AU2016250451A1 - Method for treating suspensions of solid particles in water - Google Patents
Method for treating suspensions of solid particles in water Download PDFInfo
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- AU2016250451A1 AU2016250451A1 AU2016250451A AU2016250451A AU2016250451A1 AU 2016250451 A1 AU2016250451 A1 AU 2016250451A1 AU 2016250451 A AU2016250451 A AU 2016250451A AU 2016250451 A AU2016250451 A AU 2016250451A AU 2016250451 A1 AU2016250451 A1 AU 2016250451A1
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 2
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- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 description 2
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- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
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- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 239000003027 oil sand Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- 229940047670 sodium acrylate Drugs 0.000 description 1
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- 230000009466 transformation Effects 0.000 description 1
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
METHOD FOR TREATING SUSPENSIONS OF SOLID PARTICLES IN WATER The present invention relates to a process for treating an aqueous suspension of solid particles, comprising forming a film of said suspension, and spraying a water-in-oil 5 emulsion comprising a water soluble polymer on the surface of the film. 8350325_1 (GHMatters) P104483.AU A - - - -+----- _3 Fig.1
Description
The present invention relates to a process for treating an aqueous suspension of solid particles, comprising forming a film of said suspension, and spraying a water-in-oil emulsion comprising a water soluble polymer on the surface of the film.
8350325_1 (GHMatters) P104483.AU
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2016250451 28 Oct 2016
Fig.1
-12016250451 28 Oct 2016
METHOD FOR TREATING SUSPENSIONS OF SOLID PARTICLES IN WATER
The invention relates to a method for treating a suspension of solid particles in water (also called slurry), such as mineral tailings. This method includes the step of forming a film of said suspension, and spraying a water-in-oil emulsion comprising a water soluble polymer on the surface of the film.
The invention relates to a method of mixing a water soluble polymer into an aqueous suspension of solid particles (slurry) for the purpose of increasing the viscosity of the slurry to the point where it will be able to be disposed of as a semi-solid mass.
In the mining industry, fine solids streams in an aqueous suspension need to be 10 combined with a coarse stream for the purpose of removal to a disposal site via trucking or a conveyor belt.
Suspensions of solid particles in water include all types of sludge, slurry, tailings, or waste materials. The suspensions may result from mineral ores processes. They are for instance industrial sludge or tailings and all mine wash and waste products resulting from exploiting mines, such as, for example, coal mines, diamonds mines, phosphate mines, metal mines (alumina, platinum, iron, gold, copper, silver, etc...). Suspensions can also result from drilling mud or tailings derived from the treatment of oil sand. These suspensions of solid particles generally comprise organic and/or mineral particles such as for instance clays, sediments, sand, metal oxides, oil, etc..., mixed with water.
For a long time, and even nowadays, mineral sludge produced by physical or chemical ore treatment methods were stored above ground in retention lagoons, ponds, dam or embankments in semi-liquid form. These large volumes of stored sludge therefore create a real hazard, especially if the dikes break.
Since the traditional storage solutions are obviously dangerous, more and more national regulations have been issued forbidding abandoning these zones. The regulations also call for an obligation to rehabilitate such sites, i.e. treating and consolidating, or requiring strict authorizations more and more difficult to fulfill, or in extreme cases banning the disposal of slurries in containment dams altogether.
The improvement of chemical and mechanical treatments of tailings or sludge is therefore a great challenge that needs to be addressed.
8350325_1 (GHMatters) P104483.AU
-22016250451 28 Oct 2016
There exists both chemical and/or mechanical solution to help the recovery of the solid particles in the form of a semi-solid mass than can be disposed of. The chemical solution consists in adding a flocculant to the suspension of solid particles.
The primary challenge facing the application of a flocculant is the efficient 5 transformation of the product into a relatively viscous stream. Addition of a flocculant in solution leads to rapid consumption of the flocculant and dilution of the slurry whilst adding either a dry powder or inverse emulsion (uninverted form) leads to localized high concentrations of flocculant that are not effectively used in the thickening process.
It is common practice to use synthetic or natural polymers such as coagulants, flocculants, rheology modifiers to treat slurry and tailings in order to separate the solids from the liquid, adjusting their viscosity.
Most of the time, these water soluble polymers which are combined with tailings are in a solution form. Typically, a solution only comprised between 0.5 and 3 g/l of polymer. The rest is water. When in solution, the polymer is completely dissolved in an aqueous media before being in contact with the tailings. The polymer acts immediately into the tailings making the treatment more efficient and more predictive. But the quantity of water added into the tailings may be important and it may be detrimental to the strength of the materials obtained after the treatment. A major problem is also the complexity of the process because of the need of additional equipment to dissolve the polymer in solution.
Some attempts have been made to add a water soluble polymer in different form comprising less water.
WO 96/05146 discloses a process for modifying the flow characteristics of slurries, particularly mineral slurries such as red mud from the Bayer process, using water-soluble polymeric emulsions to increase the slurries’ angle of repose. The emulsion is admixed with the slurry directly or after its dilution with a diluent. More precisely, the emulsion is added into a pipe transporting the slurry to a deposition area.
WO 01/92167 discloses a process for treating mineral slurries by combining polymeric particles of water soluble polymers with said slurries to separate solids from liquid, wherein the polymer particles are added into the pipe transporting the slurry to a deposition area.
8350325_1 (GHMatters) P104483.AU
-32016250451 28 Oct 2016
But these technologies are not efficient enough due to the inability to add the emulsion or the particles of water soluble polymer and mix them effectively with the slurry in the field. In both cases they were looking for an outcome that allowed the slurry to be pumped as a non-viscous liquid that released water on standing and the solid material became a rigid mass.
In many areas, the mining industry is no longer allowed to build new tails dams and alternative methods of disposal need to be developed. These include pressure filtration, belt press filters and centrifuges which remove more water from the slurry and allow it to become solid enough to mix with the coarse rejects and transported by truck or conveyor as a solid to be incorporated in overburden dumps and buried in the mine pit. All of these solutions are capital intensive, labor intensive and use large amounts of flocculant anyway.
There is a need to develop new and rapid processes to treat slurry and tailings to obtain a materials strong enough to be transported to a deposition area without affecting the integrity of the materials, while minimizing the need for additional equipment to remove water from the slurry after thickening in a conventional or paste thickener.
The present invention addresses the above needs by providing a process for treating an aqueous suspension of solid particles (also called slurry), comprising forming a film of said suspension, and spraying a water-in-oil emulsion comprising a water soluble polymer on the surface of the film.
Advantageously, this treatment enables to increase the viscosity of the suspension such as it is handled and transportable to a deposition area without affecting the integrity of the material. Accordingly, the process of the invention creates a semi-solid mass that can be disposed of, preferably without further dewatering.
The spraying of a water-in-oil emulsion on a film, preferably thin film, of suspension of solid particles, allows a very efficient distribution of the water soluble polymer through the suspension (slurry) and allows very rapid and efficient thickening of the slurry. The formation of a film of suspension creates a very high surface area to volume ratio in the slurry which is then sprayed with a mist of a water-in-oil emulsion of water soluble polymer which is generated using a spraying device.
The treated slurry resulted from the process of the invention has a semi-solid mass consistency, more or less solid. It is easily handled, and transportable by conventional means. The treated slurry resulted from the process of the invention may have a paste
8350325_1 (GHMatters) P104483.AU
-42016250451 28 Oct 2016 consistency. In a preferred embodiment the treated slurry does not dewater during transport to a disposal area.
In the present invention, the terms slurry and tailings are used indifferently in place of aqueous suspension of solid particles. The aqueous suspension of solid particles is preferably an aqueous suspension of mineral particles. According to a preferred embodiment the solids content is comprised between 15% and 60% by weight, preferably between 25 and 50% by weight of the suspension. In a preferred embodiment the slurry to treat is the underflow of a thickener. The thickener can be any kind of thickener such as conventional thickener or paste thickener.
In the process of the invention, the flow rate of the slurry is preferably comprised between 5 m3/h and 500m3/h.
According to a preferred embodiment the film is vertical. This film can be either linear or circular. Preferably, the film is linear. The film is more preferably vertical and linear.
This film can be formed by forcing the flow of suspension of solid particles through an aperture or various apertures, for example through a slot or multiple slots.
According to a preferred embodiment the film has a thickness comprised between 1 mm and 15 mm. The skilled person can determine the size of the apertures and/or the number of apertures to obtain such thickness.
The width of the film can be calculated from the mass flow of slurry, the velocity of the slurry film and target thickness of the film and can be easily determined by the skilled person. The width is preferably comprised between 20 cm and 250 cm.
According to a preferred embodiment, when the film is vertical and circular, the diameter of the cylinder is preferably comprised between 45 cm and 100 cm.
Preferably, the speed of the film is comprised between 2 m/s and 10 m/s.
The spraying can be made with at least one spray nozzle, preferably with at least one airless spray nozzle. Advantageously, the spraying can be made on at least one surface of the film.
When the film is vertical and linear, spray nozzles are preferably placed on both sides of the film and the water-in-oil emulsion is sprayed on both sides of the film.
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When the film is vertical and circular, a rotary atomizer is preferably placed in the center of the cylinder such that the water-in-oil emulsion is sprayed all over the internal surface of the cylinder.
Advantageously, the spraying occurs at different location on the length surface of 5 the film.
The angle between the axis of the spraying device and the film is preferably comprised between 60° and 120°, preferably between 85° and 95°.
The pressure at which the water-in-oil emulsion is sprayed is preferably comprised between 10 bar (1.106 Pa) and 200 bar (20.106 Pa).
Advantageously, the water-in-oil emulsion is sprayed to form micro droplet having a diameter preferably comprised between 0.5 pm and 150 pm, preferably between 1 pm and 50 pm. This can be easily done by adapting the spraying device and the pressure of spraying.
Water-in-oil emulsions (or inverse emulsion) are well-known in the art. In the process of the invention, the inverse emulsion is sprayed onto the film. Generally, in the field of the present invention the inverse emulsion is inverted into an oil-in-water emulsion before use in order to release the water-soluble polymer which is in the water droplets of the water-in-oil emulsion, this inversion of the inverse emulsion needs the addition of water and thus a dilution of the water-soluble polymer. In the process of the present invention, where the water-in-oil emulsion (comprising the water-soluble polymer in the water droplets of the emulsion) is sprayed onto the film, there is no need to invert the inverse emulsion. This gives a substantial advantage compared to prior art.
According to a preferred embodiment the water-in-oil emulsion of water soluble polymer comprises an oil phase, at least one water-in-oil emulsifier, optionally at least one oil-in-water emulsifier, an aqueous phase emulsified in the oil phase, said aqueous phase comprising a water soluble polymer, wherein the amount of water soluble polymer is comprised between 20% and 70% by weight based on the emulsion, preferably comprised between 30% and 50%. The oil phase and the emulsifier are typically those used in the field in the invention and are for example described in WO 96/05146 incorporated by reference.
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The total dosage of polymer added to the suspension to be treated is between 50 and 5,000 g per ton of dry solids of suspension, preferably between 250 and 2,500 g/t, and more preferably between 500 and 1,500 g/t, depending on the nature and the composition of the tailings to be treated.
According to a preferred embodiment the water soluble polymer is an acrylamide based polymer, preferably an anionic acrylamide based polymer.
The monomers useful for the preparation of the water soluble polymer according to the invention, are described hereafter.
Non-ionic monomers are preferably selected from the group comprising acrylamide; 10 methacrylamide; N-mono derivatives of acrylamide; N-mono derivatives of methacrylamide;
N,N derivatives of acrylamide; N,N derivatives of methacrylamide; acrylic esters; and methacrylic esters.
The most preferred non-ionic monomer is acrylamide.
Anionic monomers are preferably selected from the group comprising monomers 15 having a carboxylic function and salts thereof; monomers having a sulfonic acid function and salts thereof; monomers having a phosphonic acid function and salts thereof. They include for instance acrylic acid, acrylamide tertio butyl sulfonic acid, methacrylic acid, maleic acid, itaconic acid; and hemi esters thereof.
The most preferred anionic monomers are acrylic acid, acrylamide tertio butyl 20 sulfonic acid (ATBS), and salts thereof. Generally, salts are alkaline salts, alkaline earth salts or ammonium salts.
Cationic monomers are preferably selected from the group comprising dimethylaminoethyl acrylate (DMAEA) quaternized or salified; dimethylaminoethyl methacrylate (DMAEMA) quaternized or salified; diallyldimethyl ammonium chloride (DADMAC); acrylamidopropyltrimethylammonium chloride (APTAC); methacrylamidopropyltrimethylammonium chloride (MAPTAC).
Monomers having a hydrophobic character may also be used as a comonomers for the preparation of the water soluble polymer (anionic or cationic) but at a concentration in weight based on the total monomer content of less than 5%. They are preferably selected from the group comprising (meth)acrylic acid esters having an alkyl, arylalkyl or ethoxylated chain; derivatives of (meth)acrylamide having an alkyl, arylalkyl or dialkyl chain; cationic
8350325_1 (GHMatters) P104483.AU
-72016250451 28 Oct 2016 allyl derivatives; anionic or cationic hydrophobic (meth)acryloyl derivatives; and anionic or cationic monomers derivatives of (meth)acrylamide bearing a hydrophobic chain.
Polymers of the invention are linear or structured. As is known, a structured polymer is a polymer that can have the form of a star, a comb, or has pending groups of pending chains on the side of the main chain. The polymers of the invention, when structured, remain water soluble.
The polymerization can be carried out according to any polymerization techniques well known to a person skilled in the art: solution polymerization, suspension polymerization, gel polymerization, precipitation polymerization, emulsion polymerization (aqueous or reverse) followed by an isolation step in order to obtain a powder, for example a spray drying step, or micellar polymerization followed by an isolation step for example a precipitation step in order to obtain a powder.
The polymerization is generally a free radical polymerization preferably by inverse emulsion polymerization or gel polymerization. By free radical polymerization, we include free radical polymerization by means of U.V. azoic, redox or thermal initiators and also Controlled Radical Polymerization (CRP) techniques or template polymerization techniques.
According to a preferred embodiment the water soluble polymer is a synthetic polymer obtained by the polymerization of at least one non-ionic monomer selected from the group comprising acrylamide; methacrylamide; N-mono derivatives of acrylamide; Nmono derivatives of methacrylamide; N,N derivatives of acrylamide; N,N derivatives of methacrylamide; acrylic esters; and methacrylic esters, and at least one anionic monomers selected from the group comprising monomers having a carboxylic function and salts thereof; monomers having a sulfonic acid function and salts thereof; monomers having a phosphonic acid function and salts thereof.
According to a preferred embodiment the water soluble polymer has an anionicity preferably ranging from between 5 to 70 mol%, preferably from 20 to 50 mol %.
The molecular weight of the water soluble polymer is preferably comprised between 1 and 30 millions daltons, and more preferably between 3 and 20 millions daltons.
The device in which the slurry film is produced and combined with the spray of inverse emulsion is a spraying box. It comprises a box, generally in metal, in which the
8350325_1 (GHMatters) P104483.AU
-82016250451 28 Oct 2016 slurry enters, preferably via a cylinder in which aperture(s), preferably slot(s), are created generally at its bottom. This allows the formation of a slurry film. The device also comprises at least one spraying device generally preferably positioned at right angle with the slurry film, allowing a spray of the inverse emulsion on the surface of the film. More preferably, the devices comprises spraying device on both side of the slurry film. The spraying box device is preferably positioned above grounds in order to have enough place at its bottom to discharge the treated slurry in a vessel, a container, a pump, a screw, a truck, or onto a conveyor belt. The angle between the axis of the spraying device and the film is preferably comprised between 60° and 120°, preferably between 85° and 95°.
Advantageously, the process according to the invention offers a very rapid and very efficient mixing between the water soluble polymer and the suspension of solid particles. In addition, the use of an inverse emulsion enables to limit the quantity of water in the process and thus the dilution of the water-soluble polymer.
One of the significant advantages of the process of the invention is to bypass additional equipment such as filter belt press. Furthermore, the process according to the invention allows an easier transport of the treated slurry to a disposal area. Another advantage is the significant cost reduction.
The dose rate achieved is approximately 1.5 to 2 kg per ton of solids. Previous mixing techniques had only been successful at dose rates in excess of 10 kg per ton.
The treated slurry, obtained by carrying out the process of the invention, is then allowed to fall into a pump, a screw, a truck, or onto a conveyor belt that completes the mixing and allows the development of a slurry that is sufficiently stable to be disposed of, and finally the slurry is removed to a disposal area. During transport to the disposal area, the treated slurry may advantageously go through an in-line static mixer that may help the mixing between the polymer and the slurry. This may also offer a way to decrease the polymer dosage.
The treated slurry may be combined with coarse particles, such as sand, or with additives before the discharge in a disposal area. Suitable additives include, but are not limited to, flocculant, coagulant. In a specific embodiment, the treated slurry is discharge onto a coarse reject conveyor belt that transports the resulting mixture to a disposal area.
It is very interesting to note that the resulting mixture of the treated slurry and coarse did not flow back and that there is no hanging of the material in the disposal area.
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The co-disposal of the material has a high yield stress and produces a mixture with a high angle of repose which does not spread out easily.
When a coagulant is added during transport in the treated slurry it may appear a very rapid dewatering, and the final material is a firm paste.
The suspension of solid particles that enters the process according to the invention can be preliminary treated with at least one flocculent, coagulant or water soluble polymer according to the invention. This enables to first increase the viscosity of the slurry before implementing the process according to the invention.
The present invention also relates to a device to carry out the process of the invention. Such device comprises:
- a box, generally in metal, in which the slurry enters via a pipe, preferably via a cylinder;
- a pipe by which the slurry enters the box in which aperture(s), preferably slot(s), are created generally at its bottom to form a slurry film;
- at least one spraying device generally preferably positioned at right angle with the slurry film, allowing a spray of the inverse emulsion on the surface of the film.
More preferably, the devices comprise spraying device on both side of the slurry film. The spraying box device is preferably positioned above grounds in order to have enough place at its bottom to discharge the treated slurry in a vessel, a container, a pump, a screw, a truck, or onto a conveyor belt. The angle between the axis of the spraying device and the film is preferably comprised between 60° and 120°, preferably between 85° and 95°.
The invention will now be described by means of examples and figures which are only given to illustrate the subject matter of the invention, which is in no way restricted to them.
Figure 1 is a schematic side view of the spray box in which the slurry film is produced and combined with the spray of inverse emulsion. The slurry (A) enters into a cylinder (1) in the spray box (2), said cylinder having slots at the bottom. Two high pressure airless nozzles (3) are installed on each side of the spray box. The treated slurry falls into a concrete pump hopper (4), and is transportable to a disposal area.
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Figure 2 is a schematic top view of the spray box (2) with the cylinder (1), the slots (5) placed at the bottom of the cylinder (1) and the spraying device (3) on both side of the slurry film.
Figure 3 is a schematic view of the cylinder (1) that creates a slurry film (6) on which 5 an inverse emulsion is sprayed on both side of the film by four spraying devices (3).
example:
A coal slurry taken directly from the bottom of a thickener, and having a solid contents of 40% by weight, is directed to a spray box, as described in Figures 1 and 2, where the slurry is forced through a slot to create a slurry film having a thickness of 3 mm.
An inverse emulsion of a copolymer of acrylamide (70 mol%) and sodium acrylate (30 mol%), and having a molecular weight of 15 millions daltons, is sprayed by 2 or 4 high pressure airless spray nozzles depending on the volume of emulsion required to achieve the desired degree of solidification of the slurry.
The inverse emulsion is sprayed at a pressure of 90 bars. A mist of fine droplets of the inverse emulsion enters in contact with the slurry film increasing rapidly the viscosity of the slurry.
After contact between the slurry and the emulsion, the material falls into the suction of a dual piston slurry pump which then transfers the slurry onto a conveyor belt. The slurry falls onto a stream of coarse rejects on the belt and is disposed off by trucking back to the disposal area.
The dose rate achieved is only 1.5 to 2 kg per ton of solids, whereas previous mixing techniques had only been successful at dose rates in excess of 10 kg per ton.
This example shows how the process of the invention is rapid and efficient, and how it allows to treat slurry and tailings to obtain a materials strong enough to be transported to a deposition area without affecting the integrity of the materials. It also shows that the process of the invention is cost efficient compare to conventional processes.
In the claims which follow and in the preceding description of the invention, except where the context requires otherwise due to express language or necessary implication, the word “comprise” or variations such as “comprises” or “comprising” is used in an
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- ii 2016250451 28 Oct 2016 inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention.
It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country.
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| AU2016250451A AU2016250451B2 (en) | 2016-10-28 | 2016-10-28 | Method for treating suspensions of solid particles in water |
| CA2984071A CA2984071A1 (en) | 2016-10-28 | 2017-10-27 | Method for treating suspensions of solid particles in water |
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| GB862488A (en) * | 1959-07-27 | 1961-03-08 | Kurashiki Rayon Kk | Saponification apparatus and method |
| US3794299A (en) * | 1971-09-23 | 1974-02-26 | Chem Trol Pollution Services | Centrifugal reactor |
| DE2850271C3 (en) * | 1978-11-20 | 1981-10-01 | Degussa Ag, 6000 Frankfurt | Device for intensive mixing of liquids |
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