FI70378C - SAMLARE FOER MALMER MINERALER OCH FOERENINGAR - Google Patents

Description

1 70378

This invention relates to the synthesis and use of collectors highly selective for ores, minerals and compounds containing phosphate and fluoride and for ores, minerals and compounds containing copper and cobalt.

South African Patent 79/0902 (Berol Kemi Ab) describes amphoteric surfactant compounds of the general formula:

R- (O) - (A) -CH 2 -CH (OH) -CH.-N-C H, Y

π P Ä £, q ^ q

B

Wherein R is a hydrocarbon group having 7 to 24 carbon atoms, A is an oxyalkylene group having 2 to 4 carbon atoms, R 1 is a hydrocarbon group having 1 to 4 carbon atoms or hydrogen, Y is a group C00 or a group SO 2, n is 0 or 1, p is 0-5 and q is 1 or 2, use only in phosphate flotation.

20 These compounds have been found to be of limited use in the flotation of South African phosphate-bearing ores and not at all in the flotation of fluoride or copper or cobalt-containing ores.

According to the present invention there are provided amphoteric surfactants of general formula (1) and their use as collectors in the flotation of the above-mentioned ores, minerals or compounds: -NC H_ YM (1) x 2 2 n 2n wherein R is a hydrocarbon group having 1 to 21 carbon atoms 35 A is an oxyalkylene group having 2 to 4 carbon atoms x is a number from zero to fifteen 2 70378 R 1 is a hydrocarbon group having 1 to 8 carbon atoms or hydrogen n is a number from one to three Y is COO or SO 2 M is NH 4, Na, K or H.

RCOO is preferably a radical of an aliphatic fatty acid compound and may be either synthetic or naturally occurring, saturated and / or unsaturated, straight and / or branched alkyl chains which may be used as individual compounds or mixtures.

10 Suitable materials are available e.g. wheat germ oil, sunflower oil, soybean oil, sesame oil, safflower oil, poppy oil, rapeseed oil, peanut oil, olive oil, palm oil, linseed oil, palm oil, palm oil, linseed oil, linseed oil, linseed oil, linseed oil, linseed oil, linseed oil, linseed oil, linseed oil ! -, pelmito-oleic, linseed oil, linolenic, oleic and behenic acids.

may be saturated and / or unsaturated, unbranched and / or branched, aromatic and / or aliphatic.

The compounds of the invention can be prepared as follows:

The fatty acid or its alkylene oxide adduct is reacted with epichlorohydrin and the chloro-glyceryl ether formed is then reacted with either a compound of general formula: H-N-CnH2nY 111 30 or first of formula? 1 (ii)

H-N-H

35 with ammonia or a primary amine followed by a compound of general formula 3 70378 C1CnH2nY (iii>).

The reaction between the fatty acid or its alkylene oxide adduct and epichlorohydrin is carried out at a temperature in the range of 50 to 150 ° C in the presence of a catalyst. The reaction is catalyzed by Lewis acid. BF3 has been found to be particularly useful because the reaction is easily controllable.

The chloroglyceryl ether is aminated with a primary amine or ammonia in the presence of an alkali such as potassium hydroxide at a temperature in the range of 80-120 ° C. The reaction is generally carried out using a polar solvent, for example water or a lower alcohol such as methanol or ethanol.

The reaction of the secondary amine thus formed with the compound of formula (iii) is carried out in a neutralized aqueous solution for a reaction time of 2 to 6 hours at 50 to 120 ° C.

The carboxylic compound of the invention may contain fatty acids having 2 to 22 carbon atoms as described in more detail above.

Suitable monoamines are allylamine, butylamine, but monoamines having 1 to 18 carbon atoms can also be used. The compound of formula (iii) should be. (λ-monohalogenated to react rapidly with the secondary amine. Examples of preferred β-monohalogenated compounds are β-monochloroacetic acid, monohalogenated chloropropionic acid and α-monochlorobutyric acid, and λ-monochlorobutyrophenone, sulfonic acid,.

4 70378

When this method is used in flotation, pH adjusters, presses and activators can be used in known ways. As it is impossible to formulate general instructions more precisely, each ore must be treated 5 according to its chemical and physical composition.

The compound and method of the invention are illustrated by the following example.

Example 1 a) General synthesis for the preparation of polyoxyethylene fatty acid adducts

1 mole of fatty acid

Moles of alkylene oxide (e.g. ethylene oxide)

0.01 mol of base (e.g. potassium hydroxide)

The fatty acid or mixture of fatty acids, KOH and ethylene oxide is weighed into an autoclave and placed under a nitrogen pressure of 5 bar. The mixture is then slowly heated. Between 150 ° C and 170 ° C, a highly exothermic reaction takes place, which causes the temperature to rise to about 230 ° C. Cooling is initiated and the reaction mixture is cooled to room temperature.

b) General synthesis for the preparation of chloroglyceryl ether of polyoxyethylene fatty acid adducts Fatty acid adduct 1 mole of 1-chloro-2,3-epoxypropane 1 mole 25 (epichlorohydrin)

Boron trifluoroetherate 0.02 moles

The fatty acid ester and boron trifluoride are metered into the reactor and mixed. Epichlorohydrin is added at such a rate that the temperature remains below 150 ° C. After completion of the reaction, the product is washed with water.

c) General synthesis for the preparation of the amine derivative of the chloroglyceryl ether of polyoxyethylene fatty acid adducts 5 70378

1 mole of glyceryl ether

1 mole of amine (or ammonia)

1 mole of base (e.g. potassium hydroxide)

6 moles of water 5

All ingredients are added to the reactor, stirred and heated. Heat to reflux for 1 hour. Stop mixing and separate.

d) General synthesis for the preparation of the final product 10 moles of amine or ammonia derivatives 1 mole of d · monohalonic acid (iii) 1 mole

Mineral acid (eg hydrochloric acid 33%)

2 moles of base (e.g. KOH)

Water 18 moles 15 The amine derivative is neutralized with hydrochloric acid. The cK monohalic acid dissolved in 6 moles of water is added to the reactor and refluxed with stirring for 4 hours. Potassium hydroxide dissolved in 12 moles of water is slowly added to the reaction mixture. The product is then separated from the water-20 layer.

Use as collectors

The products (collectors) were used to obtain apatite from an ore having the following approximate composition: 25 Apatite 22%

Diopside 62%

Phlogopite 12%

Lime slag 2%

Other 2% 30 The flotation method used to obtain the ore in question is as follows: 1) Grind 1 kg of ore for 5 minutes.

2) Trained in a 2 kg cell at 2100 rpm.

35 3) 0.3 g of petroleum sulphonate is added.

4) Train for 2 \ minutes.

6 70378 5) 0.5 g of collector is added.

6) Train for 3 minutes.

7) Decelerate the impeller to 1100 rpm.

5 8) Foam until clean.

9) Clean in a 500 g cell at 900 rpm.

The following results were obtained by varying the collector as shown.

10 (I)

r- (a) x-ch2-ch-ch2-n-c h2 YM

x I I n n

OH R

15 CH3- (CH2) 3 a) r- (ch2-ch2-o) 2-ch2-ch (oh) -ch2-n-ch2-c-ok I! o 7 70378 I;

H os - I I

C eg QJ O ---- oj a £ • SS * ° - 1 1 CQ J____ro_ Γ- -ί - m Π u ^ (~ g r- c-) oo oo r ~ ha oo> - m 0 («. ..

Ö r · U P ~ O -,.

• H in ^ <r <T

J C___ Ο Ό CO

O 'vo o pi eg o oo.

- O 'o' oO, I 0Ä P- Ό U0 _r4 00 CO 00 U ~ l I I ...

I — I 0. -

Oavor '-— Ό oo O

c a - - - ---

HfOOeioo— CJ - O O ', _q co co or co co <o

__I -H

1 1 "——" "“ ** _ _ --- Jj oo oo ^ -P ^ c G r »O kD \ C r ~) fg esc: - <r is 03 * r \ ~ ~ * rrt os oo ρή frj * as en σ * m I o-- »= _ ^ 00“ • na Y „Y ΰ eg--« rH (Ö00r ^ OX '0, £ ro co <r υζ 0Ä I CO oo UO ^ - 1 Λ # „* 1 ό co O 'E o <r oo o ... υ co co -o □ X bs CO o Γ- ew r- · Γ-- Ό I 1-- 54 af—' (0 (0 = φ XI eg CO uo o ij.pj * ^ <r co m 77, r O uo ON o X Pi - - - UJ ^ -1 (O io g U vj cm o IO 'O' o 'ΠΓ --- "0 O-- Q) O 'CM X Q.

<u "* 1 υ a ^ O oi o <r ο 1 Jig

: * a 00 ^ 3 ^ js u * -. Y

% & --- (0 o> i -: <-ο · σ 'eg β <D (0 O oo (Ol-ro cm eg co (* Ό Ä - - I r-t ™ I - (____ (Ö

G -H o -O e- X JO eH

D C eo CO C_> ^ φ I -M 0) 0) - “- H f» II (/) 4-) 4-),.

X Φ (/) (/) "σ 'ο cj ii v ro to I«: oo <r 1 ° Y 06 x Vi -¾ .¾ u «^ - · *“' S ““ * SS, - c - 1- -1 WH ™ 1

• w a * I -Q

4-> (Ö U vO O '

H. £ CM CM

_, i 4J φ φ

"M 4-) -P

^ nj cn co 05 Μ (0 (0 • H AS λ: 5-1 Ή Ή

H (¾ K

C/O

W H CN

S 70378! m ld oo * W «.

(¾ CN Γ ~ CO]

I Oi CO CO., LTD

cd O-H - 1-

rö i — f ro r »O

4->> 1. «« »O

O, Λ ^ ^ ^ '• X

• rl r— oo σ \ Γ— | λ - *>, ai o vo o o n e M-- CU _ - _ ---—- 73 ...

O 0-3-0- 00 «3- Q ro ri« 3- • d “£ s' ^ -> - sm -rl, oS o- rsi oc 0 -H _ iH {r-« vO u "\ ^ rH 'b <n - 1 ---—- r3 U ^ o 1 c, ^ ~ ^ ä O ^! ϋ 00 r- O 1 - ^ - - _______ M-ί CN ΓΛ <r! li ^ ^ CO 00 -! 05 1 ",, Ού r · ^ ΙΛ 00 ~ ~ ~, VO U" \ V *, _J ^ C ^ ^ M CT- CO 1

0} rH

TT ^ "s B ^ ^ - °« U E £ S § 3 o ro fn JS a_ | _____ --- g - o o

® ® - Λ — o | , Oi «M I / O <N

QS - -3- «tn 05 V“ ° 3 r- -o m

I is oo n Λ * H

O 'd S I rH ro O uo I g ----- _ U O> i - - - ..

_ U —.O grH K '03> -, e> en \ co ^ N i <“" f HH? Coj ro ro j N Ϊ> 1 03 “·> ·» <* U ——————— = υ k # US ^ ° Ä oor-vo 0 \ | WO ro ro -3 · o.

w X2 ““ ----- I -H oi r- -3 - «L £ -H cc co co 3

=: * -3 ro uo O ^ ---- -P

U V * sr "rsT o" = 3 ^ '“Ί - g

OocTiOvPo _rHcjror-.Or-c X ---— & 'o <(O r <O 3 J? Ά --P-- £ ä ^ ™ g &, n- ^; "O Qt o * ~ ~ Il 1 ^, DES m CM; O, OJ ~? QJ * i — I> ij '-o 1 n rrt 03 03 v Äomo-cr.

<"J <rt nj I S-jccuroro o- II <ΐ | i2 J2" 11 ——_ i u ti * h a osa -h «a o os m tfl · · o- +5 (1) 05 O i ·. I W_ - Oi II (0 05 03 ^ (0 w

^ ^ i ä S

S rl (N

9 70378 O CN P ** Ρύ <N CO m σχ go oo

CM

- 'Ox o o

S vfl ΙΠ Ο- Γ> * \ 0 IA

* * m 00 00 00 o - O ox en m m - - -

__ _ «A

'' ™ 1 vO P- »n U m oo - O m η. m c ---

'00 Ό CM

__M ——___ Ot -O ’frt -

~~ "Ox Ox ON

co oo _ A A flj - - ''

X - oo r-. Z

On 00 00 O 0ft r-.

n ---— 1 _ u oo γμ <r 2 - <m cm;

^ <r - ia O

O -J 00 ON .μ CJeO 4J

> / tA on ca h * oo oo - c c (3 - η / —Γ 2 π r «____ - / Η Λ f * - 02 ON pn

/ -s k - ft υ ^ oo p (Q

m C 00 vD O '"I

ffi U --- 11 35 — Z -> ---- II

O I Q £ 00 O <r U I X

S _ / - s 300000 05 ^ Z ι ^ · νθ <Τ05 II «X ---

n μ cm ____Z O O O n- O

- - O I tn is .3 · u α o o c-ι q I ... X, -. -, ......

/ - * o m oo o O

X <n cn is ^ O \ om 0 Z ...

w 1 - --— CJ at cn σ> r * - I -K σ 'oo oo O J *: 1 OO CO ’* ---

0 * a a a w p.3C I

xr> - -oo 1 a frt oo mf} U ίΤ'ΓΛΓΜ, Oi ^ AA A c-> I Cij _ _ / -nDj ομτοοο ·! 3 «0 <—-- 3 om * cn cn sr $ -N re +3 I Λ ___:, 3 9 Λ r-.vOMr | § χ ^ <ϋ rt £? O - O ^ V H Π ϋ “

S i — i ___ ^ ^ ^ »c O n 3 tn Ui O

- "il, qj ω v 3 11 s H 9 9 s os. G s s« ^ “i“ 2 ί 3 C L ~ '3 ^ 2

^ 1- * ί ^ CM

10 70378

The collector was used to obtain fluorine slag (CaF2) from the granite rock material. The following method was used for fluorescent flotation.

1) 930 g of ground ore and 70 g of slime are weighed into a 5 1 kg cell and filled with water.

2) Add 0.15 g of collector.

3) Train for 2 minutes at 1300 rpm.

4) Foam until clean.

10a) Clean in a 500 g cell.

5b) Add 0.3 g of collector and prepare for 1 minute. 6b) Foam until clear.

The following results were obtained.

11 70378 j 3 I · Η r- I -A tn «d M o I o o oo <D · Α I - iH C · Η O__ S cm -H ~ o u; 8.H K ° vO 5 - oE> i -p u-t-m 5 ϋ ö <H?! ° ’$

- ^ ~ B

* °. ¢ 1 „n I 02 O cn O '..

* R ·? . £ ^ - * c & Sh 3 _ g ^ - 8 £ ^ ”IN ^ ^ Z <Tv <N <n3 _ -I — i> -1 to 4-> Γ9 _ +) 'g &% a__ ~ sgg · - qm ^ Z & -H 0ί OO 'CN "fl! IHO 00« N 05

"£ 1!> Ί 1 - -H

X H So -> o 0 I I -P · - O Si fN · ί N · Η Λ -S (§υϋνΟιΑιΛ + 3

Ζ _> J_ m oo f "· rcJ

w cn p S L ~ °. § I rö o r * <n ä = 5 I O 00 m ^ CJ C · Η -H i ____ [0 I ® C H O 2

X ° ί 9 <> - C: «i o m n O

<? 13 «| "°«, · r, - r.- O - T .S oi | § "” ^ g

^ · <R S

m <nj jij

a -: <- - M

Oi O vO <N m .1. ‘O 2 - - £ 2 d r? ~ 3 · * - Oh

rH 3w CN ^ O CO O -H

§rfr | li "*" "“ Jj

^ jn H O u ~ i Γ »ΓΊ H

Jjv (5 en oo σν? 3 J 6JQ_______pfl r — I 04 «ω <u *

I -P -P

jb -h w ω οί <X oi ~ c> v X JS «^ 12 70378 R Oleic acid A Ethylene oxide X 2

Butyl 5 n 2 y co3

M K

G R

Crude X0 ore 26.9 100

Rich 1 - Rich 2 92.2 60.7

The collector was used to obtain copper from a copper-containing oxide ore. The following method was used for copper flotation.

1. A 2 kg ore sample was ground to a fineness of 5% to 200 microns.

2. Trained for 10 minutes using 500 g / t 20 sodium ilicate.

3. Foamed for 12 minutes at 1500 rpm.

4. TEB (20 g / t) was used as the foam.

The following results were obtained.

13 70378 ------ - ^ __ ___ _ ____- | ^ Ο <Γ Ό o vo <n I si - I, -h o__ o d ^ o

H Q j> i Ο ιΛ r- O

Q &, fr cm m - 5 S '"S o - • H g 3 o vo m.

iJ Ä ffl m

O lO <T

I X O 00 -

*B

? c kä ii M !? ~ § x ϋ ~ ~ ™ «-n E> 1 rn + J ^ u - == si is * · a“ o ----———--- ^ o f ~ <n -7 * | CÄ O r- cm “-H I - ^ C -H O <t -—-

* 7 3) · Η ι-H - O X r ~ ncO

1- j, g, ä a g: ° z "·” - ~ · π ES! * «(N -U cwr '· - Λ ng 3 ___ ϋ_

X

2 I c vj- mj ~ I x o oo - ie »H 1 .— V fi - o-- = i, ä M M” ° O S- S.

t ~ </ —N 1 '' "ΠΓ 1 1 1 * 7, O CN 00

7 I -): O r * (N

*, -i. li__i_ HO 8¾ O * 'T- o -n B & «" 8 «υ · 6 ° - T- * dj? a -¾ £ S_ 00 * ^ (A <XXCX Σ g 7p β ω ^ β rt __ 70378 14 R Oleic acid Oleic acid \ A Ethylene oxide Ethylene oxide | X 2 2 '!

R 1 Butyl-Butyl and 5 n 1 1 y COO-SO 3 {_M_K__K__ G * R * G Pv; jRaw ore 7.99 100 7.96 100 i 10 Waste 6.08 72 5.57 61 j

Concentrate 38.8 28 24.38 39: * Intake R and quality G .are cumulative

Claims (6)

15 70378 A process for the foaming of ores, minerals or compounds containing phosphate, fluoride, copper or cobalt, characterized in that the foaming is carried out in the presence of an amphoteric collector of the general formula RCOO (A) CH.-CH (OH) CH "NC H. YM x Z 2 n Zn 1 o wherein R is a hydrocarbon group having 1 to 21 carbon atoms, A is an oxyalkylene group having 2 to 4 carbon atoms, is a hydrocarbon group having 1 to 18 carbon atoms or hydrogen, Y is a group COO or a group SO 2. , x is 0-15, n is 1-3 and M is hydrogen, airano-15 nium, sodium or potassium. Process according to Claim 1, characterized in that R is a hydrocarbon group having 9 to 17 carbon atoms. Process according to Claim 1, characterized in that R 1 is a hydrocarbon group having 2 to 6 carbon atoms. 4. An amphoteric compound having collecting properties, characterized in that it has the general formula 25 ROO (A) CH 2 -CH (OH) CHO-C YM x 2 2 n 2n wherein R is a hydrocarbon group having 1 to 21 carbon atoms, A is an oxyalkylene group having 2 to 4 carbon atoms, R 1 is a hydrocarbon group or hydrogen having 1 to 18 carbon atoms, Y is a group COO or a group SO 2, x is 0 to 15, n is 1 to 3 and M is hydrogen, ammonium, sodium it is potassium. Compound according to Claim 4, characterized in that R is a hydrocarbon group having 9 to 17 carbon atoms. Compound according to Claim 4, characterized in that it is a hydrocarbon group having 2 to 6 carbon atoms.