BR112018008468B1 - AMINE ORE COLLECTORS - Google Patents

Abstract

a family of amine ore collectors that uses alkoxylates allows easy adjustment of solubility and useful molecular weight, because anionic and cationic mineral collectors require varying degrees of solubility and molecular weight. the family of the present invention allows the optimization of both parameters and an increase in the efficiency of the collector.

Description

BACKGROUND OF THE INVENTION Field of the Invention

[0001] The present invention relates to the field of amine ore collectors and more particularly to an ether amine class.

Description of the Problem solved by the Invention

[0002] Many commercially important mineral ores are mined from the earth in relatively low concentration. For example, in the Mesabi strip of Minnesota, the ore consists of approximately 25% iron. Before further processing, the desired minerals must be concentrated. The present invention improves the process of concentrating the desired mineral.

SUMMARY OF THE INVENTION

[0003] The present invention relates to the field of amine ore collectors that improve the yield of the ore concentration. The use of amines with sufficient water solubility, which form water-insoluble complexes with the desired mineral, and not with competing minerals, results in a higher yield of the desired minerals. The family of amine, xanthan and dithiocarbamate collectors of the present invention does just that.

Description of the Figures

[0004] Attention is now turned to the following figures that describe the modalities of the present invention:

[0005] Figure 1 shows the synthesis of new cationic mineral collectors of ether amine.

[0006] Figure 2 shows the synthesis of new anionic mineral collectors.

[0007] Figure 3 shows the synthesis of derivatives of the cationic collectors.

[0008] Figure 4 shows the synthesis of tertiary amine derivatives.

[0009] Figure 5 shows the synthesis of polyprimary amines.

[0010] Figure 6 shows the synthesis of secondary amines and their derivatives.

DETAILED DESCRIPTION OF THE INVENTION

[0011] Mineral ores that are concentrated by flotation are dug out of the ground and ground to a predefined small particle size. The grains or ore are then treated with various active molecules on the surface and pumped into a flotation tank where dissolved air is introduced. The ore binds to the collector, which creates a water-insoluble particle. This water-insoluble complex is then brought to the surface by excluding water in the air bubbles that form when the dissolved air floats. The foam beaters maintain a thick foam head that supports the mineral on the surface until the support rod rakes can slide the mineral complex into the funnels for further processing. Ideally, the non-target components of the earth / ore mixture are left to settle to the bottom of the flotation tanks, thus concentrating the desired minerals in such a way that they can enter the next processing steps, whether by reduction, purification or other stages of processing.

[0012] The present invention uses alkoxylates as the collector's backbone. By varying the side chains on the collector and the chain length, or by increasing the number of repeated units, or by using a different chain length or alcohol conformations to initiate alkoxylation adjustments in water solubility, foam potential and density of the complete ore collector can be made. These adjustments allow the optimization of the collector, increasing the yield of the target mineral and reducing the collection of non-target minerals, such as silicates.

[0013] Figure 1 shows the synthesis of collectors of primary amine and diamine. Water is the typical water used to make polyalkoxylates. The resulting polyalkoxylates have 2 terminal hydroxyls and can react with 2 moles of acrylonitrile to form the diprimiary amine. The use of diols and polyols, such as a resorcinol, glycerin, neopentyl glycol and pentaerythritol produces multiple hydroxyls and the like products can be formed. The upper polyols, in addition to the diols, introduce branches, which is useful for lower pour points and easier handling, particularly in cold climates. While the figure shows the alkyl portion, with R being 1 to 8 carbons, this is the preferred range for the ore that is mined today. The higher carbon chains hold promise in more unusual ores, where heavier species are floating. The invention also encompasses these analogues of upper carbon chains. This analogue also applies to all subsequent numbers.

[0014] The use of a monohydric alcohol, such as methanol, ethanol, propanol or butanol results in a polyalkoxylate with only one hydroxyl terminal to react with acrylonitrile, resulting in a primary amine collector. When using alcohols with a higher number of carbons, the water solubility of both the collector and the collector-mineral complex. Non-linear alcohols, such as phenol, cyclohexanol, isopropanol or t-butanol, reduce the pour point to facilitate handling in cold climates.

[0015] A diamine can also be formed by reacting the previously formed primary amine with an additional mole of acrylonitrile, which is then reduced to form the diamine. This same addition can be done with the primary diamines to yield di- (diamines). Michael's addition of acrylonitrile to alcohol and amine is well known, as is the reduction of nitrile to amine with nickel sponge or other spongy metals, whether or not promoted with hydrogen. The reduction normally occurs at a pressure between 400 to 800 psi at less than 40 ° C over 4 to 12 hours. Michael's Addition is usually done by adding acrylonitrile to alcohol or amine at room temperature with cooling at a rate that maintains the temperature. High temperatures lead to the polymerization of acrylonitrile. If necessary, a catalytic amount of caustic can be used to accelerate Michael's addition with alcohols. Yields are usually over 96% and no additional clearance is required for a commercial product. These collectors are useful where cationic collectors are needed, such as iron ore and potassium.

[0016] Figure 2 shows the synthesis of the anionic analogues of the collectors in Figure 1. Xanthanes and dithiocarbamates. Dihyditocarbamates can be made from diamines. Anionic collectors are typically used in sulfide ores. The same solubility trends apply to anionics as compared to the cationic collectors in Figure 1. Xanthanes are synthesized by the reaction of carbon disulfide (CS2) with the alcohol group under basic conditions. Dithiocarbamates are made in a similar way, but reacting an amino group instead of an alcohol group. The result is a salt of xanthate or dithiocarbamate. The salt shown in Figure 2 is always a sodium salt, but any cationic salt is possible and part of the invention. Xanthanes and dithiocarbamates can be made as salts of amines, as well as mineral bases.

[0017] The collectors of the present invention also have additional uses. Cationic collectors are useful in personal care such as surfactants, cleaners, emollients, rheology modifiers and buffer products. Primary amines and diamines are also useful in asphalt as antistrips. Figure 3 shows several derivatives. Fatty acid amides from cationic collectors are made simply by combining the cationic collector with the desired fatty acid, usually stearic acid or coconut fatty acid and heating to remove one mole of water for each formed amide group. Amides are versatile rheology modifiers. The amphoterics of cationic collectors can be made by reacting sodium monochloroacetic acid (reflux 1: 1 molar equivalent of SMCA for approximately 8 hours), or to a salt-free form, acrylic acid or methacrylic acid can be reacted by adding the acid at room temperature or below the cationic collector with sufficient cooling to maintain the temperature below 30 ° C. Esters can be produced by reacting acid esters. A diadiction can be made to the amino group by continuing the reactions. Sulfonates can be prepared by reacting sodium vinyl sulfonate, propane sultone or butane sultone, or the upper sultones can react in a similar way to create sulfonates with a longer carbon chain between nitrogen and sulfur. Phosphonates can be produced by the reaction of phosphonic acid and formaldehyde. The derivatives of salty products from the cationic collectors in Figure 3 can be in their free form through ion exchange or be salted with any other cation. Figure 4 shows that tertiary amines can be made by reacting 2 moles of formaldehyde, followed by a reduction with a nickel sponge under conditions similar to nitrile reductions in Figure 1. Tertiary amines can then be transformed into quaternary or oxides of the mine. The methyl chloride, diethyl sulfate, ethyl benzyl chloride and benzyl chloride quaternaries are all easy reactions at room temperature that produce the quaternary analogues.

[0018] Figure 5 shows the synthesis of new collectors based on allyl polyvinyls that are then reduced to polyamines. This unique approach allows for the synthesis of polyprimal amines. The starting material can be an alcohol, an amine, a polyamine such as Tallow Diamine, common commercial name Akzo Duomeen T, or polyether amine, such as Air Products DA-14, ethoxylated amines, such as Akzo Ethomeet T12 or ethoxylated ether amines, like the Air Products E-17-5. In the case of primary amines, a second equivalent of allylic polyacrylonitrile can be added, versus secondary amines that can only accept one equivalent. Any functional alcohol or amine starting material can be reacted with the allylic polyacrylonitrile and then reduced to form the polyamine is part of this invention.

[0019] Figure 6 shows the synthesis of secondary amines. In Figure 6, the reagents are 2 moles of the same nitrile ether, but this need not be the case. R and R1 can be different and even a range of mixtures can be used, which will give a mixture of symmetrical and asymmetric secondary amines. The ether nitriles of the invention can also be reacted with alkyl nitriles, such as tallow nitrile, or more conventional ether nitriles, such as the ether nitrile formed by the synthesis of fatty alcohols such as Exxal 10 and acrylonitrile to form secondary amines asymmetric and even nitriles formed from acrylonitrile and siloxanes terminated in hydroxyl or silyl alcohols. The use of different nitriles allows the chemist to produce secondary amines with a range of hydrophobias and surfactants. The conditions for synthesis are more severe than the synthesis of primary amines. The reaction usually takes 2 hours at 220 ° C, but only about 300 psi of hydrogen pressure. Typical sponge nickel can be used, but branched beta products appear in greater quantities. A nickel carbonate catalyst will reduce the formation of this by-product. While Figure 6 shows only the synthesis of symmetric secondary amines, asymmetric secondary amines and their derivatives are part of this invention. The quaternary dimethyl shown in line 3 of Figure 6 is particularly suitable for drilling clays treated to form hydrophobic clays for use in oilfield drilling muds, as well as biodegradable fabric softeners. These dimethyl quats can be formed either as a sulfate or chloride salt, depending on the methylating agent, usually DMS or methyl chloride. The benzyl chloride quats are useful for antimicrobials and corrosion inhibitors. Ethylbenzyl and naphtha quats are also antifungal.

[0020] The symmetric tertiary amine of the first row in Figure 6 is obtained with slightly different conditions. A yield of 85% tertiary amine is obtained by reacting at a lower pressure, ~ 100 psi, for 4 to 6 hours. The corresponding asymmetric tertiary amines can be made by varying the nitriles used as starting materials in the reaction vessel. Similarly, derivatives, such as amine oxides and quaternary analogues to those presented with methyl tertiary amine, are obtained in a similar manner. Tertiary polyalkoxylate quaternaries are particularly useful as hair conditioners, particularly when a silyl nitrile is used as a starting material.

[0021] As in Figures 2, 3 and 4, the amines in Figure 5 and Figure 6 can be derived from tertiary amines, amine oxides, quaternary, sulfonates, sulfates, betaines, betaine esters, phosphonates and alkoxylates. The amine products described in this invention are used in mineral flotation, alone or in combination with other known collectors, and or with nonionic surfactants or other foaming aids, asphalt emulsifiers.

[0022] Various descriptions and illustrations have been presented to improve understanding of the present invention. One skilled in the art will know that various changes and variations are possible without departing from the spirit of the invention. Each of these changes and variations is within the scope of the present invention.

Claims (12)

1. Ore collector, characterized by the fact that it has the following structure:

where R is linear or branched, saturated or unsaturated, cyclic or acyclic from 1 to 9 carbons, R1 is chosen from -CH3, -CH2CH3. n is an integer greater than one. 2. Ore collector, according to claim 1, characterized by the fact that R = C (CH3) 3, R1 = -CH3 and n = 3. 3. Amine collector according to claim 1, characterized by the fact that R = -CH (CH2) 2, R1 = -CH3 and n = 3. 4. Amine collector according to claim 1, characterized by the fact that R = -CH3, R1 = -CH2CH3e n = 3 5. Ore collector, characterized by the fact that it has the following structure:

where R is linear or branched, saturated or unsaturated, cyclic or acyclic from 1 to 8 carbons, R1 is chosen from -H, -CH3, -CH2CH3. n is an integer greater than zero. 6. Ore collector according to claim 5, characterized by the fact that R = C (CH3) 3, R1 = -CH3 and n = 3. 7. Amine collector according to claim 5, characterized by the fact that R = -CH (CH2) 2, R1 = -CH3 and n = 3. 8. Amine collector according to claim 5, characterized by the fact that R = -CH3, R1 = -CH3 and n = 3 9. Surfactant, characterized by the fact that it has the following

where R is linear or branched, saturated or unsaturated, cyclic or acyclic from 1 to 8 carbons, R1 is chosen from -CH3, -CH2CH3. n is an integer greater than zero. 10. Surfactant, according to claim 9, characterized by the fact that R = -C (CH3) 3, R1 = -CH3 and n = 3. 11. Amine collector according to claim 9, characterized by the fact that R = -CH (CH2) 2, R1 = -CH3 and n = 3. 12. Amine collector according to claim 9, characterized by the fact that R = -CH3, R1 = -CH3 and n = 3.

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