth elemental values to provide a free-flowing solid particle stream before further separation steps are carried out. The froth is preferably heated in a muffle furnace to a temperature in the range of from about 340 to about 550C. Even though the froth typi-cally contains from about 40 to about 50% moisture, it -has been found that predrying is not desirable since this may result in the temperature in the burn-off equipment exceeding about 760C and causing sintering of the solids.
As an alternative to a muffle furnace, a Herreshof or other open hearth furnace or a fluidized bed combustion unit may be used if desired.
A significant portion of the mineral particles in the bitumen-free solids from the burn-off step will be of a size less than about 75 microns, which is in con-trast to beach sand where the opposite is the case. Typi-cally, the bitumen-free solids may contain by weight from 20 about 14 to about 18~ lron, from about 15 to about 20%
titanium, from about 5 to about 7~ zircQnium and from about .8 to about 1.1% rare earth elements.
Embodiments and examples of the invention for ~ -separating different metal values from the bitumen-free solids will now be described with reference to Figures 1 and 2 which show flow sheets of two different embodiments.
According to one embodiment of the invention, as shown in Figure 1, the bitumen-free solids from the burn-off step are slurried with water and passed to a gravity concentration circuit to remove fine gangue par-ticles with for example a particle size from about ~5 - . . , .~
-' 1 32657 1 microns and density of about 2.65 g/cm3. It has been found that a simple sedimentation vessel such as a cone classifier can be used for this purpose, the preferred value of the solid settling velocity being about 6 m/hr.
The underflow from the gravity sedimentation is subjected to dense medium separation to separate silica sand and clay from the heavy minerals. It has been found that use of dense medium with a density of about 2.95 g/cm was sufficient to effect such separation. As an alternative, a spiral circuit may be employed to effect the separation - o~ the silica sand and any residual clays from the minerals.
The heavy mineral concentrate is then subjected to low intensity magnetic separation to remove the strongly magnetic materials such as magnetite ~Fe304) and limonite.
This step is advantageously carried out with the solids in a wet state to minimize the loss of heavy minerals of rela-tively small size, for example less than about 75 microns.
The overflow from the sedimentation vessel contains the fine iron mineral which can further be processed to produce market grade iron oxide pigment.
The non-magnetic fraction is then subjected to dry high intensity magnetic separation. An induced roll magnetic separator is useful for this purpose and enables the solids to be separated into various fractions based on differences in their magnetic attractability. For example, by varying the armature current through a Frantz Isodynamic separator model L-l, it has been possible to separate the heavy mineral concentrate into five ~ractions, namely an iron-titanium slag, an iron-titanium slag with significantly enriched yttrium concentration, a rare earth mineral concentrate with significant amounts of an iron-_ g _ ~
1 32657 ~
titanium slag, a rutile concentrate with zircon contamina-tion, and a zircon concentrate with rutile contamination.
These fractions can be upgraded accordin~ to size and/or high tension separation to yield pure heavy mineral concen-trate.
Examples of this embodiment of the invention will now be described:
EXAMPLE 5 .
100 gm of hydrocarbon-free flotation concentrate was subjected to the upgrading procedure outlined in Figure 1. The results of the stream analysis are shown in Table 5.
Elemental Analysis (~ by weight) Stream # 1 2 3 4 5 6 7 8 9 Mbss (gm) 100 35 g.7 2.9 6.5 7.1 12.912.3 13.3 Ti 17 8.4 2.44.8 40 32 19 38 9.6 Zr 6.0 1.0 1.01.0 <1 ~1 1.0 9.0 29 Si 15 13 37 12 6.1 7.0 5.6 10 17 Fe 18 40 5.618 14 13 7.7 <1 <1 REE* 0.94 0.15 0.1 0 0.21 0.74 6.0 0.40 0.25 *Rare earth elements (Ce, La, m, Nd, Gd, Sm, Pr, Y) Another flotation concentrate sample (100 gm) after burn-off of bitumen was subjected to the upgrading procedure of Example 1 except that no dense medium was employed. The stream analyses are shown in Table 6.
-- 10 ~
Wt. Fraction Element in Stream (%) Stream # } ~ 3 4 5 6 7 8 9 Wt (gm)10037 - 4.8 8.57.5 13.615.011.6 Ti 18 9.0 - 9.6 38 31 22 3~ 5.4 Zr 6~01.0 ~1.0 <1 <1 1.5 13 30 Si 14 14 _18 9.8 8.4 9.8 14 26 Fe 18 36 - 30 14 12 7.5 <1 <1 REE* 0.95 0.18 - 0.45 0.15 0.694.6 0.92 0.~3 These results reveal the beneficial effect of using the dense medium to effect gangue (silica sandr rejection.
Contamination of the product streams by the silica sand is considerably reduced.
In accordance with another embodiment of the in-vention, as shown in Figure 2, it is posisble to effect reasonable separation of minerals in the bitumen-free solids from the burn-off stage by mechanical dry screening ~;
into four fractions, namely a coarse fraction, (-60 ~ 00 mesh), ~ ~
two intermediate fractions (-100 +200 mesh and -200 ~325 mesh) ~ -and a fines fraction t-326 mesh).
An example of this embodiment will now be des-cribed.
Flotation concentrate of the centrifuge tailings ~ (100 g) after burn-off to remove the residual bitumen ; separated into fractions when shaken on a mechanical shak-ing device in the process illustrated in Figure 2. The elemental analysis of this fraction is shown in Table 7A
and the distribution of the elements is shown in Table 7B.
Elemental Analysis (wt% in stream) Stream* #1 2 3 4 5 Wt of sample 100 6.7 39.5 21.3 32.5 (gm) Ti 18 13 27 19 804 Zr 5.3 1.5 4.0 15 2.0 Si 14 26 16 14 11 Fe 15 9.8 7.7 7.7 29 Ree0.88 0.13 0.682.7 0.10 *See Figure 2 for stream description Grain Size Element Distribution as Eraction of Total Can. Std.
Sieve Ti Zr Fe Si REE
-60 +1004.9 1.8 4.512.0 1.0 -100 +20058.429.5 20.243.0 30.4 -200 +32521.856.6 10.720.0 65.0 -325 14.9 12.1 64.725.0 3.7 -These results show that flotation and dry screening offer a simple process for the concentration of titanium, zirconium and rare earth heavy minerals in the intermediate size fractions (-100 + 200 mesh and -200 +325 mesh3 while con-centrating the iron in the -325 mesh fraction. These frac-tions can be thereafter advanced to further beneficiation steps to concentrate titanium-based, zirconium-based, rare earth element-based and iron-based minerals therefrom.
Other embodiments and examples of the in~ention will be readily apparent to a person ~killed in the art from the foregoing description, the scope of the invention being defined in the appended claims.
Claims (9)
1. A process for recovering metal values from aqueous tailing slurry obtained from a hot water extraction process in which bitumen is recovered from bituminous sand, said slurry containing solids comprising by weight from about 5 to about 9% titanium, from about 2 to about 5% zirconium, from about 8 to about 12% iron, from about 2 to about 5% residual bitumen and from about 50 to about 70% siliceous material, the pulp density of said tailings slurry being from about 8 to about 20% by weight solids, the process comprising ensuring that the pH of said tailings slurry is in the range of from about 8 to about 11.5, subjecting the slurry to a flotation step in a flotation vessel comprising injecting air to cause flotation of said metal values in a froth above the siliceous and other unwanted material, and removing the floating froth containing said metal values from the remainder of the slurry.
2. A process according to claim 1 wherein the slurry solids also contain by weight from about 0.3 to about 0.4%
rare earth element values, and rare earth element values report with the metal values in said froth and are removed therewith.
rare earth element values, and rare earth element values report with the metal values in said froth and are removed therewith.
3. A process according to claim 1 including adding a frothing agent comprising pine oil in said flotation step.
4. A process according to claim 3 including adding pine oil in an amount up to about 0.2 parts per 100 parts by volume of the slurry.
5. A process according to claim 1 including adding a frothing agent comprising an alkyl aryl sulphonate having the characteristics of TRETOLITE F-46TM in said flotation step.
6. A process according to claim 5 including adding an alkyl aryl sulphonate in an amount up to about 0.05 parts per 100 parts by volume of the slurry.
7. A process according to claim 1 including heating the removed froth solids to burn off residual bitumen and produce bitumen-free solids.
8. A process according to claim 7 including separating different metal values in the bitumen-free solids by means of magnetic separation.
9. A process according to claim 7 including separating different metal values in the bitumen-free solids by mechanical screening.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000527560A CA1326571C (en) | 1987-01-16 | 1987-01-16 | Recovery of metal values from oil sands tailings slurry |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000527560A CA1326571C (en) | 1987-01-16 | 1987-01-16 | Recovery of metal values from oil sands tailings slurry |
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| CA1326571C true CA1326571C (en) | 1994-01-25 |
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| CA000527560A Expired - Lifetime CA1326571C (en) | 1987-01-16 | 1987-01-16 | Recovery of metal values from oil sands tailings slurry |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7341658B2 (en) | 2002-04-18 | 2008-03-11 | Tatanium Corporation Inc. | Recovery of heavy minerals from a tar sand |
| US7695612B2 (en) | 2006-05-25 | 2010-04-13 | Titanium Corporation Inc. | Process for recovering heavy minerals from oil sand tailings |
| CN103272685A (en) * | 2013-05-15 | 2013-09-04 | 包钢集团矿山研究院（有限责任公司） | Mineral separation process for recycling iron and rare earth in baotite oxidized ore flotation tailings |
| US8852429B2 (en) | 2010-02-22 | 2014-10-07 | Titanium Corporation Inc. | Method for processing froth treatment tailings |
| WO2015051435A1 (en) * | 2013-10-10 | 2015-04-16 | Titanium Corporation Inc. | A method for producing a zirconium concentrated product from froth treatment tailings |
| CN106362858A (en) * | 2016-10-14 | 2017-02-01 | 鞍钢集团矿业有限公司 | Process for extracting cement-replacing superfine iron tailing powder from iron tailings |
| US10087372B2 (en) | 2009-04-09 | 2018-10-02 | Titanium Corporation Inc. | Methods for separating a feed material derived from a process for recovering bitumen from oil sands |
| CN109013047A (en) * | 2018-09-25 | 2018-12-18 | 李梅 | A kind of beneficiation method of sorting rare metal concentrate and quartzy feldspar concentrate |
| CN113443798A (en) * | 2020-03-27 | 2021-09-28 | 宝峨资源有限公司 | Method and treatment device for cleaning contaminated material |
-
1987
- 1987-01-16 CA CA000527560A patent/CA1326571C/en not_active Expired - Lifetime
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7341658B2 (en) | 2002-04-18 | 2008-03-11 | Tatanium Corporation Inc. | Recovery of heavy minerals from a tar sand |
| US7695612B2 (en) | 2006-05-25 | 2010-04-13 | Titanium Corporation Inc. | Process for recovering heavy minerals from oil sand tailings |
| US10087372B2 (en) | 2009-04-09 | 2018-10-02 | Titanium Corporation Inc. | Methods for separating a feed material derived from a process for recovering bitumen from oil sands |
| US8852429B2 (en) | 2010-02-22 | 2014-10-07 | Titanium Corporation Inc. | Method for processing froth treatment tailings |
| CN103272685A (en) * | 2013-05-15 | 2013-09-04 | 包钢集团矿山研究院（有限责任公司） | Mineral separation process for recycling iron and rare earth in baotite oxidized ore flotation tailings |
| CN103272685B (en) * | 2013-05-15 | 2015-09-30 | 包钢集团矿山研究院（有限责任公司） | The ore-dressing technique of iron and rare earth is reclaimed in baotite oxide ore flotation mine tailing |
| WO2015051435A1 (en) * | 2013-10-10 | 2015-04-16 | Titanium Corporation Inc. | A method for producing a zirconium concentrated product from froth treatment tailings |
| US9694367B2 (en) | 2013-10-10 | 2017-07-04 | Titanium Corporation, Inc. | Method for producing a zirconium concentrated product from froth treatment tailings |
| CN106362858A (en) * | 2016-10-14 | 2017-02-01 | 鞍钢集团矿业有限公司 | Process for extracting cement-replacing superfine iron tailing powder from iron tailings |
| CN109013047A (en) * | 2018-09-25 | 2018-12-18 | 李梅 | A kind of beneficiation method of sorting rare metal concentrate and quartzy feldspar concentrate |
| CN113443798A (en) * | 2020-03-27 | 2021-09-28 | 宝峨资源有限公司 | Method and treatment device for cleaning contaminated material |
| EP3885021A1 (en) * | 2020-03-27 | 2021-09-29 | Bauer Resources GmbH | Method and treatment plant for cleaning contaminated material |
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