FI83878C - Amphoteric compound and its use - Google Patents

Description

1 83878

The present invention relates to a novel amphoteric compound and to its use as a collection reagent in flotation.

U.S. Patent No. 4,358,368, SE Application No. 8401859-7 and ZA Application No. 83/3023 describe the use of amphoteric compounds having a tertiary amine group and a carboxyl group. These collecting reagents have good selectivity for oxide and salt type minerals, such as phosphate mineral, which are enriched in high yields and high concentrations.

It has now been found that amphoteric compounds of a new type than previously known have better selectivity as aggregating reagents in the flotation of oxide- and salt-type minerals such as phosphate, fluoride, copper, tungsten, niobium and cobalt-containing minerals. The compounds according to the invention have particularly good properties in removing phosphate minerals from iron ore. It has been found that by using amphoteric compounds, possibly in combination with cationic amine scavengers suitable for silicates, it is possible to reduce the phosphorus content of the iron concentrate to 0.03% or even lower, while the iron yield is very high. The low phosphorus content of iron concentrate facilitates the subsequent metallurgical processing of iron concentrate. The novel types of amphoteric compounds according to the invention can be collectively described by the general formula R 1 and I 13; RrVXn-VY ;-( N -CpH2p) q-N -C2H40PO3 M2 1 wherein R1 is a hydrocarbon group having 5 to 24 carbon atoms; ^ 2 3a ^ 3 ova ^ each independently hydrogen, a hydrocarbon group having 1 to 4 carbon atoms or a group R '-X -X'-Y.-Y * 1 1 1 1 mnts 2 83878 or alternatively the whole group R-, CH - CH0 I3 / 2 \ -N- (CH ~) -N- denotes the ring -N N- »'P 2p q \ / CH_— CU / 5 X is -C-;

II

X 'is -O-; Y is an alkyleneoxy group derived from an alkylene oxide having 2 to 4 carbon atoms; Y 'is -CH_-CH-CH ~ 2 | 2

OH

15 M is a monovalent cation or hydrogen; m, n and s are 0 or 1; p and q are 1, 2 or 3; and t is any number from zero to five; provided that when t and s are 0, then n is 0.

20 p is preferably 2 or 3.

The compounds of the invention can be readily prepared from commercially available starting materials using known preparation steps.

The group may be derived from an alpha-olefin containing from 8 to 20 carbon atoms, a carboxylic acid or a hydroxyl compound. Examples of suitable hydroxyl compounds or carboxylic acids are Ziegler, oxo and fatty alcohols, such as n-butanol, isobutanol, secondary butanol, n-hexanol, secondary hexanols, isohexanols, 2-ethylhexanol, n-octanol, lauryl , myristyl alcohol, cetyl alcohol, stearyl alcohol and oleyl alcohol and their corresponding carboxylic acids.

. . Not only aliphatic alcohols and carboxylic acids but also cycloaliphatic alcohols 3 83878 and aromatic hydroxyl or carboxyl compounds can be used as starting materials. Suitable cycloaliphatic alcohols include cyclohexanol and alkyl substituted cyclic alcohols. Among the suitable aromatic hydroxyl or carboxyl compounds, mention may be made in particular of synthetically produced mono-, di- and trialkyl-substituted phenols, such as octylphenol, nonylphenol, dodecylphenol, dibutylphenol and tributylphenol.

The groups Y and Y 'can be attached to the molecule in a conventional manner by reacting the appropriate starting material with alkylene oxide or epichlorohydrin. The group N-CpH2p is attached to the molecule using ethylenediamine, diethylenetriamine, triethylenetetramine and the corresponding propyleneamines and their alkyl-substituted derivatives as reactants. Alternatively, acrylonitrile can be added and then hydrogenated.

The compounds of the invention have generally shown good properties as scavenging reagents in the flotation of oxide or salt type minerals such as apatite and can be used advantageously in combination with a primary amine as a silicate scavenger in the enrichment of iron minerals from phosphorus ores.

Figure 1 shows a flow chart of one such flotation process. In step I, the iron ore, together with water, sodium hydroxide and sodium silicate, is ground to a particle size suitable for flotation. The slurry containing the ground ore is then transferred to step II, where the ore is pretreated with starch and the pH is adjusted with sodium hydroxide, whereby the iron minerals flocculate and settle. The remaining sludge is sucked off. The ore is then aerated for several minutes in step III while adding starch and adding sodium hydroxide to adjust the pH, followed in step IV by adding the primary amine and amphoteric collecting reagent and adding sodium hydroxide to adjust the pH.

4 83878

The whole is re-aerated for a few minutes. In step V, the slurry is raw foamed. The side rock that accumulates on the surface is removed as a foam product 1, and the iron mineral concentrate is removed from below and transferred, after the addition of more primary amine and sodium hydroxide to adjust the pH, in step VI for aeration. After aeration for several minutes, a second flotation is carried out, whereby the foam product 2 separates and an iron mineral concentrate is obtained.

A type of compound which is within the scope of the invention and which is easy to prepare can be collectively described by the general formula 0 R „R- 1 I2 T3 15 R-, ΟΝ (cpH2p) q N C2H4OP ° 3 M2 11 wherein R1 and M is as defined for formula I, while R 2 and R 2 represent hydrogen or an alkyl group having 1 to 4 carbon atoms, p is 2 or 3 and q is 1 to 3.

Compounds with good foaming properties can be easily prepared using alpha-olefins as starting compounds. Such compounds may be collectively represented by the formula R, R, I 13

R.CH_CHCH0 (NC H-) N C-H.OPO., Μ0 III

12 | 2 p2pq 24 32

OH

Wherein R 1, R 2, Rail and M have the meanings given in formula I, p is 2 or 3 and q is 1 to 3.

Another preferred group of compounds are compounds which are obtained e.g. using a hydroxyl compound and 35 epichlorohydrin. These compounds can be collectively described by the formula 5 83878 ΐ2 ΐ3

R1Ο-Υ.-CH-CHCH- (NC Η0) N C-H.OPO-. M_ IV

1 t 21 2 p 2p cj 2 4 3 2

OH

wherein R 1, Y, R 2, Rail, M 1 and 5 have the meanings given in formula I, p is 2 or 3 and 1 is 1 to 3.

A suitable group of compounds according to the invention further comprise compounds corresponding to the formula 10-2 R3

R1 | NCpH2p'q N C2H40PO3 M2 V

wherein R 1, R 2, Rail and M have the meanings given in formula I, p is 2 or 3 and 1 to 3.

Another group of compounds with good flotation properties and ease of preparation are further compounds of formula 20 / CH2-CH2v R1 Xm K Yt Yi * N C2H40PO3 M3

Nch - ch /

λ i VI

25 wherein Re, X, X ', Y, Y, M, which, have an account and have the meanings given in connection with formula I. Examples of different compounds suitable for use in flotation are as follows:

30 OH H

ll [T 2- + c15H31-c-NCH2CH2NCH2choOPO3 2Na

H H

li 2- +

C9H19-CH2 (j: HCH2NCH2CH2NCH2CH2PO3 ^ 2Na 35 OH

6 83878

B

I 2- + (2-ethylhexyl-O-CH2 <j: HCH2) 2 N CH2CH2NCH2CH2OPC> 3 2Na

OH

OH H

Il 2- + O-C H O-CH CHCH N CH „CH„ N CH „CH OPO., 2Na 24 21 2 22 223

5 OH

H H _ I I 2-

CicHoo_OH :: HoCHCHo (NCH „CH0) N CH CH OPO 16 33 2 | 2 222 22 3

OH

10 ^ chj-ch2 εΐ2Η25θ · 0 (ε2Β40> 2 CH2fCH2 \ / M 2Na + OH TH2— CH2 / 1 5 O CH2 ~ CH2 if / \ 2-, ♦ C. _.H- -CN N CH CH-OPO- 2Na 1 / JJ \ ✓ 2 2 λ CH- CHf 20 The flotation properties of an amphoteric compound can be further improved by carrying out a flotation hydrophobic secondary collection reagent, which secondary collection reagent is preferably a polar, water-insoluble, hydrophobic substance having amphoteric-binding compound. The amphoteric compound is usually added in an amount of 10 to 1000 g, preferably 50 to 500 g, per ton of ore, and the polar water-insoluble substance is added in an amount of 0 to 1000 g, preferably 5 to 750 g, per ton. the ratio can vary within very wide limits, but is usually between 1:20 and 20: 1, preferably between 1: 5 and 5: 1. The 35 t-mukaises called secondary kokoojareagenssiksi, preferably 7 83 878 is a polar material. If desired, a conventional emulsifier dissolved in a hydrocarbon may also be added to provide a stable aqueous emulsion and good distribution. The emulsifier may be a nonionic surfactant, which - in the case of being insoluble in water - must be incorporated into a polar substance. Suitable polar compounds include water-insoluble soaps such as lime soaps; water-insoluble surfactant alkylene oxide adducts; organic phosphate-10 compounds such as tributyl phosphate and tri (2-ethylhexyl) phosphate; as well as esters of carboxylic acids such as tributyl esters and tri (2-ethylhexyl) esters of NTA and dioctyl phthalate.

In the flotation process of the invention, the amphoteric collecting reagent can be advantageously used in combination with foaming agents. Suitable foaming agents include hydrophilic polysaccharides substituted with anionic groups. Polysaccharides with relatively low viscosity are preferred.

Substitution per molecule can vary widely, but usually ranges from one anionic substituent per polysaccharide molecule to one substituent per anhydroglucose unit. Examples of suitable polysaccharides are carboxymethylcellulose, sulfomethylcellulose, acacia, karaya gum, tragacanth, ghatic gum (Indian gum from Angeissus latifolia), alginates and starches such as starch starch, and anionic starch such as anionic starch, anionic starch,

In the flotation carried out according to the process of the invention, pH-adjusting agents as well as foaming-generating and activating agents can be added in a known manner. In most flotation methods, pH is important to achieve good separation. The flotation process of the invention is also bound to a pH of 8,838,878. It offers even better opportunities to optimize the separation of different minerals by selecting the appropriate pH value. Thus, the nature of the amphoteric compound varies considerably with pH. At pH below 5 6 it is predominantly cationic, while at pH above 10 it is predominantly anionic and at pH 6-10 it is zwitterionic. In the separation of ore containing apatite and silicate or apatite and calcite, excellent selective enrichment is achieved by carrying out the flotation process at approximately pH 8-11.

If necessary, conventional foaming and activating agents can also be added. No general rules can be drawn up, as each ore must ultimately be treated according to its chemical and physical composition.

The following examples further illustrate the substance and procedure of the invention.

Example A OH H

20 Amide C. 1d! -N-CH_CH_N-CH_CH_OH was prepared

Ibjl 2 Z Z Z

O

II

by reacting 272 g (1 mol) of C 1 H 2 Cl 2 O-CH 2 Cl 2 with 104 g (1 mol) of aminoethylethanolamine H

25 H2NCH2CH2NCH2CH2OH. The liberated methanol was evaporated at the end of the reaction. After the reaction, the reaction mixture was titrated with basic nitrogen. The yield of the amide compound was about 93%.

The amide (72 g, 0.2 mol) was then reacted with 35 g of polyphosphoric acid at 85 ° C for two hours.

Titration of the anionic group containing the surfactant compound confirmed the compound? ? ¥ 9

C. CH0 .C-N-CH ,, CH „NCH„ CH „OP (OH)„ formation. Total-l b J1 Z Z Z Z Z

The yield was 35%, and the obtained reaction product was a mass having a high viscosity of 9,838,878 and which was water-soluble after neutralization.

Example B

104 g (0.48 mol) of the epoxide 2-ethylhexyl-5 OCH 2 CH 2 H 2 were reacted at 70 ° C with 25 g (0.24 mol) of aminoethylethanolamine for two hours to form a tertiary amine.

B

i (2-ethylhexyl-OCH2CHCH2) 2NCH2CH2NCH2CH2OH.

10 Ah

The degree of amination was determined by titration with tertiary nitrogen and was found to be about 91%.

50 g (0.093 mol) of tertiary amine were then reacted at 70 ° C with 26 g of polyphosphoric acid for 2 hours.

Titration of the anionic group containing the surfactant compound confirmed the compound

B

(2-ethylhexyl-OCH2CHCH2) 2NCH2CH2NCH2CH2OP (OH) 2 OH. The reaction product obtained was a mass having a high viscosity and which was water-soluble after neutralization.

Example C

Flotation was performed according to the flow chart shown in Figure 1. Iron ore containing 34% Fe, 23.9% of it and 0.044% P mainly in the form of hematite (49%), silicate (quartz) (51%) and apatite (0.24%) was crushed with a particle diameter of 1.7 mm and ho-30 was homogenized. 600 g portions were taken from the homogenized material. The portions were further ground in a laboratory rod mill for 30 minutes together with water (400 ml), sodium hydroxide (0.40 g) and water glass (0.27 g) (38 wt% sodium silicate, weight ratio SiO 2 / NaO 2 = 3.22, 41.0 ° B§).

10 83878

The particle distribution was such that 97% of the particles passed through a 32 μm sieve.

A water-containing mineral slurry having a volume of 8 L was prepared from each portion of the ground material. The temperature was adjusted to about 20 ° C and the pH to 10.5. 0.0675 g of prehydrolysed corn starch was added and the whole was aerated with a paddle stirrer for 2 minutes.

The aerated slurry was allowed to settle for 3 minutes and the sludge was sucked off. The slurry from which the sludge had been separated was divided into four portions, and each fraction was transferred to a flotation cell and diluted with water to 0.5 L. The pH was adjusted to 10.5 with sodium hydroxide, followed by the addition of 0.0675 g of prehydrolyzed corn starch. After aeration for 2 minutes and finally adjusting the pH to 11, an anionic collecting reagent and a primary amine collecting reagent were added. The amount of primary amine was 0.0067 g and the amount of anionic collecting reagent is reported in Table 1. After additional aeration for 2 minutes, crude foaming was performed to give foam product 1 and a base concentrate containing iron mineral. The pH was again adjusted to 11 with sodium hydroxide, 0.0067 g of primary amine was added to the bottom concentrate and the whole was aerated for 2 minutes, followed by further flotation to give foam product 2 and iron mineral concentrate. The primary amines and compounds containing nionic groups used and the results obtained are shown in Table 1.

Example D

Foaming was performed on pure minerals consisting of fluoroapatite, scheelite, magnesite, quartz, olivine or fluorite. First, the minerals were ground and wet screened, from which 250-400 μπι: η fractions were taken from the screened minerals for flotation experiments. 0.2 ml of the fraction was transferred to a test tube with a diameter of 15 mm and a length of 120 mm. 10 ml of an aqueous solution having the pH and concentration for each collecting reagent according to Tables 2-4 were added, after which the mineral was aerated for 5 minutes with stirring.

After aeration, the solution and water were sucked off with an overpressure of 6 atm, and air was fed through a tube. As the water pressure dropped, the air was released and flotation occurred. The amount of foam was assessed visually. The results are shown in Tables 3-4 below, i2 83878 * · Ή 3 ΰί> GPP - d) Ο Ρ QJ φ ·. · ΓΟ Ι '' τ- + J id + J 3 -Ρ n ro ro Ρ Ρ m · γτΗ ο ο ο (D Μ Ρ 0) α • Η ο Ο · Η I Ο Ο Ο -ι — ι Ο-ι —I Ö-t

3 - I

• ro c #> (N o O, G

G I G (0 I

H Qi r \ i (N (N φ φ: (0 G) - ro ro ro G>: <0 - -H g cap ε: <a II - 3 P nj: 0 -H · ro <t cd P m p

Ρ p P • H 'Tf -S' e> (lll CD Γ- ~ <T

-ΡΦ-Η-ΗΟ O O (0 P (0 '

: OPH CP - - (0 d)> r- 00 O

> ιΦ (0ΐο o o Αί-Pfö oom ^ r n E Id dl (0: 0 -P · - • ro> i -P: (0

™ ™ ™ m φ P

S S S G -P tn l lii ·· c #> o aö

• H ro m ro CP '-' 3 M

G ---

0-3 (N CM CM

-nm wee G m 2 2 2 (OG OOO P cOt-h ·

φ III -H · - H * ΓΟ (N

C O '--- QjdPOOO

d> <0 £ £ ^ · ~ '' *

Cd) III CP OOO

• HP r- ~ r ~ r ~ P (0 - - -

(0 -ro E E E

(0 o 2 2 2 ε o i i i cN φ p

• H λ; CD 00 00— P -H

PO O O DE CO CP - 00 H * CN

CP 34 --- ^ 0 (01 cap »» »EO <N - m cr m

, ^ -HO

O P -H

1- -H I -H CO

G ™ rH

O G Π Ό «O ucs 3

«P I E PO

D E 2 O Q) P

| J Cn -Τ'1 G G

D F -H (0 - H- r- LO

<2n gfödP '' -

En E ro m - h * - 1— • h u ρ i r "oo γιο Z 3 Φ m ίο G E ΓΜ Ph

d) OK

Cn - o

(rt O E EE

φ OOO

S * "» T iJ

(0 o o p · (—l (N o Pj - O Γ '· Γ' · o El | (#> - - *

O „yp φ - CO ΓΜ LO

<n>, & p co cd cd O E> t 34 U m

CM P

G G g JS

d) «Ö e 2 h σι ^ ^ G aO o CJ 1 — i ie # '' '• H -P -n> 1 I | H- H · r ~ G -H ρ po Dj CP ro H * ro

O g K P

“C LO Q) • H —i |

G -H E CN

<W U -

G

3 -H 3 H 34-1

• H p -H

H (0 d) (0

p p τ— (N g p <- CN

m P HOP

d) Φ m ρ φ E-ι> WC> 13 83878

CN

m 2 ro

O

(¾

i O

sf

K

CM

U

K cm 2 m 2 p-t (N CM 00 mu o 2 2 Oh CM CM CM o ro ^ m m m O cm 2 2 22 2

Oh S CM

0 U ro oo ro u O

K EC O OK O

EC U — O Oh Oh U-2 U

(M CM O O

U EC CO CM

1 U EC r- ~ EC EC EC

2 O CM r- CM OO (OOOU

/ \ I U 2 U U 22 / \ -H 2 <»S3 U — 2

H T rH 2 U — 2 2 O

(/ l®2> i 'S' cm O cm 1 (1CMCME> H 2 rr2 U 2

G U U (/ 1 cm2 U cm U

Q) \ / U cn 22 2 22

CP \ / dl 2 U U — O oo u U — O

m2 2 2 2 cm 2 CM

0) I H I 2 U ~ 2 2

G 0 = 0 r — I O = U cm U U

m I:> i - o = u o ΓΟ00>, OO O 'H— H— 00

Oro 4- / ro '- oo rooo 02 0) 222 22 X I r ~ oo l / ο m

Oh-cmh-u »- * -« -

2 U ^ U - U UU

CM

O G

I-I

«H

d -n m G) -P + /

2 (/) G

! <(]) ·. . . . Q) E-i & hh— cm ro ιη> <32 14 83878 • inoooinmmoo · ιηοοοιηιηοοο PQ CO Or- r- CQi— Or- r- T T— 1—00 T- tr! k (li · ιηιηοοοιηοοιη Qj · ιηοιηι / ΐιηοοοο

<C <- CM O CM <- 00 <N

<K> <x> «· 4-> 4-> -P Gl Ή J- |

<ϋ <U

i-H I — I L> 10 rd (0 rd • o o I I I I m I I · o n I I I I o I t pinoin r- Sh in o cm τ- Ο) ^ 0) ^

C G

-Η Ή B · ooiiiioii g · oiniiiimii in in o o tN cm 3 3

-P -P

-P -P

• oinmoininooo · ininmomminoo Q) ΓΟ ONNOr-hO O 0) Γ0 CO 00 (D O MO <-

-P ^ ^ ^ -P

0 0 Λ · oomoinminom x; · Oiniiuninmoom cm oinooor "* - oo cn o cm cm oo o cm t— (0 t— ftJ r— id rd>> • mmmommmmm · inoininininooo i— 00 00 '- O * - CM CM * - CM T— CM CM ID CM '- • P Ή -P 4-1 4-> 4-) -Η Ή

• P · Ρ · Η · Ρ -Η -P

CO 4-1 -Η -H 4-) 4-) M * -P -P -P -P 4-)

rO-p 4-) 4-) 4-) -P (0 -P -p-P-P -P

O Oj -P -P -P * P · Ρ -P * P O £ 1 | -P -p -P -P * P -P * P

(d -p -P -P -P 4-) -P -P G (d 4-) -P -P -P -p -p -P G

X · Ρ · Ρ · Ρ 'P H 4) dl II) -P ^ -P -P · Ρ -P t — I -P Ui U) * P

G> -P P-PgPCDiP-PCU-P G> -P p-PgM (D> i-P <D-P

iJ -P 0tfl00 <U> iPC> J -P 0W00 <l>> iS-lG>

G> t / 1 Gi-iHG-CGirdtP-P G> W GHriGXltmtJ'-H

<cu PiuosPom> idH <ο) ΜίθθΜυ (θ> (θι-:

E- · Eh P4 «Q [nWffl« SO EH Eh hJDQtufflfflXSO

Claims (7)

1. Amphoteric compound, characterized in that it has the general formula 5 · 2 · · · · · · · · · · · · · · · · · · · · · · · · · · · · - on -NO-CO There is a hydrocarbon group containing from 5 to 24 carbon atoms; R £ 10 and Rg are independently hydrogen, a hydrocarbon group containing from 1 to 4 carbon atoms or the group R, -X-X'-Y-Y '1 mnts R0 R0 I 2 I 3 or alternatively the whole group ( ) q ~ N-CH -CH- 15 rings -N N-; XCH 2 -CH 2 X is -C-; A X 'is -O-; Y is an alkylene oxyl group derived from an alkylene oxide of 2-4 carbon atoms; Y 'is -CH-CH-CH'; Z 1 Z OH M is a monovalent cation or hydrogen; M, n and s are 0 or 1: p and q is 1, 2 or 3; and t is a tai from noil to five; provided that d and S are 0, then n is 0. 2. An amphoteric compound according to claim 1, characterized in that p is 2 or 3. Amphoteric compound according to claim 1, characterized in that it has the general formula 0 R0 Rq Il 1z I · 3 R. CN- (C H0) N CoH 2 OPOQ NL · II 1 p 2p q 24 32 19 83878 where and M is as defined in formula I, wherein R 2 and R 3 are hydrogen or an alkyl group containing 1 -4 carbon atoms, p is 2 or 3 and q is 1-3. Amphoteric compound according to claim 1 or 2, characterized in that it has the general formula R 2 R 3 R 1 CH 2 Q HCH 2 (NcpH 2 p) qN C 2 H are 2 or 3 and q is 1-3. Amphoteric compound according to claim 1 or 2, characterized in that it has the general formula R 2 R 2 R 10 -Yt-CH 2 CHCH 2 (NcpH 2 p) q NC 2 OK 2 M 2 IV OH where R 2, Y, R 2, R 3 and M has the meaning given in formula I, p is 2 or 3 and q is 1-3. Amphoteric compound according to claim 1 or 2, characterized in that it has the general formula CHO-CH0 / 2 WAVs Nv> C2H40PO3 M2 VI ch2-ch / 30 wherein R1, X, X ', Y, Y', m, n, t, s and M have the meaning given in formula I. Use of an amphoteric compound according to any one of claims 1-6, characterized in that said compound is used as a collecting reagent in the case of flotation.