US2385054A - Beneficiation of iron ore - Google Patents

Description

Patented Sept. 18, 1945 2,385,054 BENEFICIATION or mos oar:

Robert B. Booth, Springdale, and Earl C. Herkenhoil', Stamford, Conn, asslgnors to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing; Application August 11, 1943, Serial No. 498,254

15 Claims.

This invention relates to the froth flotation of oxidized iron ores and more particularly to processes using sulfonated organic carboxylic acid reagents.

The beneflciation of oxidized iron ore by froth flotation has presented a peculiarly dimcult practical problem. It is a comparatively simple matter to concentrate certain oxidized iron ores by froth flotation with a large series of promoters, such as for example oleic acid; however, the economics of iron ore utilization are such that it is necessary to obtain both good iron recovery and a relatively high grade in order to make the process economical because of the low price for which iron ore concentrates sell.

According to thepresent invention oxidized iron ore is floated using a sulfonated talloel reagent, preferably. in the presence of an unsulfonated oil, and for best results it is necessary to treat the iron ore feeds with an acid substance the anion of which is capable of forming an acid having a dissociation constant greater than 10-". Commercial results are not obtainable without the acid treatment except when very highly sulfonated talloel is used, in which case the promoter itsell is probably sufliciently acid or gives off sufficient acid to effect the necessary change on the surface of the iron ore particles.

Throughout the specification and claims the term sulfonated talloel will be used in its usual commercial sense to cover the products obtainable by reacting talloel with strong sulfuric acid. It is quite possible that both sulfonation and sulfation take place, and it is not intended that the term sulfonated talloel shall be restricted to a compound in which all. ordinary sulfur is present in the form of the sulfonic acid groups.

It is an advantage of the present invention that talloel which has been freed of lignin may be used;

and it is, of course, possible to use highly purified talloel obtained by distillation and similar processes for refining talloel. For practical operation we prefer to use sulfonated refined talloel as the results areslightly better than with the sulfonated crude product, and no material improvement is obtained when sulfonated distilled talloel is used, so that the higher cost of the latter product is normally not instilled in commercial operation. This flexibility with regard to the constitution of the reagent is of considerable importance because talloel is not a rigidly standardized chemical compound. 0n the contrary, the exact composition of talloeis will vary depending on the particular wood used in the sulfate paper process from which the black liquor soap is obtained, the part of the country in which the trees occur, and other factors. In our experience any of the widely distributed commercial refined talloels may be sulfonated to produce a reagent which will give satisfactory results in practical operation. While comparable results may be obtained with sulfonated refined or semi-refined talloel and with sulfonated distilled talloel, it should be noted that the amount of sulfonation is not necessarily the same. For example, treating distilled talloel with a smaller amount of sulfuric acid will produce a product which behaves in a manner similar to a sulfonated product obtained from reflned or semireflned talloel which has been treated with a larger amount of sulfuric acid. For example, distilled talloel treated with 30% by weight of sulfuric acid gives a product, the behaviour of which in the process of the present invention closely approximates that of ordinary refined talloel which has been treated with 50% of sulfuric acid.

It is not necessary to isolate the sulfonated talloel. On the contrary, the reaction mixture itself may be used'or it may be partially or wholly neutralized with alkali. No material difference in flotation efliciency is to be noted, and we believe that the impurities produced in the sulfonation reaction do not exert any deleterious effect on the flotation. The possibility of using crude sulfonation mixtures which are, of course, cheaper is a valuable advantage or the present invention. Any economy in reagent cost is of considerable importance in iron ore flotation by reason of the low sales price of the final product.-

It is a further advantage of the present invention that it is not limited to sulfonated talloels produced by any particular sulfonation procedure and any of the ordinary sulfonation processes may be used.

The sulfonated talloel reagent of the present invention is rather different in its characteristics from sulfonated petroleum hydrocarbons which are claimed in our copending applications, Serial No. 481,906, filed April 5, 1943, and Serial No. 491,384, filed June 18, 1943. While the present invention shares with these other applications the possibility of producing a commercially useful grade of iron ore concentrate from practically any iron ore which is available, the behavior toward acid neutralization and other factors is rather different. sulfonated petroleum hydrocarbons in general do not give useable results unless the iron ore is pre-treated with a fairly strong acid. sulfonated talloel may, however, be used alone or with additional unsulfonated oils without pre-treatment with acid where highly sulfonated material is employed. n the other hand low sulfonated talloel will'not give useful results with acid treated ore alone in the absence of unsulfonated oils, and in fact with very low degrees of sulfonation the acidtreatment may actually inhibit practical flotation. It is clear that the froth flotation of iron ore using sulfonated re-,

agents with acid pre-treatment of the ore must involve a number of factors, the full extent of which has not yet been determined. Without desiring to limit the present invention to any unproven theories we believe that one reason for the anomalous results with talloel of low degree of sulfonation may lie in the fact that in such cases the major portion of the promoter is in the form of an unsulfonated fatty acid or resin acid, and one of the drastic distinctions between sulfonated reagents and carboxylic acid reagents is that acid pre-treatment of the ore often-times inhibits flotation with the latter. i Another distinguishing featuie between sulfonated talloel and sulfonated hydrocarbons is that many of the latter give satisfactory results on acid pre-treated iron ore even though the flotation circuit may be brought to neutrality or even slight alkalinity with ordinary alkali such as soda ash. With sulfonated talloel, however, commercial results have not been obtained unless the flotation circuit itself remains acid.

It is an advantage of the present invention that the particular acid used does not appear to be critical. although results of practical utility are not obtained with weaker acids than those having a dissociation constant oflfl- It is, of course. necessary that the acid anion should not have a known depressive effect on the iron ore. Sulfuric acid gives as good results as any, and because of its great cheapness constitutes the preferred acid for practical operation. It is, however, not superior to other strong acids in the quality 'of the results obtained and its choice is, therefore, dictated primarily by economic costs rather than operative efliciency.

It is an advantage of the present invention that satisfactory results are obtainable with sulfonated talloelalone when the ore has been properly pretreated with acid. However, the sulfonated talloel may, of course, also be mixed with other sulfonated reagents such as sulfonated petroleum hydrocarbons and under some circumstances these mixed reagents possess some economical. advan-' tages. It is also possible to combine an anionic float using sulfonatedtalloel with a silica float of the concentrate using known cationic froth flotation procedures. With ordinary iron ores this double float does not give improved results and, therefore, its additional cost is not justifled. It is, however, available for the treatment of certain particularly refractory ores.

The froth flotation process of the present invention behaves normally with respect to slime, that is to say in common with many anionic flotations a small amount of slime can be tolerated. but larger amounts of slime decrease grade of concentrate and increase reagent consumption. It is, therefore, desirable to deslimefairly thoroughly, although the extreme degree of deslimin which is essential with many cationic flotations is not necessary. Ordinary good desliming practice may, therefore, be followed, and it is an advantage of the present invention that the process is not critical in this respect. 4

The process of the present invention gives excellent results with the more common oxidized iron minerals such as hematite and magnetite. It is, however, an advantage of the present invention that other iron minerals commonly present in iron ores, such as martite, limonite, siderite. goethite, and the like, may also ,be successfully floated by the procedure of the present invention.

' The invention will be described in greater detail in conjunction with the following specific examples which deal with the treatment of typical iron ores. In some cases low grade iron ores are used which present a more difllcult problem in obtaining high grades with good recoveries. The parts are by weight.

Example 1 A low grade refractory Minnesota iron ore forming a reject from iron beneflciation operations and containing about 15% Fe as hematite with some limonite mixed with a quartz gangue Promoter used With 1.62 lbsJton sulfuric With 1.62 lbsJton sulfuric sulionated talloel acid acid and an lba/ton 1...: oil

Concentrate Rgh. tail- Concentrete 11gb. teil- Concentrate Rgh. tail- Concentrate Rgh. tailpercent Fe ing percent Fe in: percent Fe ins percent Fe in Pm Parts talioel D's Assay Assay Du. Assay Db Assay an): $62 PH trib. we :1; PH an: 8.7.; Pa

Fe Fe is 100 None 31. 47 80. 26 8. 46 7. 1 No promotion 28. 48 64. 28 6. 81 7. 1 No promotion 100 39. 33 62. 77 6. 60 6. 7 No useful 110st 61. 71 46. 89 7. 08 6. 7 No useful float 100 2) 19. 94 89. 66 2. 76 6. 7 66. 37 61. 34 ll) .8 42. 76 a0. 62 l. 71 6. 7 66.67 70. 84 4. l8 2. 8 1(1) 29. 38 90. 36 1. 79 6. 6 49. 66 71. 09 82 2. 8 44. 42 92. 81 1. 01 6. 6 60. 39 88.16 1. 91 2. 8 100 30. 93 87.38 2. 16 6. 4 48. 36 61. 28 07 2. 6 36. 83 92. 62 1. 43 6. 8 66. 23 90. 67 1.19 2. 7 100 60 37. 38 83. 86 2. 39 6. 2 66. 61 72. I) 76 2. 8 43. 96 91. 70 l. 49 4. 6 62. 66 89.72 1. 31 2. 6 100 60 36.23 91.87 1.31 6.3 43.71 $1.14 .46 2.6 63.92 94.76 0.72 4.3 66.48 94.39 0.83 2.6 100 70 64. 93 81. 27 2. 87 4. 0 63. 98 68. 86 40 2. 6 62. 18 92. 76 0.96 4.0 66. 19 96. 0.- 42 2. 6 100 at 41.18 83.71 2.16 3.8 62.42 63.79 .06 2.7 66.77 93.09 0.89 3.8 67.60 92.86 1.07 2.6 100 90 63.60 66.66 4.18 3.7 62.00 66.69 .3 2.7 67.74 86.62 1.79 3.8 67.66 89.06 1.66 2.6 100 100 60.07 38.33 7.40 3.6 69.69 36.16 76 2.6 68.46 69.01 3. 70 3.66 69.11 86. 27 1.73 2.6

Certain anomalous results will be noted where 20 as hematite associated with a quartz gangue; was

sulfonated talloel was used alone or with ore treated with sulfuric acid but without any unsulionated oil. The 80% sulfonated talloel gave poorer grade than the 70% and in conjunction conditioned with 30% suli'onated distilled talloel with and without added fuel oil, sulfuric acid and both. The amount of sulfonated reagent was 2 lbs. per ton. The results appear in the followwith sulfuric acid the 60% was poorer than even 25 ing table:

523% m, Sulfcnatd talloel alone with 25$ With 5.00 lbe./ton fuel oil ig gggggggggg g gg a Concentrate Rgh. teil- Concentrate Rgh. tail- Concentrate Rgh. tail- Concentrate Rgh. tallpercent Fe ing percent Fe ing percent Fe in: percent Fe ing 61% "3}? my Amy A say Assay Assay mm pH Assay pH Assay at pH Assay a pH Fe Fe Fe 100 so 24.12 92.96 3.94 6.6 38.09 8.1.14 2.8 43.69 96.46 0.96 6.4 68. 91.% 2.16 3.8 100 20 B. 10 88. 62 8. 80 6. 7 61. 16 4. 37 2. 8 100 10 38. 12 86. 44 4. 49 6. 8 N0 1138 I11 float 100 None 39. 17 79. 87 6. 89 7. 1 No prolmotion the 20%. These grade results are not significant where they fall unusually low, because in the absence of unsulfonated oil the froth was very intense and an unusually low grade merely means that there was gangue carried along mechanical- 1y. The adverse eflect of sulfuric acid in the case of unsulfonated talloel or 10% sulfonated talloel has been discussed above, and we believe is due to the fact that in these cases the normal effect of acid with carboxylic acid promoters predominated.

Example 2 A somewhat higher grade Minnesota iron ore 5 sulfonated talloel.

Example 3 The ore of Example 1 was used to test sulfonation of different talloels. The conditioning and 50 notation procedure was the same as in Example 1.

The amount of sulfonated reagent usedwaa 1.62 lbs. per ton, except in the cas of test 3, where it was 1.08, and test 7, where it was 1.36. In each case attempts were made to operate under opwasher tailing, containing about 25% Fe mainly timum conditions for the particular talloel.

Concentrate Bo her Percentage sulionication LbsJton W at Fe Promoter used-type of talloel A at; Sulfuric acid Eff 1 3: m name. per pH cent Fe A crude talloel containing lignin 100 3.23 1. 62 62. 66 90. 88 l. 01 2. 7 Distilled tailoel-about 30% rosin acids 100 3. 2a 1. 62 64. 76 90. 83 1. 19 2. 6 Distilled talloel 00 2. 28 1. c2 c2 30 so. so 1. e7 2 7 Partial] refined Canadian talloel high in nonsaponiflable mater l 00 3. Z! 1. 62 69. 41 60. 06 6. 91 2. 6 A refined blown talloel m 3. 23 1. 62 63. 74 93. 30 0. 88 2. 8 Partially refined talloel containing some precipitated rosin 100 3. 23 l. 62 67. 71 90. 19 1. 38 2. 6 D0 00 3-23 1.62 60.46 89.66 1.36 2.6 Talloel-dlluted with 10% secondary butanol 100 0 3. 06 l. 62 so. 64 88. 65 1.66 2. 7 Distilled talloel about 30% rosin acids.... v 100 gas 86% acid)... 3. 66 1. 62 65. 35 85. 84 i. 61 2. 0 D0 100 oleum) 3.23 1.62 66.65 33.34 1.91 17 Refined talloel-aiter sullonation neutralized to methyl orangewith causticsoda ...4...-. 00 60 a 1.21 1.62 60.68 78.87 2.67 Distilled tall sulionation neutralized to methyl orange with caustic soda 100 1 8% acid)..- 1. 21 1. 62 ea 70. 99 2. 57

in one case, did not give quite as good results as sulfonated ordinary refined tailoel. However, all of the talloels gave results which may be considered satisfactory.

Eeamplc 4 the case of saponified talloel. where 4 lbs. of

sulfuric acid were used. Conditioning procedure and flotation procedure were identical with those of the two preceding examples. The metallurgical results appear in the following table:

Concentrate Rougher tail- Addition reagent percent Fe m8 Distribu- Type Lbalton Assay "on pei ceent p11 Talloel 4.58 58.40 92.53 1.25 2.8 Oleic acid 4.47 59.23 91.00 1.91 Crude oil 5. 13 56. 48 95. 21 0.83 2. 8 Chlorinated kerosene 3.88 30. 66 83. 93 3. 28 Coconut oil 3. 24 00. 07 92. 14 1. 37 Cottonseed oil 3.03 59.47 80.12 2.15 Na htilenic acids. 4. 11 56. 25 85.35 2. 45 neptaldehyde.. 4. 2o 54. 57 82. 70 2. 81 Methyl ester of talloel 4. 47 59. 59 84. 23 2. 89 Lauryl merca tan... 3. d 59. 83 83. 68 3. 22 2 8 Sa nifled tal oel.- 4.00 55.89 90. 54 1.91 2. 6 B6, fuel oil 5. 02 58. 69 91. 90 2. 2. 8

It will be apparent that good results are obtainable with all of the unsulfonated oils and are commercial with the possible exception of n-heptaldehyde where the concentrate was a little below usual commercial grade. Excellent results are obtained with talloel and coconut oil as the unsulfonated modifying agents. Good results are also obtainable with ordinary fuel oil, and the choice will be determined largely by economic considerations, primarily the relative costs of the materials. The wide choice of cheap unsuifonated modifying agents represents an advantage because of the greater flexibility of the operation. It is of course, possible to use mixtures of unsulfonated oils where such mixtures may be desirable for economic reasons.

Example 5 The It will be noted that some crude talloels gave g excellent results and that distilled tailoels. except Concentrate m. an- Mm per cent 1's in;

Fuel oil, H-M Type LbsJton Assay Pm. pH

1.02 4.0 50. 91. 2.15 3.8 1.52 0.80 50.37 90.51 0.00 2.9 2.10 3.48 56.87 91.12 1.07 2.4 I 2.48 5. 50.71 78.05 0.45 0.0 s. as s. so so. 14 0c. 21 use a. 9 3.90 180 57.50 94.24 1.10 4.0

2.10 3.50 50. 37 90.2) 0.88 3.0 4. 00 54. 57 90. 10 0- 95 0. 1 5.41 3.54 42.77 90.00 1.07 0.5 3. 25 3. 54 59. 83 77. (I) 4. N 2. 9 3. 25 4. M 57. 92 91. 72 1. 31 3. 3 3.25 3.80 58. 51 95.72 1.07 2.7 None 4. 07 43. 59 90. 45 0. 95 0. 4

oil.

I Unsulionated tslloel used in place of fuel I Saturated.

preferred because of its cheapness. The figures for acid and fuel oil are based on are rather than deslimed feed which basis was used in the table following Example 2.

Emmple 6 The flotation procedure of Example 1 and 2 was followed using the ore of Example 2. In each case a sulfonated refined talloel was used, the first and third tests employing 3.34 lbs. per ton and the second test 4 lbs. per ton. Typical acid salts were used in place of acids and the metallurgical results appear in the following table:

substantially the same results as sulfuric acid. but require larger quantities. Smaller quantities of sodium silico-fluoride may be used with some sacrifice of grade. In each case an amount of acig1 tsgalt was used which was felt to give good res Example 7 The ore and flotation procedure of Example 1 was followed using a 30% sulfonated distilled talloel as promoter, together with sulfuric acid. Part of the ore was thoroughly deslimed in accordance with good ore dressing practice, part was partially deslimed, and part was not deslimed at all. The results appear in the following table:

Assay LbsJton used Per cent Pmduct :551:13? Per Per cent cent Promoter H1804 2 f Essential] completely deslimed:

Oalc. ad. 100. 00 14. 33 100. 00 6. 84 36. 7s 14. 99 19. 54 67. 20 9. 74 78. 01 1. 60 1. 50 8. 76

It will be apparent that while desliming is desirable it need not be carried to an extreme degree. In each case the amount of reagent employed was that which gives optimum results, and it will be apparent that when the ore is undeslimed inferior grade is obtained, even though a considerably increased amount of reagent is used.

Example 8 The ore of Example 1 was used, but part of the ore was conditioned at 65% solids and part at 22% solids. The reagents used were 1.62 lbs. per ton of 30% sulfonated distilled talloel, 1.62 lbs. per ton sulfuric acid and 3.05 lbs. per ton fuel oil. The results appear in the following table:

Concentrate r Pulp density per cent cent Fe pe Tamng solids Assay Assay Distrib. peii cent pH Conditioning Flotation It will be apparent that conditioning at high solids appears to be necessary in order to get maximum results. This is in line with our experience with sulfonated hydrocarbons as promoter reagents and in this respect the present invention does not depart from optimum conditions set out in our two copending applications referred to above.

Example 9 Assay P t el'cen Product trib weight Percent Percent of Fe It will be apparent that with a soft iron ore considerable secondary shine is formed by scrubbing. However, in many cases it is desirable to remove this slime as it will be noted that an excellent recovery was made, the 69.82% actually amounting to over of the iron in the flotation feed, some 23% of the iron in the original sample being rejected as slime. The desirability of scrubbing to remove secondary slimes is largely dependent on the nature of the surface of the ore particles and is desirable with some ores and not with others. By comparing the results of Example 9 with those obtained in Example 7 on essentially completely deslimed ore, it will be apparent that considerable saving in reagents was obtained by the use of the scrubbing procedure.

Example 10 The procedure of Example 1 was followed but the various sulfonated talloels were used in three portions, immediately after preparation, one hour after preparation, and 24 hours after preparation. The sulionated talloel for the first series of three tests was 30% sulfonated distilled talloel, while that used for the second and third series was 50% sulfonated refined talloel. In the third series the sulfonated talloel was diluted as soon as made and was allowed to stand in the form of a 7.5% aqueous solution. The reagent amounts in the case of the first two series were 1.62 lbs. per ton and in the last series 3.24 lbs. per ton. Results appear in the following table:

Concentrate Lbalton pen tFe Rglntaillng Whenused Assay mso. gi Assay Distrib. percent pH Immediately after preparation 1.62 4.07 57.20 91.77 1.07 2.65 1 hour after preparation 1.62 4.07 50.59 90.67 1.31 2.7 24 hours after preparat on 1.62 4.07 60.43 46.77 6.09 2.6 Immediately after reparation 1.62 5.07 57.64 93.83 0.83 2.6 1 our alter prepstation 1.62 6.07 68.40 92.8 0.95 2.65 24 hours after preparation 1.62 5.07 42.99 3&16 9.25 2.7 Immediately after preparation 1.02 5.07 53.92 91.46 0.95 25 24hours alter preparation 1.62 5.07 52.66 89.07 1.07 2.6

It will be apparent that the sulfonated talloel keeps for a suilicient time to permit satisfactory feeding in commercial operations, but does not keep for a day. However. if it is desired to keep the talloel for longer periods this may be effected by dissolving the sulfonated talloel in water as soon asitisprepared.

The above results were obtained with sulfonated talloels which had not been neutralized, and these remarks are not completely applicable to neutralized or partially neutralized talloels.

Example 11 no discernible diflerence between natural and synthetic talloels of the same composition.

The expression oxidized iron ores" is used herein in its commonly accepted meaning to include not only iron oxide ores such as those containing magnetite, hematite, etc., but also hydroxides, carbonate, etc.

We claim:

1. A method of beneficiating oxidized iron ores by froth flotation which comprises subjecting the ore to froth flotation in the presence of an effective amount of a collector containing as its essential collecting constituent sulfonated talloel including an eifective amount of an acid substance the anion of which is a constituent of an acid having a dissociation constant of at least and which does not adversely effect flota- Lbs Concentrate Pr Mn Feed per cent Fe omoter my need, Source of are N at Fuel Fe H5804 on Assay Dlstrib.

3. 48 2. 64 4. es Minnesota-aw tailing, p 7 116111! and quartz 43. as 68. 67 80. 86 -2 2. 1.1 2. l1 3. 72 ta-a tag nlte (an. &1;

talnin r ma 3 17 4.22 5. Nandvq mytinfi 22.76 54.45 96.29 0-2 ew one ---a mans c on coni 2 w z w a. a eeni ra n a. 64.22 68.43 06. 81 0-1 ew one amsgne m c table con oentrate 61. 47 70. 32 76. 41

2.64 2.64 4.96 Minnesota-a tsconite ore, contsining hematite and uarts...- 87.88 56.89 vase 0-2 2. 64 2. ll 4. 9 Minnesota-a washer re ct from a hematite o so. 28 50. 83 89. 71 4 2. 11 2. 11 4.46 M ta-a washer tailing, con L 60 L t a tuini ng h tiie W- 18.88 I 54.69 0?. 07 0-1 ew arse -an ore con martlto aid quarts 22. 75 07.09 91. 61 0-2 I Refractory due to locking of Fe and'SiO, in due alaes.

It will be apparent that acceptable results are obtained with various iron ores, the less refrw tory ores giving commercial grade products and even the highly refractory ores giving products which can be utilized.

While the best results are obtained when sulfonated talloels are used in conjunction with other acid substances such as sulfuric acid, fair results are obtainable with some sulfonated talloels particularly when associated with unsulfonated oils without additional acid. It is difficult to determine whether the action may be due in part to some of the sulfonated talloel acting as an acid agent and some as a promoter. However, the invention is not limited in its broadest aspects to the use of an added acid substance although this constitutes the preferred procedure and in most cases gives the best commercial results.

Throughout the specification and claims natural talloel has been described, that is to say the mixture of resin and unsaturated fatty acids which is obtained by acidification of black liquor soap from the sulfate paper pulp process. In certain. localities where talloel is not readily available synthetic mixtures have been made up of resin acids and unsaturated fatty acids which behave in the same manner as natural talloel and which are referred to in the art as synthetic talloel. The term as used in the present speciflcation and claims is intended tocover the mixture of resin and unsaturated fatty acids regardless of the method by which this mixture is produced and. therefore, is intended to cover synthetic talloels as well as natural talloels. From the standpoint of froth flotation there is tion whereby a concentrate is obtained relatively rich in iron mineral and a tailing relatively poor in iron.

2. A method of beneflciating oxidized iron ores by froth flotation which comprises conditioning the ore at high solids with a reagent containing sulfonated talloel as its essential collecting conby froth flotation which comprises conditioning the ore at high solids with a reagent. containing sulfonated talloel as its essential collecting constituent and an effective amount of sulfuric acid, diluting the conditioned ore to flotation density and subjecting it to froth flotation to produce a concentrate relatively rich in iron mineral and a tailing relatively poor in iron.

4. A method according to claim 1 in which the reagent is associated with an unsulfonated oil.

5. A method according to claim 2 in which the reagent is associated with an unsulfonated oil.

6. A method according to claim 3 in which the reagent is associated with an unsulfonated oil.

'I. A method according to claim 1 in which the reagent is associated with unsulfonated talloel.

8. A method according to claim 2 in which the reagent is associated with unsulfonated talloel.

9. A method according to claim 3 in which the reagent is associated with unsulfonated talloel.

10. A method according to claim 1 in which the reagent is associated with an unsulionated glyceride oil.

11. A method according to claim 2 in which the reagent is associated with an unsultonated glyceride 011.

12. A method according to claim 3 in which the reagent is associated with an unsulfonated 10 glyceride oil.

13. A method according to claim 1 in which the reagent is associated with an unsultonated hydrocarbon oil.

14. A method according to claim 2 in which the reagent is associated with an unsuitonated hydrocarbon oil.

15. A method according to claim 3 in which the reagent is associated with an unsuitonated hydrocarbon oil.

ROBERT B. BOOTH. EARL C. HERKENHOFF.