CA1073563A - Process for beneficiation of non-sulfide ores - Google Patents

Abstract

A B S T R A C T

Improved beneficiation of non-sulfide ores by froth flotation results when the collector employed is a mixture of a naturally derived fatty acid and a partial ester of a poly-carboxylic acid having at least one free carboxylic acid group.

Description

26,~ ~73~3 1 This invention relates to a process for the bene-ficiation of non-sulfide ores. More particularly, this inven-tion relates to such a process wherein combinations of common naturally derived fatty acids of vegetable or animal oil sources and maleic half esters of ethoxylated linear alcohols as froth flotation agents provide beneficial effects.
Froth flotation is the principal means by which phosphate, barite, fluorite, permatite, taconic, magnetite, cement rock, and a host of other ores are concentrated. Its chief advabtage lies in the fact that it is a relatively ef-ficient process operating at substantially lower costs than many other processes.
Flotation is a process for separating finely ground valuable minerals from their associated gangue, or waste, or for separating valuable components one from another. In froth flotation, frothing occurs by introducing air into a pulp of finely divided ore and water containing a frothing agent.
Minerals that have a special affinity for air bubbles rise to the surface in the froth and are separated from those wet-ted by the water. The particles to be separated by frothflotation must be of a size that can be readily levitated by the air bubbles.
Agents called collectors are used in conjunction with flotation to promote recovery of the desired material.
The agents chosen must be capable of selectively coating the desired material in spite of the presence of many other min-eral species. Current theory states that the flotation sep-aration of one mineral species from another depends upon the relative wettability of surfaces. Typically, the surface--~ree energy is purportedly lowered by the adsorption of het-eropolar surface-active agents. The hydrophobic coating thus provided acts in this explanation as a bridge so that the particle may be attached to an air bubble. The practice of - 1 - ~ . , ~ff ~073~3 1 this invention is not limited by this or other theories of flotation.
A typical non-sulfide ore that is beneficiated in large tonnages commercially both domestically and abroad is phosphate rock. Typically, phosphate ore containing about 15-35% BPL [bone phosphate of lime, Ca3(PO4)2~ is concentrat-ed in very large tonnages from the Florida pebble phosphate deposits. The ore slurry from strip mining is sized at about 1 millimeter and the coarser fraction, after scrubbing to break up the balls, is a finished product. The minus 1 mm fraction is further sized at a 35 and 200 mesh. The minus 200 mesh slime is discarded. From the sizing operation, the +35 mesh material in thick slurry is treated with fatty acid, fuel oil, and caustic, ammonia, or other alkaline material and the resulting agglomerates are separated on shaking tables, spirals, or spray belts. The 35 x 200 mesh fraction is conditioned with the same type of reagents and floated by conventional froth flotation routes. Not all the silica gangue is rejected by the fatty acid flotation, so the concentrate is blunged with acid to remove collector coatings, deslimed, washed free of reagents and subjected to an amine flotation with duel oil at pH 7-8. This latter flotation, sometimes called "cleaning", removes additional silica and raises the final concentrate grade to 75-80% BPL.
Although the procedure described above is effective in recovery of non-sulfide ores from their gangue materials, there nevertheless exists the need for more effective pro-cesses which will provide increased recovery of mineral values while still providing high grade recovery. In view of the large quantities of non-sulfide ores processed by froth flo-tation, such a development can result in a substantial increase in the total amount of mineral values recovered and provide substantial economical advantages even when a modest increase . . . : ~ . ~ ' - . - : .

~073s63 in recovery is provided. It is also desirable to have an efficient collector system for use a~ reduced dosage levels without sacrificing the mineral recovery performance. Decreases in reagent consumption are significant in view of the increasing diversion of naturally derived fatty acids for nutritional and other purposes. The advantages of having a collector system which achieves savings in usage of petroleum based fuel oil for optimum mineral recovery are readily apparent to an energy intensive society. Accordingly, the provision for an improved process for froth flotation of non-sulfide minerals would fulfill a long-felt need and con-stitute a notable advance in the art. -In accordance with the present invention, there is provided a process for the beneficiation of non-sulfide ores which co~prises classify-ing the ore to provide particles of flotation size, slurrying the sized ore in aqueous medium, conditioning the slurry with an effective a unt of a combination of from about 99 to about S weight pcrcent of a fatty acid derived from a vegetable or animal oil and, correspondingly, from about 1 to about 95 weight percent of a partial ester of a polycarboxylic acid having at least one free carboxylic acid group, and floating the desired ore values by froth flotation, said partial ester having the structure:

2Q Rl - t CH2CH20 ~ CH O - C - R - C - OH

wherein R' is a primary or secondary alkyl group of about 8 to 18 carbon atoms, n is an integer of about O-10 and R is a bivalent grouping selected from (CH23 m wherein m is an integer of 1 to 6; -CH=CH-;
CHOH-CH2 - ; - CHOH-CHO~ - ;

~3-, ....~,~;
. ~, ~, . .

: . - : - , . . , . , ~ .

10735~3 ,, OH

COO~

~ -C~l2 (ortho, para, and meta~; and -C6Hlo~.
In accordance with the present invention there is also provided a synergistic collector composition for non-sulfide ores which comprises a combination of from about S to about 99 weight percent of a fatty acid derived from a vegetable or animal oil and, correspondingly, from about 95 to about 1 weigh~ percent of a partial ester of a polycarboxylic acid having at least one free carboxylic acid group, said partial ester having the ~tructure: O O
.. ..
R~-O (CH2CH~o ~ CH2CH2O - C-R-C - OH
wherein Rl is a primary or secondary alkyl group of about 8 to 18 carbon atoms, n is an integer of about 0-10, and R is a bivalent grouping selected rom --~CH2 ~ wherein m is an integer of 1 to 6; - CH = CH - ;
- CHOH~CH2- ; CHOH-CHOH - ;

CH2C ~ CHz ; ~ ; ~ ; ~ ;

~ortho, meta, and para); and -C6Hlo~.
The combination of fatty acid and partial ester enables the re~uirements for scarce fatty acids to be reduced while providing high recovery and grade. In most instances, the combination provides superior performance over that obtainable with either component alone. In many -~
instancesJ the c~mbination reduces dosage requirements for collector for the same recoVery ant grade of mineral values. In all .""~

..... .. . . . . . . ................................ . ..
.

1~73~63 1 cases, the requirements for scarce fatty acid can be si~nif-icantly reduced, while, generally, providing a boost in the recovery obtained. In certain instances, the partial ester alone cannot be effectively employed because of excessive foaming associated with such use. Attempts to abate the foam-ing by special additives adversely affects recovery and un-necessarily increases costs. However, combinations as used in the present inventions do not cause e~cessive foaming and provide an in~rease in recovery over that obtained with the fatty acid alone.
The collector composition is synergistic in its action and, therefore, provides in sum an activity not attrib- -utable to the parts that make up its composition. Such a composition is completely unpredictable and highly surpris-ing. Such compositions are quite rare and unobvious in view of the synergistic activity they provide.
The collector compositions of the present invention enable greater recovery of mineral values to be achieved at a given dosage of use, enable a given recovery of mineral values to be achieved at lower dosages of use, and enable scarce fatty acids derived from vegetable and animal oils to be partially replaced by synthetic acids which are readily available without sacrifice of recovery or grade of the min-eral values processed. The improved activity associated with ~5 the synergistic collector combinations of the present inven-tion also reduces requirements for fuel oil or other addi-tives associated with the conventional froth flotation pro-cesses involving non-sulfide ores. -There are two required ingxedients that make up the synergistic collector combinations of the present inven-tion, a fatty acid derived from a vegetable or animal oil and a partial ester of a polycarboxylic acid, the partial ester resulting in having at least one free carboxylic acid 735~3 1 group, i.e., one that is free of esterifying groups.
The partial esters used in the present invention are provided by synthesis utilizing specific polycarboxylic acids as esterifying agents. The alcohol ethoxylates may be derived from a single component or admixture of two or more alcohols. These synthetic partial esters are moderate in cost and are more readily available than currently used reagents. The synthetic acid can be produced in more con-sistent, predictable purity and quality than naturally de-rived scarce products.
In carrying out the process of the present inven-tion, a non-sulfide mineral is selected for treatment. Such minerals include phosphate, fluorite, barite, hematite, taco-nite, magnetite, cement rock, and the like that are conven-tionally processed by froth flotation. The selected mineralis screened to provide particles of flotation size according ; to the conventional procedures. Generally, the flotation size will encompass from about 30 x 150 mesh size.
After the selected mineral has been sized as indi-cated, it is slurried in aqueous medium and conditioned withthe combination of fatty acid and partial ester as well as such other additives as may be conventionally employed with the selected mineral. Such additives may include alkali or ; other pH adjustors, frother, fuel oil, foam control agents, and the like as well as are well known to the skilled artisan.
Depending upon the particular mineral to be processed, the content of mineral solids in the slurry will vary according to conventional processing. Generally, the combination of fatty acid and partial ester is used in an amount to provide a level of about 0.1 to 2.0 lbs. of the combination per ton of mineral, altho~gh variations in amounts will vary with the specific mineral being processed within conventional ranges.

- : . .

1~73563 1 In carrying out the process of the present inven- -tion, a combination of a fatty acid and a partial ester are used in admixture in froth flotation to enable a reduction in the requirements for scarce fatty acids to be achieved while maintaining high recovery and grade or improvements therein. ..
The fatty acid used in the combination is one de-rived from a vegetable or animal oil. Vegetable oils include babassu, castor, chinese tallow, coconut, cottonseed, grape-seed, hempseed, kapok, linseed, wild mustard, oiticica, olive, ouri-ouri, palm, palmkernel, peanut, perilla, poppyseed, Arg-entine rapeseed, rubberseed, safflower, seasame, soybean, sugarcane, sunflower, tall, teaseed, tung and ucuhuba oils.
Animal oils include fish and livestock. These oils contain acids ranging from six carbons to twenty-eight carbons or more which may be saturated or unsaturated, hydroxylated or not, linear or cyclic, and the like.
The partial ester used in the combination is de-rived from a polycarboxylic acid in which at least one free :
~0 carboxylic acid group is present and which partial ester has .
a structure given by:
O O
,. .......................... .
(CH2CH20 ) n CH2CH20-C-R-C-oH
wherein R' is a primary or secondary alkyl group of about - 25 8 to 18 carbon atoms, n is an integer of O-10 and R is a bi-valent grouping selected from ~CH2t--m, wherein m is an integer of 1-6; -CH=CH-; C~CH- ; - CH~CH-;

OH _ _ OH H
~H

30 1 ~ ; ~ ; ~ ;

-CH2 ~ ~
CH2 ~

1 (ortho, meta, and para), and -C6Hlo0.
Typically, the useful partial esters are reaction products of an alcohol ethoxylate of the general structure (R'-O--~CH2cH2o~ -ncH2cH2oH wherein R' is a primary or sec-ondary alkyl group of 8 to 18 carbon atoms and n is as de-fined above and di- or tribasic acids such as malic, maleic, citric, tartaric, succinic, adipic, phthalic, cyclohexyl di-carboxylic, terephthalic, and similar acids. The alcohol ethoxylates may be derived from a single component or admix-ture of two or more alcohols. Preferably the polycarboxylic acid used in forming the partial ester is maleic acid. Pref-erably the alcohol ethoxylate is such that the alkyl group contains 11 to 15 carbon atoms and n is 2. Suitable partial esters include those of the following structures: :
O ~ :

C11-15H23_30 ~CH2CH20--t2 CH2cH2oc-cH=c~-cooH;
..
C12-14H24_28 -~CH2cH2o-t2 CH2cH2oc-cH=cH-cooH;
o OH
.. .
12-14H25-29--~CH2CH20--t2 CH2CH2c_CHcH2cooH;

O OH
..
C12_14H25_29 ~CH2CH2o - t2 CH2cH2oc-cH2-c-cooH;
COOH

O OH
.. .
C16_18H33_37 -~CH2cH2o-t2 CH2CH2OC-CH2-C-CH2COOH;

COOH

O OH
.. .
C H33 37--~cH2cH2o-t4 CH2CH20C CH2 ,C 2 COOH

CH3(CH2)4- C,H--~CH2-t4 C 3 O (CH2CH20--t2CH2CH20-C-CH=CH-C-OH;

.- . - - - - - .
: .' . : ' :

1 CH3(CH2)5- CH (CH2 )5 3 ,, ~

2 2 )CH2CH2O-C-CH=CH-C-OH; and CH3 (CH2 )6 CH ~CH2 )6 C 3 (CH2CH20~2 CH2CH20-C-CH=CH-C-H' The acid and partial ester are used in the combina-tion such that the fatty acid will constitute from about 99 to about 5 weight percent and, correspondingly, the partial ester will constitute from about 1 to about 95 weight percent of the combination. The combination providing maximum re-covery will vary depending upon the specific non-sulfide ore processed and will vary among different samples of the same ores.
The principles of the present invention apply to non-sulfide ores that are processable by froth flotation in general. Typical ores are those illustrated by fluorite or fluorspar, barite or barytes, hematite, taconite, or hema-tite, phosphate rock of the pebble rock of the pebble type as found in Florida or foskorite as found in South Africa.
Other non-sulfide minerals that are processed by froth flo-tation using an acid collector may also be processed.
The synergistic activity provided by the collector combination of the present invention is illustrated with ref-erence to the sole figure of the application which shows as a straight line the expected performance of compositions of combinations of fatty acid and partial ether and as a curved line the actual performance obtained with the same composi-tions.
In order to illustrate the synergistic performance of the collector combinations of the present invention, it is necessary to carry out froth flotation of a non-sulfide ore using the ingredients separately and in combination at various ratios, the total dosage of collector composition _ g _ .

1 being the same in each instance. To illustrate the synergis-tic results with all possible non-sulfide ores and with all possible combinations of fatty acids and partial esters would represent a formidable and exhausting task that would unduly lengthen this application. Therefore, for convenience, syner-gism is illustrated by use of phosphate rock, which is most widely processed b~ froth flotation, but it is to be under-stood that similar effects are obtained with other ores and other combinations of fatty acids and partial esters so that the scope of the invention i5 not so limited.
The invention is more fully illustrated by the ex-amples which follow, wherein all parts and percentages are by weight unless otherwise specified. Three specific gen-eral procedures for froth flotation of specified ores are described below and are followed in the examples which follow.
General Procedure - Phosphate Rock Rougher Float Step 1: Secure washed and sized feed, e.g., 35 x 150 mesh screen ~ractions. Typical feed is usually a mixture o~ 23%
coarse with 77% fine flotation particles.
Step 2: Sufficient wet sample, usually 640 grams, to gi~e a dry weight equivalent of 500 yrams. The sample is washed once with about an equal amount of tap water. The water is carefully decanted to avoid loss of solids.
Step 3: The moist sample is conditioned for one minute with approximately 100 cc. of water, sufficient caustic as 5-10%
aqueous solution to obtain the pH desired (pH 9.5-9.6) a mix-ture of 50~ acid and fuel oil and additional fuel oil as nec-essary. Additional water may be necessary to give the mix-ture the consistency of "oatmeal" (about 69% solids). Theamount of caustic will vary from 4 to about 20 drops. This is adjusted with a pH meter for the correct end point. At the end of the conditioning, additional caustic may be added "
. ~ . .

~073563 1 to adjust the endpoint. However, an additional 15 seconds of conditioning is required if additional caustic is added to adjust the pH. Five to about 200 drops of acid-oil mix-ture and one-half this amount of additional oil is used, de-pending on the treatment level desired.
Step 4: Conditioned pulp is placed in an 800-gram bowl of a flotation machine and approximately 2.6 liters of water are added (enough water to bring the pulp level to lip of the container). The percent solids in the cell is then about 14~. The pulp is floated for 2 minutes with air introduced after 10 seconds of mixing. The excess water is carefully decanted from the rougher products. The tails are set aside for drying and analysis.
Step 5: The products are oven dried, weighed, and analyzed for weight percent P2O5 or BPL. Recovery of mineral values is calculated using the formula:

(Wc) (Pc) x 100 (W ) (PC) + (Wt) (Pt) wherein Wc and Wt are the dry weights of the concentrate and tailings, respectively, and Pc and Pt are the weight percent P2O5 or BPL of the concentrate or tails, respectively.
General Procedure - Barite Step 1: Charge the wet barite flotation feed, 2350 grams (37.5~ solids) into a 2-liter beaker. Start agitation. Feed is maintained at 90F. and pH of 7.9.
Step 2: Add the collector and 0.067 pound of methylisobutyl carbinol (MIBC) per ton of ore. Condition for one minute.
Step 3: Transfer the conditioned feed slurry into a labora-tory model D-l Denver flotation cell. Dilute with water to 30% solids.
Step 4: Open air inlet and begin fIotation for four minutes at 1200 RPM.

1 Step 5: Shut off air flow. Add collector and 0.022 lb./ton of MIBC. Condition for 1/2 minute.
Step 6: Continue the flotation for two minutes adding water throughout test to maintain pulp level.
Step 7: Dry the combined rougher concentrates and the tail-ings separately. Calculate percent of recovery based on weight of recovered concentrate and assay results of the con-centrate and the tailing.
General Procedure - Fluorspar Step 1: Grind a 1,000 gram of a -10 mesh ore sample in a laboratory rod mill for 11 minutes at 60% solids to produce a size distribution of 20~ + 100 mesh and 69% - 200 mesh size distribution.
Step 2: Transfer the ground ore feed into a Denver D-l flo-tation cell. Dilute to 33% solids with water.Step 3: Add 1.0 lb. of Na2CO3, 0.6 lb. of Quebracho, and 0.6 lb. of Na2SiO3 per ton of ore to the slurry. Start agi-tation at 1300 rpm and condition for 4 1/2 minutes.
Step 4: Add the collector and O.OS4 lb. of frother per ton of ore. Continue the agitation for 4 1/2 minut~s.
Step 5: Introduce air and float for 2 minutes.
Step 6: Turn off air. Add collector and 0.018 lb. of froth-er per ton of ore. Condition for 15 seconds.
Step 7: Turn on air and float for 2 minutes.
Step 3: Repeat step 6.
Step 9: Repeat step 7 but float for 1 1/2 minutes.
Step 10: Dry the combined rougher concentrates and the tail-ing. Calculate percent of recovery based on weight of rough-er concentrates and CaF2 assay results of the concentrate and the tailing.
Examples 1 - 10 Using combinations of the reconstituted tall oil fatty acid and a partial ester of maleic acid of the follow-.
.. . .~ ~ . . .

1 ing composition:

o O
.. .. .

O O

C14H ----~CH2CH20 )2 CH2cH2oc-cH = CH-c-OH, a sample of Florida phosphate rock was processed according to the General Procedure described above. In separate ex-amples, various proportions of fatty acid and partial ether were employed. In each example, the dosage of the collector combination was 0.5 pound per ton of ore and No. 5 fuel oil was used in equal amounts. Proportions and results are given in the table which follows.
Comparative Example A
Using the ore of Examples 1 - 10 and the reconsti-tuted tall oil fatty acid used therein, a run was made in which 0.5 lb./ton of the fatty acid and 0.5 lb./ton of No.
5 fuel oil were used. Results are also given in the table which follows.
Comparative Example B
Using the ore of Examples 1 10 and the partial ester used therein, a run was made in which 0.5 lb./ton of the partial ester and 0.5 lb./ton of No. 5 fuel oil were used.
Results are also given in the table which follows.

, ~L073563 _ , ~v 8 ~ ~ ~~ O
C~
, g O ~ ~ ~ ~ ~ N N O O
tr; ~ ~ N ~ ~ ~

~ 01~ w ~ 1~ t I ~ J r4 N 1~
_ ~ ! o c~
~ ¦ -- N N N C~J N N ~U N N N CU ~J

~1 ~ ~ u æ ~ ~. ~ O c ;~ ~3 ~ J N ~ 2 ~ ~ E
E~

3 ~ e ~ ¢ ~ c 3~ ~ ~~U 3 ~ 4~ g vu ~

~,, O O do 3 o 0 o d O 1l1 0 d O 0 0 0 ;g d C~ d 0 V~ V ~ b ~1rl ~

~ Q ~u~ Qo oo oo oo oo oo ~o oo o~ ;
3 ~ 0~ ~ ~ u~ ~o ~ cu0 , ~ ~ ~
pq rl N ~ 0 ~

~, . . ........ . . .
.

1~73563 1 The data given in Table I illustrates the synergis-tic effects produced by the collector combination of the pres-ent invention. Assuming that collector combination would perform normally; the recovery attributable to a particular combination would be th~ sum of recoveries attributable to the proportions of individual collectors present. Thus, for a composition of 50% fatty acid and 50% partial ester, the recovery attributable to such a composition would be calcu-lated at 50~ of the recovery obtained by fatty acid alone (38.5%) and 50% of the recovery obtained by partial ester alone (11~01%), the sum of which is 49.51% as shown in the table under the heading "Calculated Recovery t%)". In sim-ilar manner, calculated values are given for each of the com-binations employed and it can be seen that over the range of compositions studied, all combinations show synergistic effects.
To illustrate this completely unexpected phenomenon of synergism by the collector combinations of the present invention, the data of Table I was plotted as recovery against collector composition and the plot represents the sole fig~
ure of the present specification. The left hand abscissa represents a composition of 100% partial ester while the right hand abscissa represents a composition of 100% fatty acid and collector combinations represent intermediate points.
The straight line connecting the points on the left and right hand abscissas represent normal performance and correspond to the calculated values given in the table. Points repre-senting recovery values that fall about the straight line plot represent synergistic recovery values. The curved line connecting the points above the straight line represents the area of composition in which synergism is shown, which area is shaded. Thus, it can readily be seen that synergism is evident at combinations of about 10 to about 99 weight per-1 cent of fatty acid and, correspondingly, 90 to 1 weight per-cent of partial ester.
Comparative Example C
Using as collector a tall oil fatty acid composi-5 tion, a sample of Florida phosphate rock was processed accord- -ing to the General Procedure described above. The tall oil composition contained 4.2% rosin acids, 1.6% unsaponifiables, and 94.2% of fatty acids. The fatty acids had the following composition:
Polyunsaturated, Conjugated as linoleic % 8 Polyunsaturated, Nonconjugated as linoleic % 32 Oleic ~ 44 Saturated % 5 Other % 11 100 ", Results obtained are sho~n in Table I.
Comparative Example D
Using the phosphate rock of Comparative Example C and the General Procedure, a partial ester of maleic acid of the following composition was employed as collector:
O O

C12H25 ----tCH2CH20 )2CH2CH2 OC CH CH C OH 40 O O
Il .-C14H29-O - (CH2CH2O )2CH2CH2-O-C-CH-CH-C-OH 60%
Results are also shown in Table II.
Examples 11 - 13 Again using the phosphate rock of Comparative Ex- -ample C and the General Procedure, a series of runs were made in which mixtures of the collectors of Comparative Examples C and D were employed a~ collectors. Details and results are given in Table II.

: - ,. . ,. - - - ~ . : - . . . , :

~073563 o ~ o~
P~ ~ a~ ~ o cu ~
~I; ~oa) 0~ 0 LS~ o ~ ,~ ~ o ~J
C. ......
~ o a~
P~

~ ~ u~
C~ ~ C~
X ~

P;

o ~ o~ ~ cuao H 1-1 S~ ~ t!J N ~

o,o -d ~-1 O
~,, 0 P~
.-~ ~ ~
, n n _~
Cl o rt 0 ~ ~ o O C~

V V I

Z
.
.

1~73563 1 The results given in Table II show that the com-bination of fatty acid and partial ester, as taught by the present invention, provides higher recovery of BPL than can be obtained with the individual components alone while still maintaining high grade concentrate.
Comparative Example E
Using the phosphate rock of Comparative Example A and the General Procedure, a distillation tall oil fatty acid composition of the following composition was employed:
Heads 50~ Bottom 50%
Rosin Acids 0.6% 15-25 Unsaponifiables 25.0% 30-36 Fatty Acids 74.4% 34-58 The fatty acid content is of the ingredients as in the com-position of Comparative Example C except that different pro-portions are present. Results are given in Table III.
Comparative Example F
Again using the phosphate rock of Comparative Ex-ample C and the General Procedure, a partial ester of maleic acid of the following composition was used as collector:
O O

C12H25 0~--tCH2CH2 )2CH2CH20-C-CH=CH-C-OH 30%
O O
.. .. .
13 27 (CH2CH2O )2cH2cH2o-c-cH=cH-c-oH 70%
Results are shown in Table III.
Examples 14 - 16 Again using the phosphate rock of Comparative Exam-ple C and the General Procedure, a series of runs were made in which mixtures of the collectors of Comparative Examples E and F were employed as collectors. Details and results are given in Table III. ~ -.. ... .

~ ~ c~ ~ ~ ~ o o ......
C~ ~ ~ ~ C~

. U~ U~ CU o~
~, t-~o cn~ o C ~ o ~,i C~

~ I ~D N ~ ~ cr~
tR .~ 0~0 cu~o~ ' ~ ~ 0 c~
V~
~ t-o ~00 o ~ o u~
~J ......
r; ~ ~ p ~! ,~
u~ ~OC~
~3 ~i ~ ~ O E4 o C~ ~rl ~1~
:-: ~ ,, ~
H i~i ~ 1~ VJ
H ~i O 1~ ~ O
~ ~ I ~ O~ al C~ ~ ~ ~100 ~ ~ O

~ ~ 01~ 0 ~~ h ~
g3 t~ ~ ~ O O O ~ ' :~
~ 1~7 ~ ~ O
~ ~ ~0 ~ ~ 0 ~1 8 l~e ,~ 0 ~ o r~ r~ ~

1~73563 l The results given in Table III again show that the combination of fatty acid and par1:ial ester, as taught by the present invention, provides higher recovery of BPL than can ke obtained with the individual components alone while still maintaining high grade concentrate.
Comparative Example G
The procedure of Comparative Example E was followed except that a different sample of Florida phosphate rock was employed. Results are given in Table IV.
Comparative Example H
The procedure of Comparative Example D was followed except that the phosphate rock of Comparative Example G was employed. Results are given in Table IV, _Example l7 Again using the phosphate rock of Comparative Exam-ple G and the General Procedure, a run was made in which a 90:lO mixture of the collectors of Comparative Examples G
and H was employed. Results are given in Table IV.

. .

~73563 o u~
om c~
o ~ O ~
C~ n . ~1 ~ rl U~ 0 ~ cr~0 CU~O ~ .
O ~O ~ O

E~ ~ ~ t~ ,~ .
~ ~ ~ 0 ..
~ ~ I O~ U C
1~ ~

~ ~ 1~ ~ o ~ ~ .
~; ~i N ~æ CU CU CU
a ~ ~
~ C ~ 1 ~ ~0~1 O
~0 . ~ C 0~,0~ 1~ , ~ ~ ~ O ~0 ~ ~ .
..
O , ~ ~ O
~ ~ ~ :

' - . ... .. -. ~ - . : , .. . :

~6~735~3 1 The results given in Table IV again show the hi~h~r recovery values shown by combinations of the present inven-tion. A dosage of one pound per ton of ores of the 90/10 mixture, in fact, performs better than the conventional fatty acids alone at 1.3 lb./ton.
Comparative Example I
Again using the phosphate rock of Comparative Exam-ple C and the General Procedure, a run was made using a stand-ard mixture of tall oil fatty acids designated I. Details and results are given in Table V.
Comparative Example J
The procedure of Comparative Example I was followed except that a different standard mixture of tall oil fatty acids designated J was used. Details and results are given in Table V.
Comparative Example K
The procedure of Comparative Example I was again followed except in place of the tall oil fatty acid mixture there was used a partial ester (I) of the structure:
2~ CH3(cH2 ~ cH--~cH2 ~ cH3 ,.
O (CH2CH20) 2cH2cH2oc-cH=cH-c-oH~
wherein n + n' = 8 to 12 (a mixture). Details and results are given in Table V.
Example 18 The procedure of Comparative Example I was again followed except that a mixture of tall oil fatty acids I and the partial ester of Comparative Example K were used at a ratio of 95/5, respectively. Details and results are given in Table V.
Example 19 The procedure of Comparative Example I was again followed except that a mixture of tall oil fatty acids J and the partial ester of Comparative Example K were used in a .

1C~73563 1 95/5 ratio, respectively. Details and results are given in Table V.

... .. .: - . . . . - . . .. . ..

~LC~73563 S ~ o r~
~Q t, ~ , ~; ~ aD c~

o C~
CJ U~ o ~ U~
~ o t~

t- ~ ~ ,~ ~
~C . :.
I ~
r1 cr o a~
C~J C~l ~ ~ ~1 O ~ CD ~1 , ~ ~ u æ ~, q~
P O
a~ ~ ~ .
Pl~ ~ '' ~' ' ~ O O O O O
O ~ ~ ~ ~ ~ ~
P; 'O
~ p s o ~ o $ '' vl o ~ O e~ ~ d H ~ ~H P~
H 1~ :4 ? ~ .
' .

~ ~ ~ ~ ~

. . .

~073563 1The results given in Table V again show the higher results achieved by the present invention and that secondary alcohol ether ethoxylate partial esters are effective in the : -collection combination.
5Comparative Example L
Following the General Procedure described with re-spect to barite flotation, a reconstituted tall oil fatty acid was evaluated with a barite ore. Dosages and results are given in Table VI.
10Example 20 Again following the ~eneral Procedure described with respect to barite flotation, a mixture of 95 parts of the reconstituted tall oil fatty acid used in Comparative Example L and 5 parts of the partial ester of Comparative Example F. Dosages and results are given in Table VI.

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~, - - - , 3 C~735~3 l The results given in Table VI show that the col-lector combination provides higher barite recovery at higher grade than does the reconstituted tall oil fatty acid con-ventionally employed. Use of the partial ester alone with this feed was not practical because the excessive foaming produced cannot be handled on commercial equipment. Use of an effective defoamer with the partial ester alone resulted in poor barite recovery.
Comparative Example M
Following the General Procedure described for fluorspar, tall oil fatty acid was evaluated using a fluor-ite ore. Dosages and results are given in Table VII.
Example 21 Following the General Procedure described for fluorspar, a combination of 95 parts of tall oil fatty acid used in Comparative Example M and 5 parts of the partial es-ter used in Comparative Example F was evaluated using a fluor-ite ore. Dosages and results are given in Table VII.

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~ ~ _ s 1~7~563 1 The results given in Table VII show the beneficial results obtained when a combination of fatty acid and par-tial ester is employed compared to the use of fatty acid a-lone. Again, the partial ester alone caused too excessive amounts of foam to be useful in commercial equipment.
Comparative Example N
Using the General Procedure for Phosphate Rock, oleic acid derived from safflower seed was employed as col-lector using polypropylene glycol, MW 425, as frother in froth floating cement rock. Dosages and results are given in Table VIII.
Examples 22 - 26 The procedure of Comparative Example N combinations of the oleic acid of Comparative Example N and the partial ester of Comparative Example F were employed as collectors for cement rock. Compositions, dosages and results are given in Table VIII.

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1~73563 1 The results given in Table VIII show that combina-tions of the collectors used in the present inventlon improve recovery compared to that obtained with the fatty acid alone.
Use of the partial ester alone caused excessive foaming and could not be run on commercial equipment.
Comparative Example O
Using the General Procedure for Phosphate Rock, reconstituted tall oil fatty acid was employed with an equal weight of 20.5 fuel oil for flotation of Florida phosphate rock. Dosages and results are ~iven in Table IX.
Examples 27 - 36 The procedure of Comparative Example O was followed except that the collector used was a combination of recon-stituted tall oil fatty acid and the partial ester of Com-parative Example F. Compositions, dosages and results arealso given in Table IX.
Comparative Example P
The procedure of Comparative Example O was again followed except that the collector was the partial ester of Comparative Example F. Dosages and results are given in Table IX.

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1 Notes: 1. 0.5 lb./ton collector used in each run 2. 0.5 No. 5 fuel oil used in each run 3. pH 9.0-9.2 The results given in Table IX show the improved results obtained using the combinations of the present inven-tion.
Comparative Example Q
The procedure of Comparative Example O was again followed except that the usage of No. 5 fuel oil was varied.
Dosages and results are given in Table X.
Examples 37 - 39 The procedure of Example 28 was followed except that the usage of No. 5 fuel oil was varied. Dosages and results are also given in Table X.

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Claims (21)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1, A process for the beneficiation of non-sulfide ores which comprises classifying the ore to provide particles of flotation size, slurrying the sized ore in aqueous medium, conditioning the slurry with an effective amount of a combination of about 99 to about 5 weight percent of a fatty acid derived from a vegetable or animal oil and, correspondingly, from about 1 to about 95 weight percent of a partial ester of a polycarboxylic acid having at least one free carboxylic acid group, and floating the desired ore values by froth flotation, said partial ester having the structure:
wherein R1 is a primary or secondary alkyl group of about 8 to 18 carbon atoms, n is an integer of about 0-10 and R is a bivalent grouping selected from -(CH2)-m wherein m is an integer of 1 to 6; -CH=CH- ; -CHOH-CH2- ;
-CHOH-CHOH- ;

;;;;
, (ortho, meta, and para); and -C6H10-.

2. The process of Claim 1 wherein said partial ester has a structure wherein R is -CH=CH- .

3. The process of Claim 2 wherein said partial ester has a structure wherein R' is an alkyl group of 11 to 15 carbon atoms.

4. The process of Claim 1 wherein said non-sulfide ore is phosphate rock.

5. The process of Claim 1 wherein said non-sulfide ore is fluorite.

6. The process of Claim 1 wherein said non-sulfide ore is barite.

7. The process of Claim 1 wherein said non-sulfide ore is cement rock.

8. The process of Claim 3 wherein said non-sulfide ore is phosphate rock.

9. The process of Claim 3 wherein said non-sulfide ore is fluorite.

10. The process of Claim 3 wherein said non-sulfide ore is barite.

11. A synergistic collector composition for non-sulfide ores which comprises a combination of from about S to about 99 weight percent of a fatty acid derived from a vegetable or animal oil and, correspondingly, from about 95 to about 1 weight percent of a partial ester of a polycar-boxylic acid having at least one free carboxylic acid group, said partial ester having the structure:
wherein R' is a primary or secondary alkyl group of about 8 to 18 carbon atoms, n is an integer of about 0-10, and R is a bivalent grouping selected from wherein m is an integer of about 1 to 6; -CH=CH-;
-CHOH-CH2- ;
-CHOH-CHOH- ; ; ; ;

; (ortho, meta, and para); and -C6H10-.

12. The synergistic collector composition of Claim 11 wherein said fatty acid is present in the range of about 20 to 98 weight percent and, correspondingly, said partial ester is present in the range of about 80 to 2 weight percent.

13. The synergistic collector composition of Claim 11 wherein said R' of said partial ester contains 11 to 15 carbon atoms.

14. The synergistic collector composition of Claim 12 wherein said R' of said partial ester contains 11 to 15 carbon atoms.

15. The synergistic collector composition of Claim 13 wherein said n of said partial ester is the integer 2.

16, The synergistic collector composition of Claim 14 wherein said n of said partial ester is the integer 2.

17. The synergistic collector composition of Claim 11 wherein said R
of said partial ester is -CH=CH-.

18. The synergistic collector composition of Claim 12 wherein said R
of the partial ester is -CH=CH-.

19. The synergistic collector composition of Claim 15 wherein said R
of said partial ester is -CH=CH-.

20. The synergistic collector composition of Claim 16 wherein said R
of said partial ester is -CH=CH-.

21. The synergistic collector composition of Claim 11 also containing fuel oil.