TREATMENT OF TAILINGS WITH FLUE-GAS DESULFURIZATION SOLIDS

Abstract

A process for improving the dewatering characteristic of tailings is provided comprising adding flue-gas desulfurization (FGD) solids, produced when using calcium oxide to remove sulfur dioxide from flue gas or emissions, to the tailings.

Claims

1. A process for improving the dewatering characteristic of tailings comprising adding flue-gas desulfurization (FGD) solids, produced when using calcium oxide to remove sulfur dioxide from emissions, to the tailings.

2. The process as claimed in claim 1, further comprising adding a flocculant to the tailings either before, during, or after the addition of FGD solids.

3. The process as claimed in claim 2, further comprising subjecting the tailings to centrifugation or gravity settling in a tailings deposit or thickener after the addition of the FGD solids and flocculant.

4. The process as claimed in claim 2, wherein the flocculant is an anionic polymer.

5. The process as claimed in claim 4, wherein the anionic polymer is an anionic polyacrylamide.

6. The process as claimed in claim 1, wherein the tailings are oil sand tailings produced during bitumen extraction from oil sand having a solids content in the range of about 10 wt % to about 45 wt %.

7. The process as claimed in claim 6, wherein the oil sand tailings are thin fine tailings.

8. The process as claimed in claim 6, wherein the oil sand tailings are fluid fine tailings.

9. The process as claimed in claim 6, wherein the oil sand tailings are mature fine tailings.

10. The process as claimed in claim 1, further comprising adding sand to the tailings at a sand to fines ratio of about 3.5:1 to about 5:1 prior to, during, or after the addition of FGD solids to form composite tailings.

11. The process as claimed in claim 1, wherein the FGD solids are added at a dosage of about 1000 to 9000 g/tonne of tailings solids.

12. The process as claimed in claim 1, wherein the FGD solids are added at a dosage of about 1500 to 4500 g/tonne of tailings solids.

13. The process as claimed in claim 1, wherein the FGD solids are comprised of calcium sulfite hemihydrate, calcium sulfate dihydrate, calcium carbonate, calcium oxide, calcium hydroxide and petroleum coke.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Referring to the drawings wherein like reference numerals indicate similar parts throughout the several views, several aspects of the present invention are illustrated by way of example, and not by way of limitation, in detail in the figures, wherein:

[0022] FIG. 1 is a graph showing the settling rates of four composite tailings (CT) columns treated with four different concentrations of FGD solids.

[0023] FIG. 2 is a graph showing the settling rates of four CT samples treated with (1) 800 g/t slaked lime (CaO); (2) 800 g/t hydrated lime (Ca(OH).sub.2); (3) FGD solids dosage equal to the dosage of CaO; and (4) FGD solids dosage equal to the dosage of Ca(OH).sub.2.

[0024] FIG. 3 is a bar graph showing the settled volume (ml) versus time (settling rate) for a flocculated (with A3338) 3 wt % mature fine tailings suspension pretreated with either 1500 g/t gypsum or 3000 g/t FGD solids (Plant 29 Solids).

[0025] FIG. 4 is a schematic of a process for treating tailings where FGD solids can be used.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] The detailed description set forth below in connection with the appended drawings is intended as a description of various embodiments of the present invention and is not intended to represent the only embodiments contemplated by the inventor. The detailed description includes specific details for the purpose of providing a comprehensive understanding of the present invention. However, it will be apparent to those skilled in the art that the present invention may be practiced without these specific details.

[0027] The present invention relates generally to a process for improving the dewatering characteristic of tailings comprising adding flue-gas desulfurization solids (FGD solids), produced when using calcium oxide to remove sulfur dioxide from emissions, to the tailings. For commercial scale consideration, the FGD solids were assessed to determine if the solids had suitable and consistent chemistry to perform as a tailings process aid. Further, the effectiveness of FGD solids in three tailings treatment processes, the composite tailings (CT) process, accelerated dewatering and centrifugation, were tested.

[0028] As used herein, the term tailings means any tailings produced during a mining operation and, in particular, tailings derived from oil sands extraction operations that contain a fines fraction. The term is meant to include fluid fine tailings (FFT) from oil sands tailings ponds and fine tailings from ongoing oil sands extraction operations (for example, flotation tailings, thickener underflow, PSV underflow or froth treatment tailings) which may or may not bypass a tailings pond. In one embodiment, the tailings are primarily FFT, including mature fine tailings (MFT), obtained from oil sands tailings ponds given the significant quantities of such material to reclaim. However, it should be understood that the fine tailings treated according to the process of the present invention are not necessarily obtained from a tailings pond, and may also be obtained from ongoing oil sands extraction operations.

[0029] As used herein, g/tonne or g/t means an amount of FGD solids or flocculant or other process aid, in grams, added per tonne of tailings solids.

[0030] As used herein, the term flocculation refers to a process of contact and adhesion whereby the particles of a dispersion form larger-size clusters in the form of flocs or aggregates. As used herein, the term flocculant refers to a reagent which promotes flocculation by bridging colloids and other suspended particles in liquids to aggregate, forming a floc. Flocculants useful in the present invention are generally anionic polymers, which may be naturally occurring or synthetic, having relatively high molecular weights. In one embodiment, the dosage of the anionic polymeric flocculant ranges from between about 0 to about 1500 grams per tonne of solids in the tailings.

[0031] Suitable natural polymeric flocculants may be polysaccharides such as guar gum, gelatin, alginates, chitosan, and isinglass. Suitable synthetic polymeric flocculants include, but are not limited to, polyacrylamides, for example, a high molecular weight, long-chain modified polyacrylamide (PAM). PAM is a polymer (CH.sub.2CHCONH.sub.2).sub.n formed from acrylamide subunits with the following structure:

##STR00001##

It can be synthesized as a simple linear-chain structure or cross-linked, typically using N,N-methylenebisacrylamide to form a branched structure. Even though such compounds are often called polyacrylamide, many are copolymers of acrylamide and one or more other chemical species, such as an acrylic acid or a salt thereof. The modified polymer is thus conferred with a particular ionic character, i.e., changing the anionicity of the PAM. Preferably, the polyacrylamide anionic flocculants are characterized by molecular weights ranging between about 10 to about 24 million, and medium charge density (about 25-30% anionicity). It will be appreciated by those skilled in the art that various modifications (e.g., branched or straight chain modifications, charge density, molecular weight, dosage) to the flocculant may be contemplated.

EXAMPLE 1

[0032] To assess variability in product quality, a monitoring program was initiated to evaluate the FGD solids produced over time. Typical component concentrations of FGD solids are shown in Table 1, below.

TABLE-US-00001 TABLE 1 Chemical Composition of FGD Solids Chemical Common Average Formula Name Name wt. % CaSO.sub.3 .Math. H.sub.2O Calcium sulfite 44 8 hemihydrate CaSO.sub.4 .Math. 2H.sub.2O Calcium sulfate Gypsum 6 1 dihydrate CaCO.sub.3 Calcium carbonate Limestone 9 3 (calcite) CaO Calcium oxide Quicklime <1 Ca(OH).sub.2 Calcium hydroxide Slaked lime/ 30 5 hydrated lime Inerts Coke 10 2 H2O Water 1 0.5

[0033] To provide further information on the material composition, and assess water soluble components, soluble ion tests were completed for a series of FGD solid samples collected weekly during a one year period of time. The test involved preparing a 1000 part per million (ppm) mixture by adding 1 g of FGD solids into 1 Liter of deionized water and measuring the resulting ions in solution. The results of the analyses are summarized in Table 2 below.

TABLE-US-00002 TABLE 2 Water Solubles Properties Averaged Over a One-Year Period Con- Alkalinity ductivity SO.sub.4 as CaCO.sub.3 Ca pH (S/cm) (mg/L) (mg/L) (mg/L) Average 11.8 1951 34 446 206 Std 0.18 413 5 109 45 Deviation % 2% 21% 15% 24% 22% Uncertainty
The most dominant active ingredient in the FGD solids in terms of tailings process aid is the slaked or hydrated lime (Ca(OH).sub.2), augmented by the smaller but still significant gypsum content. The availability of gypsum and the presence of the fine grained inert components may explain why the FGD solids are more effective in tailings treatment than commercially available slaked lime. Table 2 shows that the soluble ion variation in FGD solids samples over the one year period compares to the established variation in FGD solids composition from the more detailed solids composition analysis. The variation over time in the lime content of about 20% is acceptable for a tailings process aid. The lower values can be used to define minimum acceptable dosages to account for both process-aid quality and process variations.

[0034] It was also discovered that FGD solids are fine grained relative to commercially available gypsum, for example, agricultural grade gypsum, and this significantly improves the rate at which the FGD solids can go into solution and effectively interact with the tailings, e.g., MFT, minerals. In particular, it was discovered that greater than 90% of the FGD solids are less than 44 m, where only around 66% of agricultural grade gypsum is less than 44 m. Thus, the dissolution time for FGD solids is shorter and the FGD solids has better material handling when preparing slurries. Table 3 below summarizes the particle size distribution (PSD) of high purity agricultural grade gypsum versus FGD solids.

TABLE-US-00003 TABLE 3 Particle Size Distribution (PSD) Gypsum Gypsum FGD FGD Solids Size % % greater Solids % greater (m) passing than % passing than 360 180 150 89.2 10.8 125 100 100 0 88 74 76.7 23.3 62 44 65.7 34.3 90 10 0 0 100 0 100

EXAMPLE 2

[0035] A test program was undertaken to assess the suitability of FGD solids as a tailings process aid in the composite tailings (CT) process. Four laboratory scale columns (2 L) were used to contain prepared CT mixtures with a nominal sand to fines ratio (SFR) of about 3.5 and a solids content of about 55 wt.%. Table 4 below shows the actual composition of the prepared CT mixtures and the associated FGD solid dosages. All four columns contained FGD solids dosages considerably larger than what is currently used in the Applicant's commercial CT process with gypsum (1200g/m.sup.3 of CT). The columns were monitored for a period of 11 days to assess the initial water release and to determine the degree of any segregation.

TABLE-US-00004 TABLE 4 Solids Mass Mass of Dosage g Dosage (wt. CT FGD Solids FGD/m.sup.3 g FGD/ Column %) (kg) added (g) CT tonne CT Test 1 55.99 2 4 3070 2000 Test 2 57.86 2 8 6253 4000 Test 3 54.03 2.2 5.2 3562 2364 Test 4 51.34 2.2 10.4 6948 4727
FIG. 1 shows the settling rate for the four prepared CT recipes described in Table 4. It can be seen that the initial settling rate is very rapid, followed by a slower settling and consolidation period. After a time period of about 4 days, settlements were similar for all 4 tests. Samples were taken from the top, middle and bottom of the columns to determine whether segregation had occurred. Segregation would be indicated by a significantly lower sand content in the upper layers, and a higher sand content in the lower layers, indicating separation or segregation of the fines from the sand matrix. It was found that the sand to fines ratio in the top, middle and bottom layers were essentially the same, indicating that little or no segregation had occurred.

[0036] The release water was also tested for quality and compared to typical recycle water (RCW). The results are shown in Table 5 below. The CT release water quality was acceptable for the FGD solid doses assessed. It did not result in material concentration increases in sodium, chloride, magnesium, or sulfate. In addition, the pH changes were consistent with operational ranges in RCW which typically varies between 8 (tailings ponds) and 11 (extraction).

TABLE-US-00005 TABLE 5 Chemistry of CT Release Water Compared to Typical Recycled Water (RCW) FGD Ion Dose Release Water Chemistry Bal- (g/m3) Ca K Mg Na Cl SO.sub.4 CO.sub.3 HCO.sub.3 pH ance 3070 (Test 1) 52 11 2 647 374 853 1 71 8.4 1.06 6253 (Test 2) 15 12 0 725 359 572 160 18 11.3 1.18 3562 (Test 3) 28 10 1 667 367 732 1 88 7.6 1.13 6948 (Test 4) 21 14 0 687 375 506 216 5 11.9 1.1 RCW 35 14 16 610 340 527 2 270 8.1 1.19 All values in mg/L except pH

EXAMPLE 3

[0037] Similar to Example 2, four laboratory scale columns (2 L) were used to contain prepared CT mixtures with a nominal sand to fines ratio (SFR) of about 3.5 and a solids content of about 55 wt.%. The CT preparations were treated with (1) 800 g/t slaked lime (CaO); (2) 800 g/t hydrated lime (Ca(OH).sub.2); (3) FGD solids dosage equal to the dosage of CaO; and (4) FGD solids dosage equal to the dosage of Ca(OH).sub.2. FIG. 2 shows the various CT samples settling rates as indicated by the decrease in the interface (m1) of the CT in the 2 L cylinders per time (min). It can be seen from FIG. 2 that the settling rate for CT made with FGD solids is superior to that with an equivalent CAO or Ca(OH).sub.2 coagulant addition.

[0038] As previously mentioned, maintaining a non-segregating mixture is critical to the performance of the CT deposit as it settles. Table 6, below, shows the analysis of the fines (44 micron) percentage at the top, middle, and bottom of the settling columns. If the CT sample is not segregating, the fines percentage will be the same top to bottom. If the coagulant dosage is inadequate, the coarse sand will settle out, leaving a higher fines percentage in the upper layer of the settling test column. Table 6 shows that, not only is the settling rate for CT superior with FGD solids, the FGD solids treated samples do not segregate.

TABLE-US-00006 TABLE 6 Analysis of the settled CT columns made with CaO, Ca(OH).sub.2, and the equivalent dosages of FGDS. Location in nominal 44 Settling dosage micron Column Coagulant gm/m.sup.3 percentage Comment Top Fraction CaO 800 39.7 some segregation Middle Fraction CaO 800 37.2 some segregation Bottom Fraction CaO 800 33.2 some segregation Middle Fraction Ca(OH)2 800 51.3 significant segregation Bottom Fraction Ca(OH)2 800 43.5 significant segregation Top Fraction FGDS 800 47.7 some Ca(OH).sub.2 eqv segregation Middle Fraction FGDS 800 33.2 some Ca(OH).sub.2 eqv segregation Bottom Fraction FGDS 800 37.8 some Ca(OH).sub.2 eqv segregation Top Fraction FGDS 800 33.3 no CaOeqv segregation Middle Fraction FGDS 800 35.5 no CaO eqv segregation Bottom Fraction FGDS 800 35.1 no CaO eqv segregation

EXAMPLE 4

[0039] In the Applicant's current Full Scale FFT centrifuge plant, gypsum is used to treat the clays present in tailings (e.g., FFT or MFT) prior to flocculant addition. It is critical to determine whether pre-treatment with FGD solids will adversely affect the flocculant performance. A sensitive way to test any effect of FGD solids (versus gypsum) is to evaluate flocculant performance in dilute suspensions. The use of a dilute suspension serves to increase the performance range compared to monitoring the effect on undiluted MFT. FIG. 3 is a bar graph showing the settling rates (settled volume in ml versus time in minute:seconds) for a 3 weight per cent MFT suspension treated with 1500g/tonne of fines gypsum (right hand bars) and 3000 g/tonne of fines FGD solids (left hand bars). The flocculant used in each case was 500 g/tonne of fines A3338, an anionic, high molecular weight polyacrylamide that is currently used in the Applicant's centrifuge plant. It can be seen that the FGD solids and gypsum pre-treatments result in essentially the same settling rates, indicating that there would be no impact on the flocculant (polymer) effectiveness when substituting FGD solids for gypsum.

[0040] To test the strength development in the centrifuge cake, several modifications to the standard viscosity and yield point test procedure were made. For instance, both the peak yield and the yield stress after 60 seconds were chosen. Four test conditions were used: MFT samples pretreated with either nothing, 3000 g/tonne of fines FGD solids, 9000 g/tonne of fines FGD solids or 1500 g/tonne of fines gypsum, followed by treatment with 400 g/tonne of fines flocculant A3338. The flocculated MFT samples were then centrifuged under standard conditions (1500 rpm for 5 minutes). For both the flocculated and centrifuged samples, the peak and remoulded yield points were determined. Table 7 summarizes these results for flocculated MFT (the average of four tests each) and Table 8 summarizes the results for the flocculated and centrifuged MFT (the average of four tests each).

TABLE-US-00007 TABLE 7 Flocculated MFT Peak Peak Remoulded Yield Yield Std Remoulded Yield Std Sample ID (Pa) Dev (Pa) Yield (Pa) Dev (Pa) MFT no 8.4 1.1 7.5 0.8 additive Gypsum 12.8 1.5 11.5 1.3 1500 g/t FGD Solids 14.5 2.7 13.5 2.5 3000 g/t FGD Solids 23.8 4.7 21.8 4.3 9000 g/t

TABLE-US-00008 TABLE 8 Flocculated and Centrifuged MFT Peak Peak Remoulded Yield Yield Std Remoulded Yield Std Sample ID (Pa) Dev (Pa) Yield (Pa) Dev (Pa) MFT no 453 67 380 54 additive Gypsum 481 39 416 30 1500 g/t FGD Solids 669 69 579 59 3000 g/t FGD Solids 782 36 691 34 9000 g/t

[0041] The data shown in Tables 7 and 8 suggests that less than two times the FGD solids dosage would be as effective as gypsum in increasing the strength of the centrifuge cake and, therefore, the throughput.

[0042] Thus, FGD solids can substitute for gypsum in the FFT centrifuge process with an increase in dosage consistent with that determined for substitution in the CT process. In the CT process, gypsum or FGD solids are the only additive. For centrifuge applications, flocculation is a critical part of the process and it has been demonstrated that the FGD solids does not affect flocculant (polymer) performance. The FGD solids dosage relative to gypsum determined from the yield point increases for both treated MFT and the centrifuge cake but is somewhat less than that determined for CT substitution, however, consistent with the three times dosage determined from the CT studies. In addition, a two or three times dosage increase is well within the range of the gypsum dosing system at the FFT centrifuge Full Scale plant.

[0043] The yield point comparisons suggest that a dosage of FGD solids at 3000 g/tonne of tailings solids would produce similar results as 1500 g/tonne of gypsum. This means approximately 1500 to 4500 g/tonne of FGD solids compared to the target gypsum dosage of 500 to 1500 g/tonne.

[0044] Without being bound to theory, it is believed that the addition of FGD solids results in a combination of yield point and viscosity improvement due to the increase in pH from the residual lime and lesser amounts of gypsum, as well as a slight strength increase due to the inert and fine powdered coke and calcium sulfite. Cation exchange with Ca.sup.2+ from the lime may also be playing a role in this case as well. The minor component of gypsum in the FGD solids may also contribute to the effectiveness to a small extent.

EXAMPLE 5

[0045] As previously mentioned, accelerated dewatering (ADW) is a tailings treatment option that uses pre-treatment of tailings, such as fluid fine tailings, with a coagulant such as gypsum (i.e., multivalent cations) followed by treatment with a flocculant such as a polyacrylamide anionic flocculant. The ADW process uses the same process additives as the centrifuge process, with a coagulant pretreatment followed by polymeric flocculant addition. A pilot study on accelerated dewatering was done using cells as deposition sites to test the use of FGD solids as a substitute for gypsum. FIG. 4 is a schematic of the process used to prepare treated tailings for deposition into cells.

[0046] As shown in FIG. 4, raw fluid fine tailings (FFT) 10 having a solids content of about 35 wt % were first diluted with recycle water 12 to a solids content of about 28 wt %, followed by the addition of coagulant 14, which was either about 1300 g/tonne gypsum (cell #1) or about 3500 g/tonne FGD solids (FGDS) (cell #3). The tailings/coagulant was then mixed in an in-line static mixer 16 and the mixture was allowed to further mix in a residence time tank 18 having mixers therein. The mixture was then treated with about 1100 g/torme flocculant (polymer) 20 and further mixed in a hydrofoil dynamic mixer 22. The flocculated FFT 24 was then deposited into cells 26.

[0047] As mentioned, cell #1 contained FFT that had been pre-treated with gypsum and cell #3 contained FFT that had been pre-treated with FGDS. After two months, the treated FFT in cell #1 had a solids content of about 52 wt % solids and cell #3 had a solids content of about 54 wt % solids, which translates to a 4.2% reduction in water volume, showing that FGDS is superior to gypsum when used as a tailings pre-treatment in accelerated dewatering.

[0048] References in the specification to one embodiment, an embodiment, etc., indicate that the embodiment described may include a particular aspect, feature, structure, or characteristic, but not every embodiment necessarily includes that aspect, feature, structure, or characteristic. Moreover, such phrases may, but do not necessarily, refer to the same embodiment referred to in other portions of the specification. Further, when a particular aspect, feature, structure, or characteristic is described in connection with an embodiment, it is within the knowledge of one skilled in the art to affect or connect such module, aspect, feature, structure, or characteristic with other embodiments, whether or not explicitly described. In other words, any module, element or feature may be combined with any other element or feature in different embodiments, unless there is an obvious or inherent incompatibility, or it is specifically excluded.

[0049] It is further noted that the claims may be drafted to exclude any optional element. As such, this statement is intended to serve as antecedent basis for the use of exclusive terminology, such as solely, only, and the like, in connection with the recitation of claim elements or use of a negative limitation. The terms preferably, preferred, prefer, optionally, may, and similar terms are used to indicate that an item, condition or step being referred to is an optional (not required) feature of the invention.

[0050] The singular forms a, an, and the include the plural reference unless the context clearly dictates otherwise. The term and/or means any one of the items, any combination of the items, or all of the items with which this term is associated. The phrase one or more is readily understood by one of skill in the art, particularly when read in context of its usage.

[0051] The term about can refer to a variation of 5%, 10%, 20%, or 25% of the value specified. For example, about 50 percent can in some embodiments carry a variation from 45 to 55 percent. For integer ranges, the term about can include one or two integers greater than and/or less than a recited integer at each end of the range. Unless indicated otherwise herein, the term about is intended to include values and ranges proximate to the recited range that are equivalent in terms of the functionality of the composition, or the embodiment.

[0052] As will be understood by one skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges recited herein also encompass any and all possible sub-ranges and combinations of sub-ranges thereof, as well as the individual values making up the range, particularly integer values. A recited range includes each specific value, integer, decimal, or identity within the range. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, or tenths. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc.

[0053] As will also be understood by one skilled in the art, all language such as up to, at least, greater than, less than, more than, or more, and the like, include the number recited and such terms refer to ranges that can be subsequently broken down into sub-ranges as discussed above. In the same manner, all ratios recited herein also include all sub-ratios falling within the broader ratio.