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Patent US5171427 - Sulfonated and carboxylate collector compositions useful in the flotation of ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsDialkylated aryl sulfonic acids or salts thereof or their mixture are useful as collectors in the flotation of minerals, particularly oxide minerals. Collector compositions comprising these salts and oleic acid are particularly useful in hard water. Collector compositions comprising these salts and sulfide...http://www.google.com/patents/US5171427?utm_source=gb-gplus-sharePatent US5171427 - Sulfonated and carboxylate collector compositions useful in the flotation of mineralsAdvanced Patent SearchPublication numberUS5171427 APublication typeGrantApplication numberUS 07/800,186Publication dateDec 15, 1992Filing dateNov 27, 1991Priority dateFeb 23, 1990Fee statusLapsedPublication number07800186, 800186, US 5171427 A, US 5171427A, US-A-5171427, US5171427 A, US5171427AInventorsRichard R. Klimpel, Donald E. Leonard, Gordon D. McCannOriginal AssigneeThe Dow Chemical CompanyExport CitationBiBTeX, EndNote, RefManPatent Citations (33), Non-Patent Citations (10), Referenced by (4), Classifications (11), Legal Events (5) External Links: USPTO, USPTO Assignment, EspacenetSulfonated and carboxylate collector compositions useful in the flotation of mineralsUS 5171427 AAbstract Dialkylated aryl sulfonic acids or salts thereof or their mixture are useful as collectors in the flotation of minerals, particularly oxide minerals. Collector compositions comprising these salts and oleic acid are particularly useful in hard water. Collector compositions comprising these salts and sulfide collectors such as xanthates are useful in flotations conducted at natural pH of the slurry.
What is claimed is: 1. A process for the recovery of minerals by froth flotation comprising subjecting an aqueous slurry comprising particulate minerals to froth flotation in the presence of a collector composition comprising (1) a sulfonic component comprising one or more dialkylated benzene monosulfonic acids or their salts and (2) a carboxylic component comprising at least one C.sub.1-24 carboxylic acid or salt thereof under conditions such that the minerals to be recovered are floated and recovered.
2. The process of claim 1 wherein the sulfonic component and carboxylic component are added to the slurry simultaneously.
3. The process of claim 1 wherein the carboxylic component is added to the slurry prior to the addition of the sulfonic component.
4. The process of claim 1 wherein the recovered mineral comprises graphite and the aqueous slurry further comprises pulped paper.
5. The process of claim 1 wherein the carboxylic component is a fatty acid or salt thereof or a mixture of such acids or salts.
6. The process of claim 5 wherein the fatty acid is selected from the group consisting of oleic, linoleic, linolenic, myristic, palmitic, strearic, palmitoleic, caprylic, capric and lauric acids or salts thereof or a mixture of such acids or salts.
7. The process of claim 6 wherein the acid is selected from the group consisting of oleic, linoleic and linolenic acids or salts thereof or a mixture of such acids or salts.
8. The process of claim 1 wherein the weight ratio of the sulfonic component to the carboxylic component is between 98:2 and 30:70.
9. The process of claim 1 wherein the collector composition is blended prior to addition to the aqueous slurry.
10. The process of claim 1 wherein the minerals are recovered from an oxide ore.
11. The process of claim 10 wherein the oxide ore is selected from the group consisting of copper oxide, iron oxide, nickel oxide, phosphorus oxide, aluminum oxide and titanium oxide ores.
12. The process of claim 1 wherein the minerals are recovered from a sulfide ore.
13. The process of claim 1 wherein the minerals are recovered from an ore comprising both sulfur-containing and oxygen-containing minerals.
14. The process of claim 1 wherein the sulfonic component and carboxylic component are blended prior to addition to the slurry.
CROSS REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of U.S. Ser. No. 628,264 now abandoned, filed Dec. 17, 1990, which is a continuation-in-part of co-pending application Ser. No. 484,038, filed Feb. 23, 1990, now issued as U.S. Pat. No. 5,015,367 which is related to application Ser. No. 336,143, filed Apr. 11, 1989, now abandoned, which is a continuation-in-part of application Ser. No. 310,272, filed Feb. 13, 1989, now abandoned.
BACKGROUND OF THE INVENTION This invention is related to the use of chemical collector compositions in the recovery of minerals by froth flotation.
The minerals and their associated gangue which are treated by froth flotation generally do not possess sufficient hydrophobicity or hydrophilicity to allow adequate separation. Therefore, various chemical reagents are often employed in froth flotation to create or enhance the properties necessary to allow separation. Collectors are used to enhance the hydrophobicity and thus the floatability of different mineral values. Collectors must have the ability to (1) attach to the desired mineral species to the relative exclusion of other species present: (2) maintain the attachment in the turbulence or shear associated with froth flotation: and (3) render the desired mineral species sufficiently hydrophobic to permit the required degree of separation.
SUMMARY OF THE INVENTION The present invention is a process for the recovery of minerals by froth flotation comprising subjecting an aqueous slurry comprising particulate minerals to froth flotation in the presence of a collector comprising (1) at least one alkylated aryl monosulfonic acid or salt thereof and (2) at least one C.sub.1-24 carboxylic acid or salt thereof under conditions such that the minerals to be recovered are floated and recovered. The recovered minerals may be the mineral that is desired or may be undesired contaminants. Additionally, the froth flotation process of this invention may utilize frothers and other flotation reagents known in the art.
The flotation process of this invention results in improvements in selectivity and thus the grade of minerals recovered from oxide and/or sulfide ores while generally maintaining or increasing overall recovery levels of the mineral desired to be recovered. It is surprising that the use of sulfonic acids or salts thereof in conjunction with the carboxylic acids or salts thereof results in improvements in selectivity and/or recovery of mineral values when compared to the use of either the sulfonic or carboxylic component alone. The use of the combination is particularly effective in water containing metal salts such as the hard water typically encountered in mineral processing.
DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS The flotation process of this invention is useful in the recovery of mineral values from a variety of ores, including oxide ores as well as sulfide ores and mixed ores. The oxide or oxygen-containing minerals which may be treated by the practice of this invention include carbonates, sulfates, hydroxides and silicates as well as oxides.
Non-limiting examples of specific oxide ores which may be collected by froth flotation using the process of this invention include those containing cassiterite, hematite, cuprite, vallerite, calcite, talc, kaolin, apatite, dolomite, bauxite, spinel, corundum, laterite, azurite, rutile, magnetite, columbite, ilmenite, smithsonite, anglesite, soheelite, chromite, cerussite, pyrolusite, malachite, chrysocolla, zincite, massicot, bixbyite, anatase, brookite, tungstite, uraninite, gummite, brucite, manganite, psilomelane, goethite, limonite, chrysoberyl, microlite, tantalite, topaz and samarskite. One skilled in the art will recognize that the froth flotation process of this invention will be useful for the processing of additional ores including oxide ores, wherein oxide is defined to include carbonates, hydroxides, sulfates and silicates as well as oxides.
In one embodiment, the aryl monosulfonic acid or sulfonate of this invention comprises an aromatic core having up to about five alkyl substituents and a sulfonic acid or sulfonate moiety. For purposes of this invention, the term sulfonate will include both the sulfonic acid moiety and the sulfonate moiety. It is preferred that this embodiment of the monosulfonate have two to three alkyl substituents and more preferred that it have two. The aromatic core preferably comprises phenol, benzene, napthalene, anthracene and compounds corresponding to the formula ##STR1## wherein X represents a covalent bond: --(CO)--; or R wherein R is a linear or branched alkyl group having one to three carbon atoms. It is preferred that the aromatic core is benzene, napthalene or biphenyl and more preferred that it is benzene or napthalene and most preferred that it is benzene.
The two or more alkyl substituents may be the same or may be different and may be ortho, para or meta to each other with para and meta being preferred and para being more preferred. The alkyl groups may be the same or different and may be substituted or unsubstituted and preferably contain from 3 to about 24 carbon atoms. More preferably each of the alkyl groups contains from about 6 to about 18 carbon atoms and most preferably about 8 to about 12 carbon atoms. The alkyl groups will contain a total of at least about 10, preferably at least about 12 and more preferably at least about 16 carbon atoms. The maximum total number of carbon atoms in the alkyl groups is preferably no greater than about 32 and more preferably no greater than about 24. The alkyl groups can be linear, cyclic or branched with linear or branched being preferred. The monosulfonates are available commercially or may be prepared by methods known in the art. For example, they may be prepared by alkylation of aryl centers using nucleophilic aromatic alkylation using alkyl halides, alcohols or alkenes as the alkylation agent with appropriate catalysts.
In this embodiment of the present invention, the aryl monosulfonate contains at least two alkyl substituents. It will be recognized by one skilled in the art that methods of production of substituted aryl monosulfonates will sometimes result in mixtures of non-substituted, mono-substituted, di-substituted and higher substituted aryl sulfonates. Such mixtures are operable in the practice of this invention. It is preferred that at least about 15 percent of the alkylated aryl sulfonates contain two or more alkyl substituents. More preferably at least about 35 percent of the alkylated aryl sulfonates contain at least two alkyl substituents and most preferably at least about 50 percent of the alkylated aryl sulfonates contain at least two alkyl substituents.
The aryl monosulfonate collector of this embodiment of the invention is preferably a dialkylated or higher alkylated benzene sulfonate collector and corresponds to the following formula or to a mixture of compounds corresponding to the formula: ##STR2## wherein each R is independently in each occurrence a saturated alkyl or substituted saturated alkyl radical or an unsaturated alkyl or substituted unsaturated alkyl radical: m is at least two and no greater than five: each M is independently hydrogen, an alkali metal, alkaline earth metal, or ammonium or substituted ammonium. Preferably, the R group(s) are independently in each occurrence an alkyl group having from about three to about 24, more preferably from about 6 to about 18 carbon atoms and most preferably about 8 to about 12 carbon atoms with the proviso that the total number of carbon atoms in the alkyl groups is at least 10, preferably at least about 12 and preferably at least 16 and no greater than about 32, preferably no greater than about 24. The alkyl groups can be linear, branched or cyclic with linear or branched radicals being preferred. The M.sup.+ ammonium ion radicals are of the formula (R').sub.3 HN.sup.+ wherein each R' is independently hydrogen, a C.sub.1 -C.sub.4 alkyl or a C.sub.1 -C.sub.4 hydroxyalkyl radical. Illustrative C.sub.1 -C.sub.4 alkyl and hydroxyalkyl radicals include methyl, ethyl, propyl, isopropyl, butyl, hydroxymethyl and hydroxyethyl. Typical ammonium ion radicals include ammonium (N.sup.+ H.sub.4), methylammonium (CH.sub.3 N.sup.+ H.sub.3), ethylammonium (C.sub.2 H.sub.5 N.sup.+ H.sub.3), dimethylammonium ((CH.sub.3).sub.2 N.sup.+ H.sub.2), methylethylammonium (CH.sub.3 N.sup.+ H.sub.2 C.sub.2 H.sub.5), trimethylammonium ((CH.sub.3).sub.3 N.sup.+ H), dimethylbutylammonium ((CH.sub.3).sub.2 N.sup.+ HC.sub.4 H.sub.9), hydroxyethylammonium (HOCH.sub.2 CH.sub.2 N.sup.+ H.sub.3) and methylhydroxyethylammonium (CH.sub.3 N.sup.+ H.sub.2 CH.sub.2 CH.sub.2 OH). Preferably, each M is hydrogen, sodium, calcium, potassium or ammonium.
In a particular version of this preferred embodiment of the dialkylated aryl sulfonate, the alkyl groups are different. In this embodiment, it is preferred that one alkyl group is a C.sub.1-3 alkyl group and the second alkyl group is a C.sub.10-24 alkyl group. In the preparation of these unsymmetrical sulfonates, alphaolefins, alkyl halides and alcohols having sufficient carbon atoms to provide the desired hydrophobicity are used as alkylating agents. Typically, groups having from 10 to 24, preferably from 16 to 24 carbon atoms are used. The species which is alklyated is typically toluene, cumene, ethyl benzene, xylene. The alklyated species is sulfonated by methods known in the art.
In a second preferred embodiment of this invention, the alkylated aryl monosulfonic acid or salt thereof is the alkylated diaryl oxide sulfonic acid or sulfonate described in U.S. Pat. No. 5,015,367. In a preferred embodiment, this monosulfonate is a diphenyl oxide collector and corresponds to the following formula or to a mixture of compounds corresponding to the formula: ##STR3## wherein each R is independently a saturated alkyl or substituted saturated alkyl radical or an unsaturated alkyl or substituted unsaturated alkyl radical; each m and n is independently 0, 1 or 2: each M is as defined above. Each x and y may independently by 0 or 1 with the proviso that the sum of x and y is one. Preferably, the R group(s) is independently an alkyl group having from about 1 to about 24, more preferably from about 6 to about 24 carbon atoms, even more preferably about 6 to about 16 carbon atoms and most preferably about 10 to about 16 carbon atoms. The alkyl groups can be linear, branched or cyclic with linear or branched radicals being preferred. It is also preferred that m and n are each one. The M.sup.+ ammonium ion radicals are of the formula (R').sub.3 HN.sup.+ wherein each R' is independently hydrogen, a C.sub.1 -C.sub.4 alkyl or a C.sub.1 -C.sub.4 hydroxyalkyl radical. Illustrative C.sub.1 -C.sub.4 alkyl and hydroxyalkyl radicals include methyl, ethyl, propyl, isopropyl, butyl, hydroxymethyl and hydroxyethyl. Typical ammonium ion radicals include ammonium (N.sup.+ H.sub.4), methylammonium (CH.sub.3 N.sup.+ H.sub.3), ethylammonium (C.sub.2 H.sub.5 N.sup.+ H.sub.3), dimethylammonium ((CH.sub.3).sub.2 N.sup.+ H.sub.2), methylethylammonium (CH.sub.3 N.sup.+ H.sub.2 C.sub.2 H.sub.5), trimethylammonium ((CH.sub.3).sub.3 N.sup.+ H), dimethylbutylammonium ((CH.sub.3).sub.2 N.sup.+ HC.sub.4 H.sub.9), hydroxyethylammonium (HOCH.sub.2 CH.sub.2 N.sup.+ H.sub.3) and methylhydroxyethylammonium (CH.sub.3 N.sup.+ H.sub.2 CH.sub.2 CH.sub.2 OH). Preferably, each M is hydrogen, sodium, calcium, potassium or ammonium.
The second required component of the collector is a C.sub.1-24 carboxylic acid or salt thereof. Examples of useful materials include acetic acid, citric acid, tartaric acid, maleic acid, oxalic acid, ethylenediamine dicarboxylic acid, ethyleneamine tetracarboxylic acid and fatty acids. Fatty acids or their salts are particularly preferred. Illustrative, but non-limiting examples of such acids include oleic acid, linoleic acid, linolenic acid, myristic acid, palmitic acid, strearic acid, palmitoleic acid, caprylic acid, capric acid, lauric acid and mixtures thereof. One example of a mixture of fatty acids is tall oil. Preferred fatty acids include oleic acid, linoleic acid, linolenic acid and mixtures thereof. The fatty acids may be used in the acid form or may be used in salt form. As used herein, the terms "acid" and"carboxylate" include both the acid and salt form.
The collector comprising the monosulfonate and the carboxylate is particularly useful when hard water is used in the flotation process. In the context of this invention, hard water is water having an equivalent conductivity of ionic strength equal to or greater than that of 50 ppm Na.sup.+ equivalents. An effective amount of carboxylate is that amount which, when replacing an equal amount of sulfonate, results in improved recovery of the desired mineral. The amount of carboxylate used is preferably at least about 1 weight percent, more preferably at least about 2 weight percent and most preferably at least about 5 weight percent, based on the combined weight of the sulfonate and carboxylate. The maximum amount of carboxylate used is preferably no greater than about 50 weight percent, more preferably no greater than about 40 weight percent, and most preferably no greater than about 30 weight percent. As will be recognized by one skilled in the art, the optimum amount of carboxylate used will depend on the degree of hardness of the water used in flotation, the minerals to be recovered and other variables in the flotation process.
The carboxylate may be added to the flotation system prior to the addition of the sulfonate or they may be added simultaneously. It is preferred, however, that the sulfonate and carboxylate be formulated and then added to the flotation system. The collector composition may be formulated in a water based mixture or a hydrocarbon based mixture depending on the particular application. When a water formulation is used, the sulfonate and/or the carboxylate are in the salt form. When a hydrocarbon based formulation is used, one or both of the carboxylate and sulfonate are in the acid form. Typical hydrocarbon formulations would include any saturated hydrocarbon, kerosene, fuel oil, alcohols, alkylene oxide compounds, and organic solvents such dodecene, dimethylsulfoxide, limonene and dicyclopentadiene.
The type of collector formulation and whether the acid or salt form is used also impacts the preferred ratio of sulfonate to carboxylate. When the salt form is used, the amount of carboxylate used is preferably at least about 1 weight percent, more preferably at least about 2 weight percent and most preferably at least about 5 weight percent, based on the combined weight of the sulfonate and carboxylate. The maximum amount of carboxylate used is preferably no greater than about 60 weight percent, more preferably no greater than about 40 weight percent, and most preferably no greater than about 25 weight percent. When the acid form is used, the amount of carboxylate used is preferably at least about 1 weight percent, more preferably at least about 5 weight percent and most preferably at least about 10 weight percent, based on the combined weight of the sulfonate and carboxylate. The maximum amount of carboxylate used is preferably no greater than about 70 weight percent, more preferably no greater than about 50 weight percent, and most preferably no greater than about 30 weight percent.
In preferred embodiments, both the sulfonic and carboxylic components are in either the salt form or the acid form. Mixed formulations where one is a salt and the other an acid are possible, but are generally not preferred. The acid form, or hydrocarbon based formulations, are generally preferred in those situations where pH regulators are used to raise the pH above 7. In those instances where the flotation is conducted at a natural pH, it is typically preferred to use the salt form or water based formulations.
The collector composition can be used in any concentration which gives the desired selectivity and recovery of the desired mineral values. In particular, the concentration used is dependent upon the particular mineral to be recovered, the grade of the ore to be subjected to the froth flotation process and the desired quality of the mineral to be recovered.
Additional factors to be considered in determining dosage levels include the amount of surface area of the ore to be treated. As will be recognized by one skilled in the art, the smaller the particle size, the greater the surface area of the ore and the greater the amount of collector reagents needed to obtain adequate recoveries and grades. Typically, oxide mineral ores must be ground finer than sulfide ores and thus require very high collector dosages or the removal of the finest particles by desliming. Conventional processes for the flotation of oxide minerals typically require a desliming step to remove the fines present and thus permit the process to function with acceptable collector dosage levels. The collector composition of the present invention functions at acceptable dosage levels with or without desliming.
Preferably, the concentration of the collector, including the sulfonate and carboxylate, is at least about 0.001 kg/metric ton, more preferably at least about 0.05 kg/metric ton. It is also preferred that the total concentration of the collector is no greater than about 5.0 kg/metric ton and more preferred that it is no greater than about 2.5 kg/metric ton. In general, to obtain optimum performance from the collector, it is most advantageous to begin at low dosage levels and increase the dosage level until the desired effect is achieved. While the increases in recovery and grade obtained by the practice of this invention increase with increasing dosage, it will be recognized by those skilled in the art that at some point the increase in recovery and grade obtained by higher dosage is offset by the increased cost of the flotation chemicals. It will also be recognized by those skilled in the art that varying collector dosages are required depending on the type of ore and other conditions of flotation. Additionally, the collector dosage required has been found to be related to the amount of mineral to be collected. In those situations where a small amount of a mineral susceptible to flotation using the process of this invention, a very low collector dosage is needed due to the selectivity of the collector.
It has been found advantageous in the recovery of certain minerals to add the collector composition to the flotation system in stages. By staged addition, it is meant that a part of the collector dose is added: froth concentrate is collected: an additional portion of the collector is added: and froth concentrate is again collected. The total amount of collector used is preferably not changed when it is added in stages. This staged addition can be repeated several times to obtain optimum recovery and grade. The number of stages in which the collector is added is limited only by practical and economic constraints. Preferably, no more than about six stages are used.
In addition to the collector of this invention, other conventional reagents or additives may be used in the flotation process. Examples of such additives include various depressants and dispersants well-known to those skilled in the art. Additionally, the use of hydroxy-containing compounds such as alkanol amines or alkylene glycols has been found to useful in improving the selectivity to the desired mineral values in systems containing silica or siliceous gangue. In addition, frothers may be and typically are used. Frothers are well known in the art and reference is made thereto for the purposes of this invention. Examples of useful frothers include polyglycol ethers and lower molecular weight frothing alcohols. Additionally, the collectors of this invention may be used with hydrocarbon as an extender. Examples of hydrocarbons useful in this context include are those hydrocarbons typically used in flotation. Non-limiting examples of such hydrocarbons include fuel oil, kerosene and motor oil.
The collector composition of this invention may also be used in conjunction with other collectors. For example, it has been found that in the flotation of sulfide mineral containing ores, the use of the collector of this invention with sulfide thiol collectors such as xanthates, dithiol phosphates and trithiol carbonates is advantageous. The use of a collector composition comprising both sulfide collectors and alkylated aryl monosulfonate collectors is particularly advantageous when it is desired to conduct the flotation at natural or non-elevated slurry pH.
The collector composition of this invention may also be used in conjunction with other conventional collectors in other ways. For example, the collector of this invention may be used in a two-stage flotation in which the first flotation using the collector of this invention recovers primarily oxide minerals while a second stage flotation using conventional collectors recovers primarily sulfide minerals or additional oxide minerals. When used in conjunction with conventional collectors, a two-stage flotation may be used wherein the first stage comprises the process of this invention and is done at the natural pH of the slurry. The second stage involves conventional collectors and is conducted at an elevated pH. It should be noted that in some circumstances, it may be desirable to reverse the stages. Such a two-stage process has the advantages of using less additives to adjust pH and also permits a more complete recovery of the desired minerals by conducting flotation under different conditions.
A particular advantage of the collector of the present invention is that additional additives are not required to adjust the pH of the flotation slurry. The flotation process utilizing the collector of the present invention operates effectively at typical natural ore pH's ranging from about 5 or lower to about 9. This is particularly important when considering the cost of reagents needed to adjust slurry pH from a natural pH of around 7.0 or lower to 9.0 or 10.0 or above which is typically necessary using conventional carboxylic xanthate collectors. As noted above, a collector composition comprising the collector of the present invention and a xanthate collector is effective at a lower pH than a xanthate collector used alone.
It is possible to take advantage of the tendency of different minerals to float at different pH levels using the process of this invention. This makes it possible to do one flotation at one pH to optimize flotation of a particular species. The pH can then be adjusted for a subsequent run to optimize flotation of a different species thus facilitating separation of various minerals found together.
EXAMPLE 1--SEPARATION OF APATITE AND SILICA A series of 30-g samples of a -10 mesh (U.S.) mixture of 10 percent apatite (Ca.sub.5 (Cl,F)[PO.sub.4 ].sub.3) and 90 percent silica (SiO.sub.2) is prepared. Each sample of ore is ground with 15 g of water in a rod mill (2.5 inch diameter with 0.5 inch rods) for 240 revolutions. The water used contains 5 parts Na.sup.+, 4 parts Ca.sup.++, 2 parts Mg.sup.++, and 1 part Fe.sup.+++ in the appropriate amounts to produce the ionic strengths indicated in the Table I. The ionic strengths are measured in Na.sup.+ equivalents using a conductivity cell. The resulting pulp is transferred to a 300 ml flotation cell.
The pH of the slurry is left at natural ore pH of 6.7. After addition of the collector (in the sodium salt form) as shown in Table I, the slurry is allowed to condition for one minute. Next, the frother, a polyglycol ether available commercially from The Dow Chemical Co. as Dowfroth brand frother, is added in an amount equivalent to 0.050 kg per ton of dry ore and the slurry is allowed to condition an additional minute.
The float cell is agitated at 1800 RPM and air is introduced at a rate of 2.7 liters per minute. The froth concentrate is collected by standard hand paddling for four minutes after the start of the introduction of air into the cell. Samples of the concentrate and the tailings are dried and analyzed as described in the previous examples. The results obtained are presented in Table I below.
TABLE I__________________________________________________________________________                    Phosphorus                            Ionic               Dosage                    Recovery and                            Strength of               (kg/met-                    Grade   Water (ppmRun   Collector        ric ton)                    Rec Gr  Na+)__________________________________________________________________________ 1 Dodecyl benzene sulfonate               0.150                    0.614                        0.141                            1000   Oleate.sup.1     0.150 2 Di-dodecyl benzene sulfonate               0.150                    0.887                        0.140                            1000   Oleate.sup.1     0.050 3 Di-dodecyl benzene sulfonate               0.150                    0.904                        0.138                            1000   Oleate.sup.1     0.100 4 Di-dodecyl benzene sulfonate               0.150                    0.783                        0.136                            1000   Oleate.sup.1     0.150 5 Di-dodecyl benzene sulfonate               0.150                    0.865                        0.141                             100   oleate.sup.1     0.150 6 Di-dodecyl benzene sulfonate               0.150                    0.840                        0.136                             250   Oleate.sup.1     0.150 7 Di-dodecyl benzene sulfonate               0.150                    0.802                        0.135                             500   Oleate.sup.1     0.150 8 Di-dodecyl benzene sulfonate               0.150                    0.607                        0.137                            1000   Oleate.sup.2     0.150 9 Di-dodecyl benzene sulfonate               0.150                    0.575                        0.137                            1000   Oleate.sup.3     0.15010 Di-nonyl napthalene sulfonate               0.150                    0.866                        0.142                            1000   Oleate.sup.1     0.15011 C.sub.24 benzene sulfonate               0.150                    0.629                        0.136                            1000   Oleate.sup.1     0.15012 Mixture of di-octyl, di-nonyl and di-               0.150                    0.734                        0.140                            1000   decyl benzene sulfonate   Oleate.sup.1     0.15013 Mixture of di-octyl, di-nonyl and di-               0.150                    0.681                        0.140                            1000   decyl napthalene sulfonate   Oleate.sup.1     0.15014 Dodecyl diphenyl oxide sulfonate               0.150                    0.607                        0.135                            1000   Oleate.sup.1     0.05015 Di-dodecyl diphenyl oxide sulfonate               0.150                    0.886                        0.140                            1000   Oleate.sup.1     0.05016 Di-dodecyl diphenyl oxide sulfonate               0.150                    0.914                        0.144                            1000   Oleate.sup.1     0.10017 Di-dodecyl diphenyl oxide sulfonate               0.150                    0.810                        0.138                            1000   Oleate.sup.1     0.15018 Di-dodecyl diphenyl oxide sulfonate               0.150                    0.934                        0.140                             100   Oleate.sup.1     0.15019 Di-dodecyl diphenyl oxide sulfonate               0.150                    0.888                        0.139                             250   Oleate.sup.1     0.15020 Di-dodecyl diphenyl oxide sulfonate               0.150                    0.846                        0.137                             500   Oleate.sup.1     0.15021 Di-dodecyl diphenyl sulfonate               0.150                    0.629                        0.140                            1000   Oleate.sup.2     0.15022 Didodecyl diphenyl sulfonate.sup.3               0.150                    0.583                        0.139                            1000   Oleate.sup.3     0.15023 Di-dodecyl benzene sulfonate               0.150                    0.811                        0.140                            1000   Tall oil fatty acid, sodium salt.sup.1               0.15024 Di-dodecyl benzene sulfonate               0.150                    0.762                        0.137                            1000   Oxalic acid, sodium salt.sup.1               0.15025 Di-dodecyl benzene sulfonate               0.150                    0.714                        0.136                            1000   Tartaric acid, sodium salt.sup.1               0.15026 Di-dodecyl benzene sulfonate               0.150                    0.704                        0.139                            1000   Dodecanate.sup.1 0.15027 Di-dodecyl benzene sulfonate               0.150                    0.639                        0.135                            1000   Citric acid, sodium salt.sup.1               0.15028 Di-dodecyl benzene sulfonate               0.150                    0.711                        0.138                            1000   Ethylene diamine dicarboxylate.sup.1               0.15029 Di-dodecyl benzene sulfonate               0.150                    0.754                        0.139                            1000   Ethylene diamine tetracarboxylate.sup.1               0.15030 Di-dodecyl benzene sulfonate               0.150                    0.685                        0.136                            1000   Hydroxy ethyl iminodiacetate.sup.1               0.15031 Di-dodecyl benzene sulfonate               0.125                    0.876                        0.141                             100   Oleate.sup.1     0.02532 Di-dodecyl benzene sulfonate               0.125                    0.867                        0.140                             250   Oleate.sup.1     0.02533 Di-dodecyl benzene sulfonate               0.125                    0.844                        0.139                             500   Oleate.sup.1     0.02534 Di-dodecyl benzene sulfonate               0.125                    0.830                        0.138                            1000   Oleate.sup.1     0.02535 Di-dodecyl benzene sulfonate               0.150                    0.641                        0.134                            1000   Oleate.sup.4     0.15036 Di-dodecyl diphenyl oxide sulfonate               0.150                    0.651                        0.132                            1000   Oleate.sup.4     0.150.sup. 37.sup.5   Dodecyl benzene sulfonate               0.300                    0.066                        0.084                            1000.sup. 38.sup.5   Di-dodecyl benzene sulfonate               0.150                    0.610                        0.135                            1000.sup. 39.sup.5   Di-dodecyl benzene sulfonate               0.300                    0.755                        0.108                            1000.sup. 40.sup.5   Di-nonyl napthalene sulfonate               0.300                    0.514                        0.124                            1000.sup. 41.sup.5   Di-dodecyl diphenyloxide sulfonate               0.300                    0.761                        0.112                            1000.sup.  42.sup.5   Oleate           0.300                    0.666                        0.134                            1000.sup. 43.sup.5   Sodium salt of tall oil fatty acid               0.300                    0.655                        0.119                            1000.sup. 44.sup.5   C.sub.24 benzene sulfonate               0.300                    0.188                        0.125                            1000__________________________________________________________________________ .sup.1 Components blended together before addition to cell. .sup.2 Components added to cell separately and simultaneously. .sup.3 Carboxylate added to cell first, conditioned for one minute followed by addition of sulfonate. .sup.4 Sulfonate added to cell first, conditioned for one minute followed by carboxylic addition. .sup.5 Not an embodiment of the invention.
The data in Table I demonstrate the effectiveness of the present invention. It is of particular interest to note that the collector composition results in efficient recovery of the desired minerals in water containing high amounts of salts. When compared with either the sulfonate or carboxylate component alone, the combination results in enhanced recoveries. The importance of preferred ratios of sulfonate to carboxylate is demonstrated in, for example, Runs 15-17 and Runs 2-4.
EXAMPLE 2--HALLIMOND TUBE FLOTATION OF RUTILE, APATITE, HEMATITE AND SILICA About 1.1 g of either the specified mineral or silica is sized to about -60 to +120 U.S. mesh and placed in a small bottle with about 20 ml of deionized water. The mixture is shaken 30 seconds and then the water phase containing some suspended fine solids or slimes is decanted. This desliming step is repeated several times.
A 150-ml portion of deionized water is placed in a 250-ml glass beaker. Next, 2.0 ml of a 0.10 molar solution of potassium nitrate is added as a buffer electrolyte. The pH is adjusted to 6.5 with the addition of 0.10N HCl and/or 0.10N NaOH. Next, a 1.0-g portion of the deslimed mineral is added along with deionized water to bring the total volume to about 180 ml. The specified sulfonate collector and sodium oleate are preblended, added to the slurry and allowed to condition with stirring for 15 minutes. The pH is monitored and adjusted as necessary using HCl and NaOH. All collectors indicated are first converted to the Na.sup.+ salt form before addition.
The floated and unfloated material is filtered out of the slurry and oven dried at 100 recoveries of each mineral and silica are reported in Table I below. After each test, all equipment is washed with concentrated HCl and rinsed with 0.10N NaOH and deionized water before the next run.
The recovery of each mineral and silica, respectively, reported is that fractional portion of the original mineral placed in the Hallimond tube that is recovered. Thus, a recovery of 1.00 indicates that all of the material is recovered. It should be noted that although the recovery of each mineral and silica, respectively, is reported together, the data is actually collected in four experiments done under identical conditions. It should further be noted that a low silica recovery suggests a selectivity to the the desired minerals. The values given for the various mineral recoveries generally are correct to .+-05 and those for silica recovery are generally correct to .+-03.
The ion concentrations are indicated for those runs where metal ions have been deliberately added to the processing water for flotation. The ratio of metal ions added is five parts Na.sup.+, two parts Mg.sup.++, and one part Fe.sup.+++ with the total amount of these ions added being determined by measuring the ionic strength of the water in equivalent Na.sup.+ concentration as measured by a conductivity cell.
TABLE II__________________________________________________________________________                                      Ionic                Sodium                Strength           Dosage                Oleate                     Fractional Recovery                                      WaterRun Collector (Na + Salt)           (kg/kg)                (kg/kg)                     Rutile                         Apatite                             Hematite                                  Silica                                      (ppm/Na+)__________________________________________________________________________1   Di-dodecyl benzene           0.045                0.005                     0.617                         0.568                             0.500                                  0.043                                      1000    monosulfonate2   Di-dodecyl benzene           0.040                0.010                     0.880                         0.863                             0.781                                  0.046                                      1000    monosulfonate3   Mixture of di-octyl,           0.045                0.005                     0.575                         0.540                             0.483                                  0.043                                      1000    dinonyl, di-decyl    benzene monosulfonate4   Mixture of di-octyl,           0.040                0.010                     0.862                         0.837                             0.757                                  0.046                                      1000    dinonyl, di-decyl    benzene monosulfonate5   Mixture of C.sub.21, C.sub.22,           0.045                0.005                     0.663                         0.619                             0.567                                  0.044                                      1000    C.sub.23 toluene benzene    sulfonate6   Mixture of C.sub.21, C.sub.22,           0.040                0.010                     0.942                         0.897                             0.825                                  0.048                                      1000    C.sub.23 toluene benzene    sulfonate7   Di-dodecyl diphenyl           0.045                0.005                     0.777                         0.654                             0.607                                  0.035                                      1000    oxide monosulfonate8   Di-dodecyl diphenyl           0.040                0.010                     0.968                         0.921                             0.858                                  0.042                                      1000    oxide monosulfonate.sup. 9.sup.1    Di-dodecyl benzene           0.050                0.000                     0.466                         0.391                             0.337                                  0.041                                      1000    monosulfonate.sup. 10.sup.1    Mixture of di-octyl,           0.050                0.000                     0.414                         0.404                             0.319                                  0.039                                      1000    dinonyl, di-decyl    benzene monosulfonate.sup. 11.sup.1    Mixture of C.sub.21, C.sub.22,           0.050                0.000                     0.515                         0.460                             0.398                                  0.041                                      1000    C.sub.23 toluene benzene    sulfonate.sup. 12.sup.1    Sodium Oleate           0.000                0.050                     0.607                         0.533                             0.477                                  0.037                                      1000__________________________________________________________________________ .sup.1 Not an embodiment of the invention
The above information demonstrates the effect of ratio of sulfonate to carboxylate and also shows that the combination of sulfonate and carboxylate functions better than either alone.
EXAMPLE 3--FLOTATION OF MINERALS The procedure of Example 2 is followed with the exception that various oxide and sulfide minerals are used in place of the ores specified in Example 2. All runs are conducted at a pH of 8 The collector used is 0.018 of C.sub.12 alkylated benzene sulfonic acid and 0.006 kg of oleic acid per kg of mineral. The sulfonic and oleic components are pre-blended prior to addition to the cell. In all runs, the ratio of metal ions added is five parts Na.sup.+, two parts Mg.sup.++, and one part Fe.sup.+++ with the total amount of these ions added being sufficient to result in measured ionic strength of the water being equivalent to Na.sup.+ of 1000 ppm as measured by a conductivity cell. The results obtained are shown in Table III below.
TABLE III______________________________________               Fractional MineralMineral             Recovery______________________________________Silica (SiO.sub.2)  0.041Cassiterite (SnO.sub.2)               0.833Bauxite [Al(OH).sub.3 ]               0.663Calcite (CaCO.sub.3)               0.707Chromite (FeCr.sub.2 O.sub.4)               0.839Dolomite [CaMg(CO.sub.3).sub.2 ]               0.666Malachite [Cu.sub.2 CO.sub.3 (OH).sub.2 ]               0.715Chrysocolla [Cu.sub.2 H.sub.2 Si.sub.2 O.sub.5 (OH).sub.4 ]               0.715Hematite (Fe.sub.2 O.sub.3)               0.417Corundum (A.sub.2 O.sub.3)               0.739Rutile (TiO.sub.2)  0.915Apatite [Ca.sub.5 (Cl.sub.1 F)[PO.sub.4 ].sub.3 ]               0.804Nickel Oxide (NiO)  0.494Galena (PbS)        0.862Chalcopyrite (CuFeS.sub.2)               0.860Chalcocite (Cu.sub.2 S)               0.825Pyrite (FeS.sub.2)  0.595Tourmaline          0.884Sphalerite (ZnS)    0.797Pentlandite [Ni(FeS)].sup.1               0.746Barite (BaSO.sub.4) 0.725Molybdenite (MoS.sub.2)               0.900Cerussite (PbCO.sub.3)               0.839Calcite (CaCO.sub.3)               0.355Beryl (Be.sub.3 Al.sub.2 Si.sub.6 O.sub.18)               0.818Covellite (CuS)     0.766Zircon (ZrSiO.sub.4)               0.784Graphite (C)        0.922Topaz [Al.sub.2 SiO.sub.4 (F.sub.1 OH).sub.2 ]               0.875Scheelite (CaWO.sub.4)               0.794Anatase (TiO.sub.2) 0.860Boehmite (.sub.Υ AlO.OH)               0.611Diaspore (αAlO.OH)               0.718Goethite (HFeO.sub.2)               0.733______________________________________ .sup.1 Sample includes some pyrrhotite.
The data in Table III demonstrates the broad range of minerals which may be floated using the collector composition and process of this invention.
EXAMPLE 4--FLOTATION OF MIXED COPPER SULFIDE ORE CONTAINING MOLYBDENUM A series of 30-gram samples of a -10 Mesh (U.S.) ore from Arizona containing a mixture of various copper oxide minerals and copper sulfide minerals plus minor amounts of molybdenum minerals is prepared. The grade of copper in the ore is 0.013 and the grade of the molybdenum is 0.00016. Each sample of ore is ground in a laboratory swing mill for 10 seconds and the resulting fines are transferred to a 300 ml flotation cell. The water used contains 600 ppm Ca.sup.++, 20 ppm Fe.sup.+++, 140 ppm SO4.sup.= and 50 ppm Mg.sup.++.
Each run is conducted at a natural ore slurry pH of 6.5. The collector composition (in the sodium salt form) is added at a total dosage of 0.150 kg/ton of dry ore and the slurry is allowed to condition for one minute. Ore concentrate is collected by standard hand paddling between zero and four minutes. Just before flotation is initiated, a frother, a polyglycol ether available commercially from The Dow Chemical Company as Dowfroth kg/ton of dry ore.
The float cell in all runs is agitated at 1800 RPM and air is introduced at a rate of 2.7 liters per minute. Samples of the concentrates and the tailings are then dried and analyzed as described in the previous examples. The results obtained are presented in Table IV below.
TABLE IV______________________________________              Dosage              (kg/              metric  Cu   Cu    Mo   MoRun  Collector     ton)    Rec  Grade Rec  Grade______________________________________1    di-Dodecyl benzene              0.145   0.724                           0.150 0.783                                      0.038monosulfonateSodium Oleate 0.0052    di-Dodecyl benzene              0.140   0.777                           0.161 0.848                                      0.043monosulfonateSodium Oleate 0.0103    di-Dodecyl benzene              0.135   0.765                           0.161 0.829                                      0.042monosulfonateSodium Oleate 0.0154    di-Dodecyl benzene              0.120   0.708                           0.153 0.767                                      0.038monosulfonateSodium Oleate 0.0305    di-Dodecyl benzene              0.105   0.605                           0.137 0.657                                      0.028monosulfonateSodium Oleate 0.0456    di-Dodecyl    0.140   0.837                           0.176 0.900                                      0.048diphenyloxidemonosulfonateSodium Oleate 0.010______________________________________
The data in the above table demonstrate the effectiveness of the present invention in the recovery of copper and molybdenum. In particular, it shows that, in this system, the ratio of sulfonate to oleate collector that is most effective is ranges from 30:1 to 2:1.
EXAMPLE 5--FLOTATION OF IRON OXIDE ORE A series of 600-g samples of iron oxide ore from Michigan is prepared. The ore contains a mixture of hematite, martite, goethite and magnetite mineral species. Each 600-g sample is ground along with 400 g of water containing 300 ppm Ca.sup.+, 10 ppm Fe.sup.+++, 80 ppm SO4.sup.=, 20 ppm Cl.sup.- and 40 ppm Mg.sup.++ in a rod mill at about 60 RPM for 10 minutes. The resulting pulp is transferred to an Agitair 3000 ml flotation cell outfitted with an automated paddle removal system. The collector is added and the slurry is allowed to condition for one minute. Next, an amount of a polyglycol ether frother equivalent to 40 g per ton of dry ore is added followed by another minute of conditioning.
The float cell is agitated at 900 RPM and air is introduced at a rate of 9.0 liters per minute. Samples of the froth concentrate are collected at four minutes after the start of the air flow. Samples of the froth concentrate and the tailings are dried, weighed and pulverized for analysis. They are then dissolved in acid, and the iron content determined by the use of a D C. Plasma Spectrometer. Using the assay data, the fractional recoveries and grades are calculated using standard mass balance formulas. The results are shown in Table V below.
TABLE V______________________________________                Dosage                (kg/metricRun   Collector      ton)      Fe Rec                                Fe Grade______________________________________ 1.sup.1 di-Dodecyl benzene                0.600     0.588 0.489 sulfonate 2.sup.1 Di-dodecyl benzene                0.300     0.401 0.500 sulfonate 3.sup.1 Oleate         0.600     0.488 0.477 4.sup.1 Oleate         0.300     0.337 0.438 5    Di-dodecyl benzene                0.300     0.694 0.523 sulfonate Oleate.sup.3   0.300 6.sup.1 Mixture of di-octyl                0.300     0.417 0.513 and di-nonyl benzene sulfonates.sup.2 7    Mixture of di-octyl                0.300     0.703 0.541 and di-nonyl benzene sulfonates.sup.2 Oleic Acid.sup.3                0.300 8.sup.1 Di-dodecyl benzene                0.600     0.504 0.483 sulfonic acid 9    Di-dodecyl benzene                0.550     0.663 0.483 sulfonic acid Oleic acid.sup.3                0.05010    Di-dodecyl benzene                0.500     0.723 0.526 sulfonic acid Oleic acid.sup.3                0.10011    Di-dodecyl benzene                0.450     0.735 0.528 sulfonic acid Oleic acid.sup.3                0.15012    Di-dodecyl benzene                0.400     0.663 0.510 sulfonic acid Oleic acid.sup.3                0.20013    Di-dodecyl benzene                0.300     0.582 0.487 sulfonic acid Oleic acid.sup.3                0.30014    Di-dodecyl benzene                0.538     0.585 0.481 sulfonic acid Tall oil fatty acid.sup.3                0.06215    Di-dodecyl benzene                0.475     0.668 0.544 sulfonic acid Tall oil fatty acid.sup.3                0.12516    Di-dodecyl benzene                0.300     0.602 0.548 sulfonic acid Tall oil fatty acid.sup.3                0.30017    Di-dodecyl benzene                0.5375    0.527 0.491 sulfonic acid Oxalic acid.sup.3                0.062518    Di-dodecyl benzene                0.475     0.647 0.529 sulfonic acid Oxalic acid.sup.3                0.12519    Di-dodecyl benzene                0.300     0.556 0.488 sulfonic acid Oxalic acid.sup.3                0.30020    Di-dodecyl benzene                0.538     0.511 0.476 sulfonic acid Tartaric acid.sup.3                0.06221    Di-dodecyl benzene                0.475     0.587 0.532 sulfonic acid Tartaric acid.sup.3                0.12522    Di-dodecyl benzene                0.300     0.530 0.519 sulfonic acid Tartaric acid.sup.3                0.30023    Di-dodecyl benzene                0.538     0.540 0.484 sulfonic acid Dodecanoic acid.sup.3                0.06224    Di-dodecyl benzene                0.475     0.627 0.530 sulfonic acid Dodecanoic acid.sup.3                0.12525    Di-dodecyl benzene                0.300     0.563 0.544 sulfonic acid Dodecanoic acid.sup.3                0.30026.sup.1 Tall oil fatty acid                0.600     0.437 0.45427.sup.1 Tall oil fatty acid                0.300     0.314 0.43228.sup.1 Oxalic acid    0.600     &lt;0.1  --29.sup.1 Tartaric acid  0.600     &lt;0.1  --30.sup.1 Dodecanoic acid                0.600     0.288 0.434______________________________________ .sup.1 Not an embodiment of the invention. .sup.2 The collector is a mixture of components listed. .sup.3 The two components are mixed together before addition to cell.
The above data show the effectiveness of the present invention. It is of particular interest to note the difference in recovery obtained when using either the sulfonate or carboxylate alone as compared to using the collector composition of this invention.
EXAMPLE 6--SEPARATION OF APATITE AND SILICA The procedure outlined in Example 1 is used in this example. The apatite used in a different ore and the water has 600 ppm Ca.sup.++, 20 ppm Fe.sup.+++, 140 ppm SO.sub.4.sup.=, and 50 ppm Mg.sup.++. All collectors are in the acid form. The results obtained are shown in Table VI below:
TABLE VI______________________________________         Dosage  Phosphorus Recovery         (kg/metric                 and GradeRun   Collector     ton)      Rec    Grade______________________________________ 1.sup.1 Oleic Acid    0.025     0.249  0.141 2.sup.1 Oleic Acid    0.050     0.350  0.139 3.sup.1 Oleic Acid    0.075     0.538  0.136 4.sup.1 Oleic Acid    0.150     0.671  0.134 5    di-Dodecyl benzene               0.150     0.534  0.139 sulfonic acid 6    di-Dodecyl benzene               0.125     0.449  0.141 sulfonic acid 7    di-Dodecyl benzene               0.100     0.308  0.142 sulfonic acid 8    di-Dodecyl benzene               0.075     0.217  0.144 sulfonic acid 9.sup.2 Oleic Acid    0.025     0.637  0.135 di-Dodecyl benzene               0.125 sulfonic acid10.sup.2 Oleic Acid    0.050     0.753  0.133 di-Dodecyl benzene               0.100 sulfonic acid11.sup.2 Oleic Acid    0.075     0.814  0.132 di-Dodecyl benzene               0.075 sulfonic acid12.sup.2 Oleic Acid    0.100     0.729  0.130 di-Dodecyl benzene               0.050 sulfonic acid13.sup.3 Oleic Acid    0.075     0.790  0.133 di-Dodecyl benzene               0.075 sulfonic acid14.sup.4 Oleic Acid    0.075     0.636  0.136 di-Dodecyl benzene               0.075 sulfonic acid15.sup.2 Fatty Acid.sup.5               0.075     0.833  0.133 di-Dodecyl benzene               0.075 sulfonic acid16.sup.3 Fatty Acid.sup.5               0.075     0.805  0.132 di-Dodecyl benzene               0.075 sulfonic acid17.sup.4 Fatty Acid.sup.5               0.075     0.648  0.135 di-Dodecyl benzene               0.075 sulfonic acid18.sup.6 Fatty Acid.sup.5               0.075     0.863  0.141 di-Dodecyl benzene               0.075 sulfonic acid19.sup.6 Fatty Acid.sup.5               0.050     0.885  0.142 di-Dodecyl benzene               0.010 sulfonic acid______________________________________ .sup.1 Not an embodiment of the invention. .sup.2 Two components mixed together before addition to cell. .sup.3 First component added to cell, conditioned for one minute followed by second component added to cell conditioned for one minute. .sup.4 Second component added to cell, conditioned for one minute followe by addition of first component added to cell conditioned for one minute. .sup.5 Mixture of oleic, linoleic and linoleic acids. .sup.6 Mixture added to grinding step.
The data in Table VI above shows that higher collector dosages are required in the presence of the hard water used in this example. The advantage of mixing the sulfonic and carboxylic acids together prior to being added either to the float cell (Runs 9-12 and 15) or the grinding step (18-19) is demonstrated.
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS1102874 *May 8, 1913Jul 7, 1914Minerals Separation LtdOre concentration.US2285394 *Jul 24, 1940Jun 9, 1942Hugh W CokeFlotation methodUS2373305 *Oct 7, 1942Apr 10, 1945American Cyanamid CoTungsten ore flotationUS2442455 *Aug 23, 1944Jun 1, 1948American Cyanamid CoConcentration of nonmicaceous, water-insoluble alkaline-earth metal salt mineralsUS2698088 *Apr 26, 1952Dec 28, 1954Pryor Edmund JamesSeparation of minerals by froth flotationUS2861687 *Sep 9, 1955Nov 25, 1958Southwestern Eng CoFlotation of heavy metal oxidesUS3122500 *Jan 24, 1962Feb 25, 1964Magnet Cove Barium CorpFlotation of bariteUS3214018 *Oct 8, 1962Oct 26, 1965Feldspar CorpFroth flotation of micaceous mineralsUS3292787 *Jan 9, 1964Dec 20, 1966Grace W R & CoPhosphate flotation processUS3377234 *Sep 5, 1963Apr 9, 1968Garden State Paper Co IncDe-inking printed waste cellulosic stock utilizing an admixture of alkyl sulfates and alkyl aryl sulfonatesUS3405802 *Jul 8, 1965Oct 15, 1968Phosphate Dev Corp LtdFlotation of apatiteUS4081363 *May 29, 1975Mar 28, 1978American Cyanamid CompanyMineral beneficiation by froth flotation: use of alcohol ethoxylate partial esters of polycarboxylic acidsUS4110207 *Jan 5, 1976Aug 29, 1978American Cyanamid CompanyProcess for flotation of non-sulfide oresUS4139482 *Dec 21, 1977Feb 13, 1979American Cyanamid CompanyCombination of a fatty acid and an N-sulfodicarboxylic acid asparate as collectors for non-sulfide oresUS4158623 *Dec 21, 1977Jun 19, 1979American Cyanamid CompanyProcess for froth flotation of phosphate oresUS4172029 *May 11, 1978Oct 23, 1979The Dow Chemical CompanyPhosphate flotation processUS4231841 *Oct 17, 1978Nov 4, 1980Montedison S.P.A.Process for the de-inking of printed waste paperUS4308133 *Jun 20, 1980Dec 29, 1981The Dow Chemical CompanyFroth promotor for flotation of coalUS4309282 *Apr 14, 1980Jan 5, 1982American Cyanamid CompanyProcess of phosphate ore beneficiation in the presence of residual organic polymeric flocculantsUS4376011 *Oct 14, 1980Mar 8, 1983Hoechst AktiengesellschaftProcess for removing pigments from waste paperUS4486301 *Jan 16, 1984Dec 4, 1984Tennessee Valley AuthorityMethod of beneficiating high carbonate phosphate oreUS4507198 *Dec 20, 1982Mar 26, 1985Thiotech, Inc.Flotation collectors and methodsUS4586982 *Aug 27, 1984May 6, 1986Akzona IncorporatedProcess for the de-inking of printed waste paperUS4959123 *Feb 2, 1988Sep 25, 1990Chemische Fabrik Gruenau GmbhProcess for deinking printed waste paperUS4964949 *Jun 22, 1988Oct 23, 1990Kao CorporationDeinking composition for reclamation of waste paperUS5015367 *Feb 23, 1990May 14, 1991The Dow Chemical CompanyAlkylated diaryl oxide monosulfonate collectors useful in the floatation of mineralsUS5022983 *Aug 17, 1989Jun 11, 1991Southern Illinois University FoundationProcess for cleaning of coal and separation of mineral matter and pyrite therefrom, and composition useful in the processUS5057209 *Feb 23, 1990Oct 15, 1991The Dow Chemical CompanyDepression of the flotation of silica or siliceous gangue in mineral flotationDD144208A1 * Title not availableJPS58149394A * Title not availableJPS60155793A * Title not availableSE326417B * Title not availableSU717195A1 * Title not available* Cited by examinerNon-Patent CitationsReference1"An Electrochemical Characterization of Pyrite from Coal and Ore Sources" by Briceno et al.--Int'l Journal of Mineral Processing--1987.2"Characterization of Pyrite from Coal Sources" by Esposito, Chander and Aplan, Process Minerology VIII, 1987.3"Flotation" vol. 2--Fuerstenau, Editor; Published by AIMMPE New York--1976.4"Mineral and Coal Flotation Circuits" by Lynch, Johnson, Manlapig and Thorn, Advisory Editor--Fuerstenau, Elsevier Scientific Publication 5 *An Electrochemical Characterization of Pyrite from Coal and Ore Sources by Briceno et al. Int l Journal of Mineral Processing 1987.6 *Characterization of Pyrite from Coal Sources by Esposito, Chander and Aplan, Process Minerology VIII, 1987.7 *Comparative Study of the Surface Properties and the Reactivities of Coal Pyrite and Mineral Pyrite by Lai et al. Society of Mining Engineers, Mar. 1989.8Comparative Study of the Surface Properties and the Reactivities of Coal Pyrite and Mineral Pyrite by Lai et al.--Society of Mining Engineers, Mar. 1989.9 *Flotation vol. 2 Fuerstenau, Editor; Published by AIMMPE New York 1976.10 *Mineral and Coal Flotation Circuits by Lynch, Johnson, Manlapig and Thorn, Advisory Editor Fuerstenau, Elsevier Scientific Publication 1981, pp. 13 18.* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS5314073 *May 3, 1993May 24, 1994Eastman Kodak CompanyPhosphate flotation using sulfo-polyestersUS5527426 *May 5, 1994Jun 18, 1996Westvaco CorporationMagnetic deinking of waste papersUS5929408 *Sep 26, 1996Jul 27, 1999Cytec Technology Corp.Compositions and methods for ore beneficiationDE19925660A1 *Jun 4, 1999Dec 7, 2000Uvr Fia Gmbh VerfahrensentwickRecovery of tiny particles of precious beryl, e.g. emerald, useful as colored pigment in precious stone lacquer, involves flotation of mica shale using frother and then of beryl minerals by adding collector* Cited by examinerClassifications U.S. Classification209/166, 162/7, 162/5, 162/8, 252/61International ClassificationB03D1/004, B03D1/012Cooperative ClassificationB03D1/004, B03D1/012European ClassificationB03D1/004, B03D1/012Legal EventsDateCodeEventDescriptionFeb 20, 2001FPExpired due to failure to pay maintenance feeEffective date: 20001215Dec 17, 2000LAPSLapse for failure to pay maintenance feesJul 11, 2000REMIMaintenance fee reminder mailedJan 19, 1996FPAYFee paymentYear of fee payment: 4Sep 14, 1992ASAssignmentOwner name: DOW CHEMICAL COMPANY, THE, MICHIGANFree format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:KLIMPEL, RICHARD R.;LEONARD, DONALD E.;MCCANN, GORDON D.;REEL/FRAME:006270/0082;SIGNING DATES FROM 19911126 TO 19911127RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services©2012 Google


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AF-S DX NIKKOR 10-24mm f/3.5-4.5G ED AF-S DX Zoom-Nikkor 12-24mm f/4G IF-ED AF-S NIKKOR 14-24mm f/2.8G ED AF-S NIKKOR 16-35mm f/4G ED VR AF-S Zoom-Nikkor 17-35mm f/2.8D IF-ED AF Zoom-Nikkor 18-35mm f/3.5-4.5D IF-ED 9/14 7/11 11/14 12/17 10/13 8/11 — — 114˚-84˚ 107˚-63˚ 104˚-62˚ 100˚-62˚ 109˚-61˚ 99˚-61˚ 90˚-61˚ 83˚-44˚ 79˚-44˚ 76˚-44˚ 7 7 9 9 9 7 22-29 22 22 22 22 22-32 0.24/0.8 (0.22/0.7)*1 0.3/1 0.28/0.9*4 0.28/0.9 0.28/0.9 0.33/1.1 1/5 1/8.3 1/6.7 1/4 1/4.6 1/6.7 460/16.2 465/16.4 970/34.2 680/24.0 745/26.3 370/13.0 77 77 — 77 77 77 Snap-on Snap-on Slip-on Snap-on Snap-on Snap-on HB-23 (provided) HB-23 (provided) Built-in HB-23 (provided) HB-23 (provided) HB-23 (provided) CL-1118 (provided) CL-S2 (optional) CL-M3 (provided) CL-1120 (provided) CL-76 (provided) CL-S2 (optional)
AF-S DX NIKKOR 16-85mm f/3.5-5.6G ED VR AF-S DX Zoom-Nikkor 17-55mm f/2.8G IF-ED AF-S DX NIKKOR 18-55mm f/3.5-5.6G VR AF-S DX Zoom-Nikkor 18-55mm f/3.5-5.6G ED II AF-S DX NIKKOR 18-105mm f/3.5-5.6G ED VR AF-S DX NIKKOR 18-200mm f/3.5-5.6G ED VR II AF-S NIKKOR 24-70mm f/2.8G ED AF Zoom-Nikkor 24-85mm f/2.8-4D IF AF-S NIKKOR 24-120mm f/4G ED VR AF-S NIKKOR 28-300mm f/3.5-5.6G ED VR 11/17 10/14 8/11 5/7 11/15 12/16 11/15 11/15 13/17 14/19 — — — — — — 84˚-34˚20' 84˚-28˚30' 84˚-20˚20' 75˚-8˚10' 83˚-18˚50' 79˚-28˚50' 76˚-28˚50' 76˚-28˚50' 76˚-15˚20' 76˚-8˚ 61˚-22˚50' 61˚-18˚50' 61˚-13˚20' 53˚-5˚20' 7 9 7 7 7 7 9 9 9 9 22-36 22 22-36 22-38 22-38 22-36 22 22-32 22 22-38 0.38/1.3 0.36/1.2*5 0.28/0.9 0.28/0.9 0.45/1.48 0.5/1.6 0.38/1.2*6 0.5/1.6 (0.21/0.7)*3 0.45/1.5 0.5/1.6 1/4.6 1/5 1/3.2 1/3.2 1/5 1/4.5 1/3.7 1/5.9 (1/2)*3 1/4.2 1/3.1 485/17.1 755/26.6 265/9.4 205/7.2 420/14.8 565/19.9 900/31.7 545/19.2 710/25 800/28.2 72 x 85/2.8 x 3.4 85.5 x 110.5/3.4 x 4.4 73 x 79.5/2.9 x 3.1 70.5 x 74/2.8 x 2.9 76 x 89/2.9 x 3.5 77 x 96.5/3.0 x 3.8 83 x 133/3.3 x 5.2 78.5 x 82.5/3.1 x 3.2 84 x 103.5/3.3 x 4.1 83 x 114.5/3.3 x 4.5 67 77 52 52 67 72 77 72 77 77 Snap-on Snap-on Snap-on Snap-on Snap-on Snap-on Snap-on Snap-on Snap-on Snap-on HB-39 (provided) HB-31 (provided) HB-45 (optional) HB-45 (optional) HB-32 (provided) HB-35 (provided) HB-40 (provided) HB-25 (provided) HB-53 (provided) HB-50 (provided) CL-1015 (provided) CL-1120 (provided) CL-0815 (optional) CL-0815 (optional)*9 CL-1018 (provided) CL-1018 (provided) CL-M3 (provided) CL-S2 (optional) CL-1218 (provided) CL-1120 (provided)
AF-S DX VR Zoom-Nikkor 55-200mm f/4-5.6G IF-ED AF-S DX Zoom-Nikkor 55-200mm f/4-5.6G ED (black, silver) AF-S DX NIKKOR 55-300mm f/4.5-5.6G ED VR AF-S NIKKOR 70-200mm f/2.8G ED VR II*7 AF-S VR Zoom-Nikkor 70-300mm f/4.5-5.6G IF-ED AF Zoom-Nikkor 70-300mm f/4-5.6G (black, silver) AF Zoom-Nikkor 80-200mm f/2.8D ED*7 AF VR Zoom-Nikkor 80-400mm f/4.5-5.6D ED*7 AF-S NIKKOR 200-400mm f/4G ED VR II 11/15 9/13 11/17 16/21 12/17 9/13 11/16 11/17 17/24 — — — 34˚20'-12˚20' 34˚20'-8˚10' 34˚20'-8˚10' 30˚10'-12˚20' 30˚10'-6˚10' 12˚20'-6˚10' 28˚50'-8˚ 28˚50'-8˚ 28˚50'-5˚20' 22˚50'-8˚ 22˚50'-5˚20' 22˚50'-5˚20' 20˚-8˚ 20˚-4˚ 8˚-4˚ 7 9 9 9 9 9 9 9 9 22-32 22-32 22-29 22 32-40 32-45 22 32-40 32 1.1/3.6 0.95/3.1 1.4/4.59 1.4/4.6 1.5/4.9 1.5/4.9 1.8/6 (1.5/4.9)*2 2.3/7.5 2/6.6(1.95/6.4)*1 1/4.4 1/3.5 1/3.6 1/8.6 1/4 1/3.9 1/7.1 (1/5.9)*2 1/4.8 1/3.7(1/3.6)*1 335/11.8 255/9.0 530/18.7 1540(1460)/54.3 (51.5)*8 745/26.3 425/15.0 1300/45.9 1360(1210)/48.0 (42.7)*8 3360/118.5 73 x 99.5/2.9 x 3.9 68 x 79/2.7 x 3.1 76.5 x 123/13.0 x 4.8 87 x 205.5/3.4 x 8.2 80 x 143.5/3.1 x 5.6 74 x 116.5/2.9 x 4.6 87 x 187/3.4 x 7.4 91 x 171/3.6 x 6.7 124 x 365.5/4.9 x 14.4 52 52 58 77 67 62 77 77 52 Snap-on Snap-on Snap-on Snap-on Snap-on Snap-on Snap-on Snap-on Slip-on HB-37 (provided) HB-34 (provided) HB-57 (provided) HB-48 (provided) HB-36 (provided) HB-26 (provided) HB-7 (optional) HB-24 (provided) HK-30 (provided) CL-0918 (provided) CL-0815 (provided) CL-1020(provided) CL-M2 (provided) CL-1022 (provided) CL-S4 (optional) CL-43A (provided) CL-M1 (provided) CL-L2 (provided)
114˚ 94˚ 84˚ 84˚ 74˚ — 63˚ 62˚ 46˚ 46˚ 46˚ 28˚30' 28˚30' 23˚20' 18˚ 13˚40' 12˚20' 8˚10' 8˚10' 6˚10' 5˚ 4˚10'
90˚ 70˚ 61˚ 61˚ 53˚ 44˚ 44˚ 44˚ 31˚30' 31˚30' 31˚30' 18˚50' 18˚50' 15˚20' 12˚ 9˚ 8˚ 5˚20' 5˚20' 4˚ 3˚10' 2˚40'
— 180˚ 39˚40' 39˚40' — 23˚20' 12˚20' 84˚ 51˚ 28˚30'
180˚ 107˚ 26˚30' 26˚30' 18˚50' 15˚20' 8˚ 61˚ 34˚50' 18˚50'
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text:
Lyndhurst Collection Paisley Red/ Multi Rug (8' Square) | Overstock.com Shopping - Great Deals on Safavieh Round/Oval/Square
$157.24 Compare $315.95 Save
$158.71 (50%)
Item #: 12913177
The Lyndhurst Collection presents this versatile area rug for interior design. This eight-foot rug is decorated with a vivid paisley detail. Its red background is eye-catching and fits well with similar shades. Use this rug for any living space or room....more
Lyndhurst Collection Paisley Beige/ Multi Rug (8' Square) Sale $163.79 Was $181.99 Compare $202.88 Save 19% (36) Lyndhurst Collection Persian Treasure Red/ Black Rug (8' Square) Sale $182.58 Was $202.87 Compare $315.95 Save 42% (24) Handmade Diamond Bakhtiari Multi/ Red Wool Rug (8' Square) Sale $265.49 Was $294.99 Compare $461.54 Save 42% (7) Lyndhurst Collection Sage/ Ivory Rug (8' Square) Sale $170.99 Was $189.99(17) Lyndhurst Collection Paisley Red/ Multi Rug (8' Round) Sale $152.99 Was $169.99 Compare $315.95 Save 52% (4) Hand-made Alliyah Delhi Rust/ Gold New Zealand Wool Rug (8' Square) Sale $258.29 Was $286.99 Compare $319.00 Save 19% (2) Lyndhurst Floral Motif Greyish Blue/ Ivory Rug (8' Square) Sale $193.49 Was $214.99 Compare $304.62 Save 36% (17) Handmade Heritage Oushak Light Green/Beige Wool Rug (8' Square) Sale $253.97 Was $282.19 Compare $444.74 Save 43% (2) Amalfi Paradise Area Rug (8' Round) Sale $162.89 Was $180.99(22) Lyndhurst Collection Heritage Ivory/ Ivory Rug (8' Square) Sale $185.39 Was $205.99 Compare $304.62 Save 39% (16) Handmade Majesty Light Brown/ Beige Wool Rug (8' Square) Sale $296.09 Was $328.99 Compare $549.99 Save 46% (21) Lyndhurst Collection Red/ Black Rug (8' Square) Today $170.99 Compare $315.95 Save 46% (7) Safavieh Handmade Golden Jaipur Green/ Rust Wool Rug (6' Square) Sale $161.09 Was $178.99 Compare $296.95 Save 46% (5) Lyndhurst Collection Floral Burgundy/ Ivory Rug (8' Square) Sale $153.89 Was $170.99 Compare $383.62 Save 60% (4) Lyndhurst Collection Paisley Beige/ Multi Rug (7' Square) Sale $141.29 Was $156.99(4) Lyndhurst Traditional Multicolor/ Ivory Rug (8' Square) Sale $168.29 Was $186.99 Compare $202.88 Save 17% (3) Nourison Hand-tufted Versailles Palace Brick/ Ivory Rug (8' x 8') Square Add to cart to see special price Lyndhurst Collection Paisley Red/ Multi Rug (6' Square) Sale $92.69 Was $102.99 Compare $130.41 Save 29% (7) Next Sponsored Links What's This?
http://www.overstock.com/Home-Garden/Lyndhurst-Collection-Paisley-Red-Multi-Rug-8-Square/5034130/product.html
How did the color on site compare with the actual product? The color is REALLY RED. The picture online looks as though it is more brown, but it isn't! If you want a RED rug, this is for you.
How accurate was the on site description of the product? Well, the description does say RED paisly, but the picture displays more brown tones.
toniduke
dmclancy
This is a bright rug!
The color of this rug is a red/rust. It leans more to the rust side, but it is much brighter than the photo shows. I only wish it was a bit more muted and not so bright. It is a fairly thin rug, but for the price it is fair. The 8x8 is a great size and they are hard to find in stores.I think I am going to keep it as of now. I will live with it a few more days. I want to watch it through most of the day as light changes.
Ordered this rug for guest room,love the colors and pattern, very nice for price.Color is a deep brick red, which is just what I wanted,with a darker basil green and lighter sage green design.Looks very nice!
I love the colors in this rug. It matched my room perfectly. The rug is not real thick, but is very soft to the touch and looks like a quality rug on the floor. Very good price for the size!
Please tell us about the quality of the product. nice and soft, not real thick but feels good to walk on
Paisley really stands out.
I placed this rug under the dining table originally, but it didn't finally 'fit' with the surrounds. Also, the rug's pile is high enough that you have to pick up your chair each time you shift position at the table which is a lot of work, so I moved it to an entry-way in a rustic room and it fits well there. It picks up the energy in that room which was otherwise sort of dull.
How did the color on site compare with the actual product? The pattern in the picture appears more muted than in actual fact. The colors are accurate.
I was disappointed and returned the rug. I will say that Overstock makes returns as easy as possible and I'm grateful for that.
How did the color on site compare with the actual product? What I couldn't see on the monitor is that there are distinct orange threads throughout the red border.
Please tell us about the quality of the product. Very thin pile.
How accurate was the on site description of the product? You have to see the rug in person. I won't be ordering any more rugs online.
tiamiga
Submit Cancel what are the cleaning care instructions?
kathy0917 on Nov 6, 2013
Submit Cancel Hello kathy0917, This beautiful rug has received excellent reviews! Vacuum your rug at least once a week. Get a professional cleaning done every one to two years. Blot spills as quickly as possible with a white cloth; then spot treat. I hope this helps. Thanks for shopping with us.

value: This website is an American internet retailer selling primarily furniture headquartered in Midvale, Utah, near Salt Lake City.


text:
Baby Jogger City Tour Stroller Garnet - 1980151 for sale online | eBay
Jun 18, 2019, 06:38:28 PM PDT
Get it by Tuesday, Jul 23 from Towson, Maryland
We are an authorized Baby Jogger dealer and full warranty will apply! Folds small for big adventures! This fully featured stroller includes a near flat recline, UV 50+ extended canopy, and a comfortable, padded seat.
Sold bycapitalkidz (42311)100.0% Positive feedbackContact seller
0047406140459
1985294407
Folding, Basket, Adjustable Back Rest, Hood/Canopy, Five-point Harness, Rain Cover, Adjustable Leg Rest, Auto-Locking, Adjustable Handles, Carry Handle, Lightweight Buggy, Cup Holder, Lockable Swivel Wheels, One-Hand Push, Hanging Bag, Special Needs
Baby Jogger 2015 Universal Parent Console Brand BJ90000
Baby Jogger 2016 Child Tray for City Premier Single Stroller H1
item 1 Baby Jogger City Tour Stroller- Garnet - Similar to Nano Brand New Free Shipping -Baby Jogger City Tour Stroller- Garnet - Similar to Nano Brand New Free Shipping
item 2 Baby Jogger City Tour Lightweight Compact Travel Stroller garnet w Bag NEW -Baby Jogger City Tour Lightweight Compact Travel Stroller garnet w Bag NEW
item 3 Baby Jogger City Tour Stroller, Garnet -Baby Jogger City Tour Stroller, Garnet
Baby Trend Pathway 35 Jogger Travel System Optic Green TJ75B71B Infant Car Seat
$245.97 New
GB Qbit Plus Compact Lightweight One Hand Fold Travel Stroller Dragonfire Red
Baby Jogger City Select Bassinet Kit 50927
Mountain Buggy 2015 Plus One Inline Double Stroller With Second Seat Black
Double Stroller Infant Toddler Ultra Sit & Stand Baby Trend Millennium Raspberry
Maxi-Cosi Adora Travel System in Graphic Flower TR398EMO
Austlen ENTOURAGE Expandable Stroller Silver and Navy Compact 150 LB Capacity
by epul203Aug 23, 2017
Great product, similar to displayed in the retail shop with very good price. Folded easy and super small to be carried or stored in the car.
by jhonathan84May 26, 2017
100% Recommend and good quality
Travel System Baby Girl Lightweight Infant Car Seat Stroller Combo Daphne NEW

value: This website is an American multinational e-commerce corporation based in San Jose, California, that facilitates consumer-to-consumer and business-to-consumer sales through its website.


text:
Danielle Lloyd's friend convicted of 'Ocean's Eleven' robbery despite model's alibi evidence | Daily Mail Online
'Ocean's Eleven' robber convicted despite Danielle Lloyd's alibi evidence
Updated: 13:36 EST, 14 April 2011
A man has been found guilty of carrying out a building society robbery after jurors seemingly rejected glamour model Danielle Lloyd's alibi evidence.
Craig Mason, 32, was part of a gang of armed robbers who carried out a terrifying crimewave across East Anglia with military precision.
It is conceivable that Miss Lloyd may face perjury charges arising from the evidence she gave in court, although there is no information to suggest this is being contemplated.
Craig Mason has been found guilty of a building society robbery after jurors seemingly rejected Danielle Lloyd's alibi evidence
The raiders were led by master technician Danny Speed, 29, who has been likened by one Flying Squad officer to the character played by George Clooney in the film Ocean’s Eleven.
In the film, an elite gang steal millions of dollars from a Las Vegas casino using brilliant planning and meticulous execution.
Former Miss Great Britain Miss Lloyd, 26, appeared as an alibi witness for Mason, and told jurors he was at her West End charity event at the time of one of the raids in Brightlingsea, Essex.
Ex-EastEnders star Billy Murray charged with beating wife and daughter 'after late-night row'
But after a retrial, the jury at Snaresbrook Crown Court found him guilty of the seaside heist and a second robbery of the Nationwide in Holt, Norfolk.
Mason and other gang members armed themselves with machetes, a sledgehammer and an axe and escaped with £161,000 from the hold-ups.
The powerboat racing enthusiast denied any involvement with either of the robberies.
Miss Lloyd told both juries Mason attended the Field of Women breast cancer fundraiser at the Embassy nightclub in the early hours of October 11, 2007.
CCTV from inside Nationwide, Holt in Norfolk, shows gang members smashing their way into the branch
One of the armed robbers is seen handing cash boxes from the building society through the broken door to a fellow gang member outside
Miss Lloyd said: 'I saw him a couple of times throughout the night.
'I was very busy trying to organise everything and speak to everybody there.' She said they left the fundraiser for a party in Chigwell, Essex, at around 3am.
Miss Lloyd said she slept on a sofa at her friend's house and remembered Mason crashing out on another settee.
But the jury of seven men and five women found Mason guilty of the Brightlingsea raid by a majority of ten to two.
Mason was convicted of the Holt heist by a unanimous verdict.
Danielle Lloyd leaves court after giving evidence
Earlier this year Speed - dubbed Mr Meticulous for his brilliant planning - was jailed for 20 years.
Speed, who splashed out on luxury motors including a BMW X5 and is thought to have invested in property, may have been responsible for carrying out raids totalling £2million.
In one attack, his gang of robbers wore camouflage fatigues to blend in with American servicemen in the town during a heist in Mildenhall, Suffolk - home to a large U.S. military airbase.
Snaresbrook Crown Court had heard how Mason, Speed, Speed's cousin Lee Watson, and a fourth man Mark Richards, 29, carried out the raid in Holt.
Mason and Richards were also involved in the £80,000 raid in Brightlingsea in which a G4S custodian was beaten round the head and neck with a pick axe handle.
Jurors heard three gloves were found in the black holdall and DNA from Mason and Richards was found.
He said in both cases the chance the DNA was from anyone other than the two men 'was one in a billion'.
Three months later on January 29, 2008, the robbers struck in Holt, stealing £81,000.
The gang had been staying at the Lawns hotel opposite the Nationwide and it is thought they later returned to the guesthouse bar to toast their success as the police sirens sounded.
The robbers left behind them a sledgehammer and a black holdall.
The getaway car - a blue Vauxhall Vectra - was found abandoned in the village with two machetes inside. A swab taken from the back-seat of the car had traces of DNA from Mason and Speed.
A copy of Autotrader magazine with Mason's fingerprints on was discovered at the Lawns Hotel and a machete matching those found in the getaway vehicle was found discarded behind the guesthouse.
Mason, of Harrow Drive, Hornchurch, Essex, denied two counts of conspiracy to rob.
In March this year, Watson, 42, was jailed for 16 years and Andrew McCracken, 31, was jailed for 15 years following a 12-week trial.
Richards, described as Speed's 'lieutenant', was jailed for 13 years.
Speed, of Eisenhower Drive, Beckton, east London, was convicted of five counts of conspiracy to rob between November 3, 2005, and September 28 last year.
McCracken, of Earlsdown House, Barking, Essex, was convicted of two counts conspiracy to rob.
Watson, of the same address as Speed, was convicted of three counts of conspiracy to rob and having a firearm with intent.
Mason was remanded in custody to be sentenced on April 20.
Danielle Lloyd's friend convicted of 'Ocean's Eleven' robbery despite model's alibi evidence

value: This website is the website of the Daily Mail, a newspaper in the United Kingdom, and of its sister paper The Mail on Sunday. MailOnline is a division of dmg media, which is owned by Daily Mail and General Trust plc.


text:
The Grammar of the English Verb Phrase : a Comprehensive Analysis. (eBook, 2006) [WorldCat.org]
I thought you might be interested in this item at http://www.worldcat.org/oclc/476023418 Title: The Grammar of the English Verb Phrase : a Comprehensive Analysis. Author: Renaat Declerck Publisher: Berlin : Walter de Gruyter, 2006. ISBN/ISSN: 9783110199888 3110199882 OCLC:476023418
The Grammar of the English Verb Phrase : a Comprehensive Analysis.
9783110199888 3110199882
476023418
The Grammar of the English Tense System forms the first volume of a four-volume set, The Grammar of the English Verb Phrase. Read more...
"There is a wealth of data which have been carefully and closely examined, laying open several important distinctions. This book spells out its intellectual assumptions, and follows them through consistently."Nikolas Gisborne in: English Language and Linguistics 12-3/2008 "This is unquestionably a challanging book that no one with a serous interest in tense in English can affort to ignore."Peter C. Collins in: Folia Linguistica 41/2007 "There is a wealth of data which have been carefully and closely examined, laying open several important distinctions. This book spells out its intellectual assumptions, and follows them through consistently."Nikolas Gisborne in: English Language and Linguistics 12-3/2008 "This is unquestionably a challanging book that no one with a serous interest in tense in English can affort to ignore."Peter C. Collins in: Folia Linguistica 41/2007 -There is a wealth of data which have been carefully and closely examined, laying open several important distinctions. This book spells out its intellectual assumptions, and follows them through consistently.-Nikolas Gisborne in: English Language and Linguistics 12-3/2008 -This is unquestionably a challanging book that no one with a serous interest in tense in English can affort to ignore.-Peter C. Collins in: Folia Linguistica 41/2007 Read more...
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<http://worldcat.org/entity/work/data/794024965#CreativeWork/>
schema:isSimilarTo <http://www.worldcat.org/oclc/476023418> ; # The Grammar of the English Verb Phrase : a Comprehensive Analysis.
<http://worldcat.org/isbn/9783110199888>
schema:isbn "3110199882" ;
schema:isbn "9783110199888" ;
<http://www.worldcat.org/title/-/oclc/476023418>
schema:about <http://www.worldcat.org/oclc/476023418> ; # The Grammar of the English Verb Phrase : a Comprehensive Analysis.
<http://www.worldcat.org/title/-/oclc/476023418#PublicationEvent/berlin_walter_de_gruyter_2006>
schema:location <http://experiment.worldcat.org/entity/work/data/794024965#Place/berlin> ; # Berlin
schema:organizer <http://experiment.worldcat.org/entity/work/data/794024965#Agent/walter_de_gruyter> ; # Walter de Gruyter
<https://ebookcentral.proquest.com/lib/ucm/detail.action?docID=280193>
The Grammar of the English Verb Phrase : a Comprehensive Analysis./Renaat Declerck; Berlin : Walter de Gruyter, 2006.

value: This website is a union catalog that itemizes the collections of 15,637 libraries in 107 countries that participate in the OCLC global cooperative. It is operated by OCLC, Inc.


text:
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Great Deal towels
A great towel set. The colors are right in for summer
It took while to find towels that actually cover the length of the chair and these are great! All summer long we got asked where we got these towels!
The grandkids used this towel almost every day during the past summer and it held up fantastically. Nice and soft to the touch but very absorbent. Held up to weekly washings. At end of summer design was slightly worn, but being used every day was to be expected. Still in good shape and ready and waiting for next summer.
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