AU2016344360B2

AU2016344360B2 - Amine mining collectors

Info

Publication number: AU2016344360B2
Application number: AU2016344360A
Authority: AU
Inventors: Thomas P. Daly
Original assignee: Individual
Current assignee: Individual
Priority date: 2015-10-27
Filing date: 2016-10-26
Publication date: 2021-05-27
Anticipated expiration: 2036-10-26
Also published as: CA3003268A1; CL2019003065A1; BR112018008468B1; CL2018001091A1; ZA201802746B; AU2021221877B2; CA3251295A1; CN108349854A; AU2016344360A1; WO2017075003A1; AU2021221877A1; BR112018008468A2; PE20181315A1

Abstract

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

Description

Amine Mining Collectors

BACKGROUND

Field of the Invention

The present invention relates to the field of amine mining collectors and more

particularly to a class of ether amines.

Description of the Problem Solved by the Invention

Many commercially important mineral ores are mined from the earth in relatively low

concentration. For instance, in Minnesota's Mesabi range, the ore consists of approximately

25% iron. Prior to further processing, the desired minerals must be concentrated. The

present invention improves the process of concentrating the desired mineral.

The preceding discussion of the background art is intended to facilitate an

understanding of the present invention only. The discussion is not an acknowledgement or

admission that any of the material referred to is or was part of the common general

knowledge as at the priority date of the application.

SUMMARY OF THE INVENTION

The present invention relates to the field of amine mining collectors that improve the

yield of ore concentration. The use of amines with sufficient water solubility, that form strong

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, xanthate and dithiocarbamate

collectors of the present invention does just that. N The present invention provides an amine mining collector of the following structure:

R,O ( O),,- NH2 R

wherein R is linear or branched, saturated or unsaturated, cyclic or acyclic from 1 to 9

carbons, R 1 is chosen from -CH3, -CH2CH3. n is an integer greater than one.

In an embodiment R=-C(CH3)3, R 1=-CH3 and n=3.

In an embodiment R=-CH(CH2)2,R 1 =-CH3, and n=3.

In an embodiment R=-CH3, R1 =-CH2CH3, and n=3

The present invention further provides a mining collector of the following structure:

S

R OnO s- Na'

wherein R is linear or branched, saturated or unsaturated, cyclic or acyclic from 1 to 8

carbons, R 1 is chosen from -H, -CH3, -CH2CH3; n is an integer greater than zero.

In an embodiment R=-C(CH3)3, R 1=-CH3 and n=3.

In an embodiment R=-CH(CH2)2,R 1 =-CH3, and n=3.

In an embodiment R=-CH3, R1 =-CH3, and n=3

The present invention further provides a surfactant of the following structure:

,CH 3 0 N--O

R 1 OH 3

carbons, R 1 is chosen from -CH3, -CH2CH3; n is an integer greater than zero.

In an embodiment R =-C(CH3)3, R 1=-CH3 and n=3.

In an embodiment R=-CH(CH2)2,R 1 =-CH3, and n=3.

In an embodiment R=-CH3, R1 =-CH3, and n=3. N The present invention further provides a mining collector of the following structure:

R,, O),-_NH NH2 R

wherein R is linear or branched, saturated or unsaturated, cyclic or acyclic from 1 to 22

In an embodiment R=-C(CH3)3, R 1=-CH3 and n=3.

In an embodiment R=-CH(CH2)2,R 1 =-CH3, and n=3.

In an embodiment R=-CH3, R1 =-CH2CH3, and n=3.

In an embodiment R=-CH3, R1=-CH3, and n=3.

In an embodiment R=-CH2CH3, R1=-CH3, and n=3.

In an embodiment R=-CH2CH3, R1=-CH2 CH3, and n=3.

In an embodiment R=-CH2CH2CH3, R1=-CH3, and n=3.

In an embodiment R=-CH2CH2CH3, R1=-CH2CH3, and n=3.

In an embodiment R=-C(CH3)3, R1=-CH2CH3 and n=3.

In an embodiment R=-CH(CH2)2, R1=-CH2CH3, and n=3.

The present invention further provides a quaternary amine corrosion inhibitor of the

following structure:

CH 3

0+ ) 0l - A R1 N-D A R CH3

carbons, R 1 is chosen from -H, -CH3, -CH2CH3; n is an integer greater than zero; D is -CH3,

CH2C6H5, -CH(CH2CH3)C6H5, -CH2CH3, -CH2C10H7; and A" is chosen from Cl" or SO3"

In an embodiment D=-CH3, R=-C(CH3)2, R1=-CH3, D=-CH3, A-Cl" and n=3.

In an embodiment D=-CH2C6H5, R=-C(CH3)2, R1 =-CH3, A"=CI", and n=3.

In an embodiment D=-CH3, R=-CH3, R=-CH2CH3, A"-=Cl"-, and n=3.

S S- O SS

M+ R M+

where R 1 is chosen from -H, -CH3, -CH2CH3; n is an integer greater than zero; M+ is a cation.

In an embodiment M+ is Na+, R 1=-CH3 and n=3.

In an embodiment M+ is Na+, R 1=-CH3 and n=1.

In an embodiment M+ is Na+, R 1=-CH3 and n=5.

The present invention further provides an amine mining collector of the following N structure:

R,O ( O NH2

R

carbons, R 1 is chosen from -CH3, -CH2CH3; n is an integer greater than one and less than

100.

The present invention further provides a surfactant of the following structure:

,CH 3 0 N--O

R 1 OH 3

carbons, R 1 is chosen from -CH3, -CH2CH3; n is an integer greater than zero and less than

100.

R,O t O), ,- NH NH2 n R

carbons, R 1 is chosen from -H, -CH3, -CH2CH3; n is an integer greater than zero and less than

100.

following structure:

CH 3

R1O 0 + rOi-D AA

R CH3

carbons; R 1 is chosen from -H, -CH3, -CH2CH3. n is an integer greater than zero and less

than 100; D is -CH3, -CH2C6H5, -CH(CH2CH3)C6H5, -CH2CH3, -CH2C10H7; and A"- is

chosen from Cl" or SO3".

Description of the Figures

Attention is now directed to the following figures that describe embodiments of the present

invention. A description of the figures which are directed to these embodiments is as follows:

Fig. 1 shows the synthesis of novel ether amine cationic mineral collectors.

Fig. 2 shows the synthesis of novel anionic mineral collectors.

Fig. 3 shows the synthesis of derivatives of the cationic collectors.

Fig. 4 shows the synthesis of tertiary amine derivatives.

Fig. 5 shows the synthesis of polyprimary amines.

Fig. 6 shows the synthesis of secondary amines and derivatives.

DETAILED DESCRIPTION OF THE INVENTION

Mineral ores that are concentrated by floatation are dug out of the ground and ground

to a predefined small particle size. The grains or ore are then treated with various surface

active molecules and pumped into a floatation pond where dissolved air is introduced. The

ore binds to the collector, that creates a water insoluble particle. This water insoluble

complex is then floated to the surface by exclusion from the water into the air bubbles that

form in dissolved air floatation. Frothers keep a thick head of foam that supports the mineral

at the surface until rakes of booms can skim the mineral complex into hoppers for further

processing. Ideally, the non target components of the dirt / ore mixture are left to settle to the

bottom of the floatation ponds, thus concentrating the desired minerals to an extent that they

can then enter the next processing steps, be it reduction, purification or other processing

steps.

The present invention utilizes alkoxylates as the backbone of the collector. By varying

the side chains on the collector and the chain length, either though increasing the number of

repeating units, or by utilizing different chain length or conformations of alcohols to initiate the

alkoxylation adjustments to the water solubility, frothing potential and density of the mineral

collector complex can be made. These adjustments allow for the optimization of the collector,

by increasing the yield of the target mineral and reducing the collection of non-target minerals,

such as silicates.

Figure 1 shows the synthesis of primary amine and diamine collectors. Water is typical

used to make polyalkoxylates. The resulting polyalkoxylates have 2 terminal hydroxyls and

can react with 2 moles of acrylonitrile to form the di-primary amine. The use of diols and

polyols, such as resorcinol, glycerin, neopentyl glycol, and pentaerythritol produce multiple

hydroxyls and the analogous products can be formed. The higher polyols beyond dios,

introduce branching, which is useful for lower pour points and easier handling, particularly in cold climates. While the figure shows the alkyl portion, R being from 1 to 8 carbons, this is the preferred range for the ore that is mined today. Higher carbon chains show promise in more unusual ores where heavier species are being floated. The invention covers these higher carbon chain analogs as well. This analog holds true for all subsequent figures as well.

The use of a monohydric alcohol, such as methanol, ethanol, propanol or butanol

results in a polyalkoxylate with just one terminal hydroxyl to react the acrylonitrile with,

resulting in a primary amine collector. Utilizing higher carbon number alcohols reduces the

water solubility of both the collector and the collector-mineral complex. Non-linear alcohols,

like phenol, cylcohexanol, isopropanol, or t-butanol reduces the pour point for easier handling

in cold climates.

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). The Michael Addition of

acrylonitrile to the alcohol and the amine is well known, as is the reduction of the nitrile to the

amine with sponge nickel or other sponge metals, either promoted or not, with hydrogen. The

reduction typically takes place at a pressure between 400 to 800 psi at less than 40 C over 4

to 12 hours. The Michael Addition is typically done by adding acrylonitrile to the alcohol or

amine at ambient temperature with cooling at such a rate as to maintain temperature.

Elevated temperatures lead to polymerization of the acrylonitrile. If needed, a catalytic

amount of caustic may be used to accelerate the Michael Addition with alcohols. The yields

are typically in excess of 96% and no further purification is necessary for a commercial

product. These collectors are useful where cationic collectors are required, such as iron ore

and potash.

Figure 2 shows the synthesis of the anionic analogs of the collectors in Figure 1. The

xanthates and dithiocarbamates. The di-dithiocarbamates may be made from the diamines.

The anionic collectors are typically used in sulfide ores. The same solubility trends apply to

the anionics as to the cationic collectors of Figure 1. The xanthates are synthesized by

reacting carbon disulfide (CS2) with the alcohol group under basic conditions. The

dithiocarbamates are made similarly, but reacting an amino group instead of an alcohol group.

The result is a salt of the 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. The xanthates and

dithiocarbamates can be made as the salts of amines, as well as of mineral bases.

The collectors of the present invention have additional uses as well. The cationic

collectors have utility in personal care as surfactants, cleaners, emollients, rheology modifiers,

and to buffer the products. The primary amines and diamines also have utility in asphalt as

antistrips. Figure 3 shows several derivatives. Amides with fatty acids of the cationic

collectors are made simply by combining the cationic collector with the desired fatty acid,

typically stearic acid or coconut fatty acid and heating to remove a mole of water for each

amide group formed. The amides are versatile rheology modifiers. Amphoterics of the

cationic collectors can be made through the reaction of sodium monochloroacetic acid (reflux

1:1 molar equivalents of SMCA for approximately 8 hours), or for a salt free form, acrylic acid

or methacrylic acid may be reacted by adding the acid at ambient temperature or below to the

cationic collector with sufficient cooling to keep the temperature below 30 C. The esters can

be made by reacting the esters of the acids. A diaddition can be made to the amino group by

continuing the reactions. Sulfonates can be made by reacting sodium vinyl sulfonate,

propane sultone or butane sultone, or higher sultones can be reacted similarly to create the

sulfonates with a longer carbon chain between the nitrogen and the sulfur. Phosphonates can

be made by reacting phosphonic acid and formaldehyde. The salted products derivatives of 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 sponge nickel under similar conditions to the nitrile reductions in

Figure 1. The tertiary amines can then be made into quaternaries or amine oxides. The

quaternaries of methyl chloride, diethylsulfate, ethyl benzyl chloride, and benzyl chloride are

all facile reactions at ambient temperature that yield the analogous quaternaries.

Figure 5 shows the synthesis of novel collectors based on allylic polynitriles that are

then reduced to the polyamines. This unique approach allows for the synthesis of

polyprimary amines. The starting material may be an alcohol, an amine, a polyamine such as

Tallow Diamine, common trade name Akzo Duomeen T, or polyether amine, such as Air

Products DA-14, ethoxylated amines, such as Akzo Ethomeet T12, or ethoxylated ether

amines, such as Air Products E-17-5. In the case of primary amines, a second equivalent of

the allylic polyacrylonitrile can be added, versus the secondary amines that can only accept

one equivalent. Any alcohol or amine functional starting material may be reacted with the

allylic polyacrylonitrile and then reduced to form the polyamine is part of this invention.

Figure 6 shows the synthesis of the secondary amines. In Figure 6, the reactants are 2

moles of the same ether nitrile, but this need not be the case. R and R 1 may be different and

even a wide range of blends may be used which will give a mixture of symmetric and

asymmetric secondary amines. The ether nitriles of the invention may also be reacted 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

asymmetric secondary amines and even the nitriles formed from acrylonitrile and hydroxyl

terminated siloxanes or silyl alcohols. The use of differing nitriles allows the chemist to

produce secondary amines with a range of hydrophobicities and surfactancies. Conditions for the synthesis are more severe than the synthesis of the primary amines. The reaction generally takes 2 hrs at 220 C, but only about 300 psi pressure of hydrogen. Typical sponge nickel may be used, but beta branched products to appear in larger quantities. A nickel carbonate catalyst will reduce this byproduct formation. While Figure 6 only shows the synthesis of symmetric secondary amines, the asymmetric secondary amines and their derivatives are part of this invention. The dimethyl quaternary shown in row 3 of Figure 6 is particularly well suited to treated drilling clays to form hydrophobic clays for use in oilfield drilling muds, as well as biodegradeable fabric softeners. These dimethyl quats me be formed as either the sulfate or chloride salt depending on the methylating agent, typically

DMS or methyl chloride. The bezyl chloride quats are useful for antimicrobials and corrosion

inhibitors. The ethylbenzyl and naphtha quats are anti-fungal as well.

The symmetric tertiary amine of the first row of Figure 6 is obtained with slightly

different conditions. An 85% yield of tertiary amine is obtainable by running the reaction at

alower pressure, -100 psi, for 4-6 hrs. The corresponding asymmetric tertiary amines can be

made by varying the nitriles used as starting materials in the reaction vessel. Similarly, the

derivatives, such as amine oxides, and quaternaries analogous to the those shown with the

methyl tertiary amine are similarly obtained. The tertiary polyalkoxylate quaternaries are

particularly useful as hair conditioners, particularly when a silyl nitrile is used as a starting

material.

Similar to Figures 2, 3, and 4, the amines in Figure 5 and Figure 6 can be derivatized

into tertiary amines, amine oxides, quaternaries, sulfonates, sulfates, betaines, betaine

esters, phosphonates and alkoxylates. The amine products taught in this invention are used

in mineral floatation, either alone or in combination with other known collectors, and or with

non-ionic surfactants or other frothing aids, asphalt emulsifiers.

Several descriptions and illustrations have been presented to enhance understanding

of the present invention. One skilled in the art will know that numerous changes and

variations are possible without departing from the spirit of the invention. Each of these

changes and variations are within the scope of the present invention.

The method steps, processes, and operations described herein are not to be construed

as necessarily requiring their performance in the particular order discussed or illustrated,

unless specifically identified as an order of performance. It is also to be understood that

additional or alternative steps may be employed.

The terminology used herein is for the purpose of describing particular example

embodiments only and is not intended to be limiting. As used herein, the singular forms "a",

"an" and "the" may be intended to include the plural forms as well, unless the context clearly

indicates otherwise. The terms "comprise", "comprises," "comprising," "including," and

"having," or variations thereof are inclusive and therefore specify the presence of stated

features, integers, steps, operations, elements, and/or components, but do not preclude the

presence or addition of one or more other features, integers, steps, operations, elements,

components, and/or groups thereof..

Claims

Claims:

1) An amine mining collector of the following structure:

R,OO NH2

R1

100.

2) The amine mining collector of claim 1 wherein R=-C(CH3)3, R 1=-CH3 and n=3.

3) The amine mining collector of claim 1 wherein R=-CH(CH2)2,R=-CH3, and n=3.

4) The amine mining collector of claim 1 wherein R=-CH3, R 1=-CH2CH3, and n=3

5) A surfactant of the following structure:

,CH 3 R 0 N---O

R 1 OH 3

100.

6) The surfactant of claim 5 wherein R =-C(CH3)3, R 1=-CH3 and n=3.

7) The surfactant of claim 5 wherein R=-CH(CH2)2,R1 =-CH3, and n=3.

8) The surfactant of claim 5 wherein R=-CH3, R 1=-CH3, and n=3.

9) A mining collector of the following structure:

R,OO NHNH2

carbons, R 1 is chosen from H, -CH3, -CH2CH3; n is an integer greater than zero and less than

100.

10) The mining collector of Claim 9 wherein R=-C(CH3)3, R 1=-CH3 and n=3.

11) The mining collector of claim 9 wherein R=-CH(CH2)2,R 1 =-CH3, and n=3.

12) The mining collector of claim 9 wherein R=-CH3, R 1=-CH2CH3, and n=3.

13) A quaternary amine corrosion inhibitor of the following structure:

CH 3

R OO N-D A

R CH3

carbons; R 1 is chosen from -H, -CH3, -CH2CH3; n is an integer greater than zero and less than

100; D is -CH3, -CH2C6H5, -CH(CH2CH3)C6H5, -CH2CH3, -CH2C10H7; and A" is chosen

from Cl" or SO3".

14) The quaternary amine corrosion inhibitor of Claim 13 wherein D=-CH3, R=-C(CH3)2, R 1=

CH3, D=-CH3, A = Cl" and n=3.

15) The quaternary amine corrosion inhibitor of claim 13 wherein D=-CH2C6H5, R=-C(CH3)2,

R1=-CH3, A"=C", and n=3.

16) The quaternary amine corrosion inhibitor of claim 13 wherein D=-CH3, R=-CH3, R1=

CH2CH3, A"=C", and n=3.