CA1100239A

CA1100239A - Emulsified ether amines and process for using same in froth flotation

Info

Publication number: CA1100239A
Application number: CA288,899A
Authority: CA
Inventors: Robert E. Lawlor; Dale H. Johnson; Harold C. Nemeth
Original assignee: Individual
Current assignee: Individual
Priority date: 1976-10-18
Filing date: 1977-10-17
Publication date: 1981-04-28
Also published as: BR7706938A

Abstract

Abstract of the Disclosure Emulsifiable ether monoamines and diamines are shown to be stable compositions, suitable for use in a froth flotation process. The emulsified forms of the amines are effective substitutes for the ether amine acid salts for use in mineral beneficiation, corrosion inhibition, water treatment and the like.

Description

llOQ2;~9 Il BACKGROUND OF THE INVENTION
This invention relates to dispersed forms of primary ¦ aliphatic ether monoamines and diamines and more particularly to ¦.such amines in the form of an emulsifiable composition and as aqueous emulsions and a process for making the same.
i This lnvention also relates to a process for using ¦Iprimary aliphatic ether amines and diamines as cationic silica ¦Icollectors in the froth flotation of ores, for example, a~ cationic ¦¦sllica collectors in the rroth flotation of iron ore.

2;~9 Froth flotation is a common process applied in the art of separating or concentrating minerals from ore or the like. Briefly, the flotation process usually comprises grinding crushed ore, classifying the ground ore in water, treating the classified ore by flotation to remove one or more minerals while the remainder of the minerals of the ore remain behind, thick-ening and filtering the separated concentrate, and thereafter treating the same for the ultimate use of the separated mine-rals. In carrying out the flotation step, a collector is added to the ore dispersed in the water, other agents such as depres-sants and frothers may be added, and air is introduced into the pulp to form a froth, and the froth, containing certain of the mineral components is withdrawn.
Ether monoamines and diamines have been known to be effective collecting agents for use in a froth flotation pro-cess. Such amines have little water solubility and are thus not easily utilized in the aqueous froth flotation process.
In U.S. Patent No. 3,363,758, primary aliphatic ether amine acid salts are shown to be useful forms of such amines, which are thus rendered water dispersible. However, the use of such ether amine salts creates other processing problems, es-pecially promotion of corrosion of the physical apparatus utilized in the process. There is, therefore, a need for a process for utilizing ether amines in froth flotation which process is not attendant with the problems created by using acid salts.
SUMMARY OF THE INVENTION
It has now been discovered that primary aliphatic ether monoamines and diamines may be emulsified by utilizing certain emulsifying agents. Such emulsified ether amines may then be utilized in mineral beneficiation, corrosion inhibi-tion, water treatment, and the like without the attendant 2~}9 problems, such as corrosion promotion, which are present when the acid salts of such amines are employed for such purposes.
In accordance with a broad aspect of the invention, there is provided a pre-emulsion mixture comprising an ether amine selected fromthe group consisting of primary aliphatic monoamines and diamines, and an emulsifying agent present in an amount less than 20 percent, by weight, said amount of emul-sifying agent being effective to form a stable aqueous emulsion containing up to 15 percent amine, by weight.

-2a-2;~9 The ether amines which are useful in the practice of this invention are primary aliphatic ether monoamines and di-amines. The ether amines which are especially useful are those amines represented by the general formula R-0-R'-NH2, where R
is a straight or branched chain aliphatic radical, preferably an alkyl radical, and R' is a straight or branched chain alkyl-ene group or linkage or R' is the divalent radical:
- R"' R"

H H H
where R" and R"' are independently selected from the group con-sisting of hydrogen and methyl. R preferably has 6 to 22 carbon atoms, and more preferably 7 to 15 carbon atoms, and this R may be an alkyl group with 1 to 4 methyl branches, such as the alkyl group derived from an oxo alcohol or mixtures of such alcohols, e.g., isooctyl alcohol, 3,4,4-trimethyl l-hexanol, decyl alcohol, and tridecyl alcohol. Where R' is said alkylene linkage, R' preferably has 2 to 6 carbon atoms and more prefer-ably 3 carbon atoms.
Representative ether monoamines and ether diamines are shown in columns 3, 4 and 5 and U.S. Patent No. 3,363,758.
It has been found that ether monoamines and diamines of the type described above may be combined with certain emul-sifying agents and thus rendered in a dispersible form. Typic-ally, the emulsifying agent is present in an amount less than 20 percent, by weight, based on the total weight of the amine/
emulsifier system. Such a combination of the amine with the emulsifying agent shall hereinafter be referred to as a pre-emulsion mixture. Also present in the pre-emulsion mixture may be a carrier for the emulsifying agent and/or impurities in the 2~9 ether amine. Such carriers and/or impurities may be present in varying amounts, usually not more than 20 percent by weight of the pre-emulsion mixture, and do not have a substantial ef-fect on said -3a-I ~1~ ( a ~ I

I . I
¦ mixture. When certain impurities, such as unreacted long-chain alcohols, are present, it is desirable to utilize a larger amount of emulsifying a6~nt than when no such impurity is present.
In processes such as the froth flotation of ore, it is the practice to use the ether amines at a concentration of approximately 2.5 to about 8 percent, based on the weight, of the amine, 5 percent being most preferred.
A typical ether amine emulsion contains up to about 15 parts of ether amine, about 1 to about 10 percent being preferred and about 2 to about 8 percent being most preferred. The emulsifying agent is usually present at a concentration of ~rom about 2.5 to about 20.0 percent, based on the weight o~ the amines ~ Water is, thus, usually present in~an amount of from about 70 to about 98 percent, by weight. Of course~ a portion of the water may be replaced with other carriers for the emulsifying agent or impurities such as free alcohol. In the froth flotation process, the emulsion _ ., ,..., ... .
is metered into the pulp at levels of from about 50 to about 500 grams of ether amine per ton of ore to be beneficiated.
.- . .. ,, ~ ,, ., _ _ ,,, . ,. ., . ._ .__ Tables I, II, and III show various pre-emulsion systems which have been utilized to make ether amine emulsions. The numerical entry shows the l weight percent o~ emulsifying agent that was combined-with the balance of ether amine. The weight percent of emulsifying agent is not expressed on an active basis, but rather at the amount of emulsifier composition utilized, as commercially available. ~hus, in Table I, the weight percent of emulsifier must be multiplied by the activity of the emulsifier, expressed as a per-centage in the Tables, to determine the actual wei~ht percent Qf activa emulsifier that was employed. The pre-emulsion systems were all utilized to make aqueous emulsions containing 5 percent, by weight, or ether amine.
~hose pre-emulsion systems which produced stab-le emulsions of the ether amines are indicated with an asterisk (*) on the Tables.
It is especially evident from the foregoing Tables that a high degree 3o of selectivity must be utilized when choosing an emulstfier for any given ether amine.
In the ~ables, Armeen~ A-13 and Duomeen~ A-13 are Armak Company~s . . I , - :
' - ~ .
, . , . , . . . ..... . . .

2~9 !'`l I
!~ trademarks for the ether monoamine and ether diamine, respectively, made - - ), from isotridecylalcohol, acrylonitrile, and hydrogen. ArmeenR EA-25 and i¦ DuomeenR E.4-25 are Armak Company's trademarks for the ether monoamine and ¦~ ether diamine made from an alcohol mixture comprised mainly of C12-C15 alcohols~
5 ¦1` approximately equal amounts of all chain lengths being present, ArmeenR EA-80 i and DuomeenR EA-80 are Armak Company's trademarks for the ether monoamine l and ether diamine made from an alcohol mixture comprised of 5-6~ C6 alcohols, --- 55~ C8 alcohols, and the remainder C10 alcohols, acrylonitrile and hydrogen.
ArmeenR EA-80-S refers to the ether amine composition as described above, which has been substantially stripped of free alcohol which is usually present at a level of about 15~, by weight, in the commercially available ether amine composition. By comparing the pre-emulsion systems formed with the alcohol-stripped material to the systems formed with the non-stripped ether amine, it is apparent that more emulsifier must be present to form a stable aqueous emulsion when the non-stripped ether amine is employed, than - ¦ whcn the lcohol stripped ether _ine i~ e~plo~ed.

I ' ., . ~ .. ~
~ ' .. .
. ~5~

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N I ~ ~ i , ~ .t~'i ~ O O
W . O~
, bls(2-hydroxyethyl) . . ~ 'cocoamine - 100~, ~, o~ ', o i oo ~ ~ ~ ~ . , ~ j ~ ~ ,polyoxyethylene(15) _ ~ ' ~ ~ ~ O ' O O Icocoamine - 10~%

~. ~ , , , ~ bis(2-hydroxyethyl) o ~ I I I o tallowamine - 10~ ,}
c, .. i I ~_ i - . . i ~L ~ ~ polyoxyethylene (5).' ,j . tallowamine - lO~jj _ I -~- !
' ' i ~ polyoxyethylene(l~5)!
, ~ ~ ~ 1, ~ o ~ allowamine _ loc%
~"t, ~ j ot, !* ~,o i ~ ~ I __ l . I
~ ~ . . ~, olyoxyethylene(5) D ~ L ~ ~o leylamine -100%
~ ,,, _ _ _ . ~ I e~
~ ~ ! ~c ~c ~ N NrN'tris(2 hydroxy ~5 i'_5 - I I ~ o Il o 1,3 diamino pro- 1~
. ~ ~p~ne -100% ¦
~, ~ -; i - IN, N,N'polyoxyethylene, ,- ,5 . ~ ~ . (15)-N-tallow-1,3 I, o .p t I o diamino propane-100 .t, ~ - ~ . , ~;o o ~ o o ~I o ~ ~ i ~ w ~ dlmethyldicocoamm-' ;~o5c~ ,o looct~ ~O il ~ I o~o ImiUm chloride- 75%
D ~, ~ * * * * ; * ~ . i .

3 OD . ~ ' ~ t 1 ~ ltrimethylcoco~ mon-!
~ ~, ~5 , 0~ ! 'i ~ ~o o ¦ lum chloride- 50 %
~ ~ _ .~. , , ~ ~ I
5 ~ ' ~ 1 ~ ~ t ~ ~o~ , trlmethyltallow II
o I ,~ ~ O O ¦ammonium chlor-~ ~5 `. ,* ~ * ~ t ~" * I lde - 50% II
._,_,.. . ~. .:_.. ~. _.. _. _.. _ _. _.. __. _.. ~._ .__- --- -- j- - - ---------------- ! I
¦ ~ ~ o ~ ~ Ildimethyldi(hydro- I~
~5 ~ o j o ~ ~ 0~00 igenated-tallow) 1, ,~ tot ~ , *~ ammonium chlor- ,I
-------.~ ~ ide - 75% 5 5 ~ ~ ethylpolyoxyethy-~~ ~ I ' ¦ 'lene(15) cocoammon-ium chloride-100% :
~ ~ I t ~n 1 1 ii . I j , ! . ` . ~ethyl-2-hydrOxyeth- !¦
o ~ldicocoammonium . ~ chloride- 75% ll ~N~ I oO~ ~~ ~ ' ~ methylbls~2-hydro- !'-o o ~,. . . . j ~yethyl) cocoammon-`l o o oI~ a o o o . O I lium chlorlde-75 ~ ¦¦

'`` r T ~ lloc2~s ll c c i ~ i w ~i lw ~ w w W ; W jz ~; :z Z ~
2 Z : 2 ~ i ,W W W
W P .W ~D . ~ :~ ~
JFi W .~0 0 :1 L _ ` ;,, . ~i ~,, 1 methylbis(2-hydroxy, o ~t o ~ O O ¦ethyl)oleylammon-' * ` ~ ~ ` . * .ium chloride- 72%

¦ . Imethylpolyoxyethy-~' ~ ~ I lene(l5)octade . ~ o~ ammonium chloride- ~' * , ~ : i ! i 100% , i ' '' , ~, ~, ~ ¦methylbis(2-hydrox- !
.~ i . . . . . ~yethyl) tallowamm-!onium chloride- 75%~
* ' * j# ,I t N ' I~ ~)ii ' i 'I 0~rt ~ bis(2-hydroxyethyl), ~ ~ o o, o cocoamine oxide-50g ~It '. ~rt , ~St i ¦ ~ ? i ll ; ~ ~ I i ~,¦ ¦bis(2-hydroxyethyl) . . ~ , ,, tt~llowamine oxide-: ~ ~ ¦ . . 5% .,~, # I jt . j . .ll H
, , t~ ~ - ~ Idimethyl cocoamine .,' H
w. w ~w l j ~ o ~, . loxide - 40% l .
. w ~ ,w , I ,i ,i # ~* .,* 1, I ~ i . , I I ,, I dimethyl(hydrogen-w i ~w i , ~, ' ated-tallow) amine w w ; ,`ol loxide - 40%
* ~ I l I ~ ~ I .N-cocoaminobutyric '` . ~! Acid - 55%
~rt . ~
I , i~ ~,~ , ,polyoxyethylene(15), . ~ ~ I i ;~ ~ ~ Il : glycol tallate-100%:
~ oo j ~ I
.
, I ~ ~ I ~ ~ polyoxyethylene glycol.
. ~ ~ , I I . , o , 400 monooleate-100%i ~ , ~ o~o , l 1 . , 11 polyoxyethylene glycol . ~ `~ ~ i O I400 monolaurate-100 a~
polyoxyethylene glycol ~ !~ ; ~ I . 600 monooleate-100%I

~ ! ~ ¦ 7 I I I 1 1. Il ~.~ I ~,., . Il W i~ W ' W W D ~ 239 W i W~ ` W i ~ ~ W ¦
l I l I i N ~ H ` 0~ CO
: . ~n I w o ! ~ j' W ~o 1, l c~ o ~ Polyoxyethylene glycol~
~ I a~ o ~ o,1000 monostearate-l I W I I I w~ ! ~o~ i Sodium Laurylsul- i o O O ,fate - 30 % ji . ~ ~ ITrlethanolamine '~
. ~ i O loleate -100%

.i I ~' ¦Sodiumoleate -100% i I ~ ~ ISodium laurylether !, ~ O isulfonate- 60%
1 ~i ',Sodium laurylben- .
zene sufonate- 40% il . ~ - ~ ~Oleic acid diethanol ¦ to ,amide- 100% ijl : . ¦ ~ iTriethanol amine 7 I o ¦lauryl sulfate-40% ~
,Span~80 -100% H
O~ O~ ¦ ~ - H

: ~ ~ ~ I ~ ~ o I o '~Tween~80 - 10~
~ o~ tt~ I ~
.. I .1 -I i I' a~ !, ~ '' o ~ ISpan~80/Tween~D80 . . . . . ~ 1 mixture by wei-,jght- 100%
3 , I I
I ~ o hleYlsarcosine-. I ~ I 1 5~
i t ' i ~ ~ Amphoteric Complex l!
. ¦ ~ j j o o ~Cocoamido com- ,¦
¦ I i `pound - 34%
Polyethoxylated(5),l octyl phenol-100% il i ~ I 1 ~"~ Polyethoxylated(g) , nonyl phenol-100~

~ I I - 1 1 1- `~ 11 il 11~2~9 ~, ! . I
~I For purposes of comparing the utility of the emulsified ether amines _ _ta_the ether_amine acid_ealts~ as ~aught i~_U ~ o j~ emulsion systems of the present inventic~ were compared to an acid salt of ¦~ an ether amine, sold under the trademark Arosurf MG-83 by Ashland Chemical ¦~ Company. For all three compositions the ether amine was a N-(tridecoxy-n- , -i propyl)-1,3 propylene diamine. A pre-emulsion mixture containing 5 parts of DuomeenR EA-13 ether diamine and 1 part of polyethoxyethylene(l5) cocoamine ("A") and a pre-emulsion mixture containing 5 parts of DuomeenR EA-13 ether diam~ne and 0.5 part of polyethoxyethylene (15) cocoamine and 0.5 part of di-methyldicocoam~onium chloride, -75 percent active ("B") were utilized to make aqueous emulsions containing 5~ amine by weight. Said emulsions were compared to a 5~ solution formed from ArosurfR MG-83 ether amine salt, N-¦ (tridecoxy-N-propyl)-1,3 propylene diamine which had been 40 percent neutralize, 1 ¦ with acetic acid ("C") in a typical froth flotation process in which silica ¦ i8 removed from oxidized taconite ores. The compositions were used at a level ¦ of 0.31 pounds of reagent per ton of ore. ~he results of the comparison ¦ are shown in Table IV.
~ I . , , ¦ TABLE IV

Compos_tion Grade of FeJ~ Recovery-~
A 61.60 80.22 B 62.04 & .89 -C 62.16 82.75 From the foregoing it is apparent that emulsified ether amines are are effective substitutes for the ether amine acid salts for the flotation of silica from iron ore.

~,, . ~ - , -,., ~ , , .,. , ,, .~ . ;, ~.

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:-

1. A pre-emulsion mixture comprising an ether amine selected from the group consisting of primary aliphatic mono-amines and diamines, and an emulsifying agent present in an amount less than 20 percent, by weight, said amount of emulsifying agent being effective to form a stable aqueous emulsion containing up to 15 percent amine, by weight.

2. The mixture of claim 1 wherein said ether amine is defined by the formula R-O-R'-NH2, where R is a straight chain or branched chain aliphatic radical and R' is a straight chain or branched chain alkylene group or the divalent radical:

wherein R" and R''' are independently selected from the group consisting of hydrogen and methyl.

3. The mixture of claim 2 wherein R contains 6 to 22 carbon atoms and R" and R''' are hydrogen.

4. The mixture of claim 2 wherein R contains 7 to 15 carbon atoms and R' is an alkylene linkage containing 3 carbon atoms.

5. me mixture of claim 4 wherein said aqueous emulsion contains from about 2 to about 8 percent amine, by weight.

6. The mixture of claim 1 wherein the aqueous emulsion contains from about 1 to about 10 percent amine, by weight, R contains 7 to 15 carbon atoms, R' is the divalent radical wherein both R" and R''' are hydrogen and the emulsifying agent is present in an amount of from about 2.5 to about 20 percent, based on the weight of said mixture.

7. The mixture of claim 1 wherein the aqueous emulsion contains from about 2 to about 8 percent amine.

8. The mixture of claim 1 wherein the emulsifying agent is present in an amount of from about 2.5 to about 20 percent, based on the weight of said mixture.

9. The mixture of claim 1 wherein the emulsifying agent is present in an amount of from about 1 to about 5 percent, based on the weight of said mixture.

10. An aqueous emulsion comprising (1) up to about 15 parts of an ether amine selected from the group consisting of primary aliphatic ether monoamines and diamines, (2) from about 2.5 to about 20 percent of an emulsifying agent based on the weight of said ether amine, and (3) from about 70 to about 98 parts of water.

11. The emulsion of claim 10 wherein said ether amine is defined by the formula R-O-R'-NH2, where R is a straight chain or branched chain aliphatic radical and R' is a straight chain or branched chain alkylene group or the divalent radical:

wherein R" and R''' are independently selected from the group consisting of hydrogen and methyl.

12. The emulsion of claim 11 wherein the aqueous emulsion contains from about 1 to about 10 percent amine, by weight.

13. The emulsion of claim 12 wherein R contains 6 to 22 carbon atoms.

14. The emulsion of claim 12 wherein R is an alkylene linkage containing 2 to 6 carbon atoms.

15. The emulsion of claim 12 wherein R' is the divalent radical wherein both R" and R''' are hydrogen.

16. In a froth flotation process for separating mineral components of an ore from said ore, wherein said ore is frothed in the presence of an aqueous medium contain-ing a water dispersible ether amine selected from the group consisting of primary aliphatic ether monoamines and diamines, the improvement comprising providing said ether amine in the form of an aqueous emulsion containing from about 2.5 to about 20.0 percent emulsifying agent, based on the weight of said ether amine.

17. The process of claim 16 wherein said emulsion contains from about 1 to about 10 percent amine, by weight, said amine being defined by the formula R-O-R'-NH2, where R is a straight chain or branched chain aliphatic radical and R' is a straight chain or branched chain alkylene group or the divalent radical:

wherein R" and R''' are independently selected from the group consisting of hydrogen and methyl.