AERO XANTHATE PRODUCTS

*

AERO XANTHATE PRODUCTS

AMERICAN CYANAMID COMPANY

CYANAMID CANADA,INC.

CYANAMID INTERNATIONAL DIVISIONS

C>1972 AMERICAN CYANAMID COMPANY.REGISTERED TRADEMARK OF AMERICAN CYANAMID COMPANY

TABLE OF CONTENTS

PageINTRODUCTION. ... ... 1

USES & SPECIAL APPUCATIONS ; 2PHYSICAL & CHEMICAL PROPERTIES... , 4

A Specific Gravity 4B Solubility e .., 11C Stability 16D Determination of Active Xanthate in

Xanthate Solutions by the Acetone Method. . . . . .. . .

HANDLING SHIPMENTS ... ... A EquipmentRequired B Procedures for Dissolution & Unloading. . . . . . . . . . . .

SAFETY DISCUSSION ... A General B Safety Precautions in Handling C Medical Management TABLES

...24

...26

...26

...27

... 31

...31

...32

...34

6...19

89

...1012

...13

...14

...1520

. . . . . .. 2122

.. 2328

29

1-SUMMARY OF PHYSICAL & CHEMICALPROPERTIES OF AERO XANTHATE SOLUTIONS.

2-CARBON DISULFIDE FORMATION. . . . . . . . . . . . . . .

FIGURES1-Specific Gravity of AERO 317 Xanthate 2-Specific Gravity of AERO 325 Xanthate . ... 3-Specific Gravity of AERO 343 Xanthate.. .. . ... 4-Specific Gravity of AERO 350 Xanthate. . . . . . . . . . .

5-Solubility of AERO 317 Xanthate. 6-Solubility of AERO 325 Xanthate. . . . . . . . . . . . . .. . . .

7 -Solubility of AERO 343 Xanthate. . . . . . . . . .. . . . . ...8-Solubility of AERO 350 Xanthate. . . . . . . . . . . . . . . .. ,9-Decomposition of AERO 317 Xanthate... . . . . . . . . .

1D-Decomposition of AERO 325 Xanthate. . . . . . .. . ..11-Decomposition of AERO 343 Xanthate. . . . . . . . . . .

12-Decomposition of AERO 350 Xanthate 13-Equipment Setup for Dissolving & Unloading 14-Water Requirements for AERO Xanthate Solutions

(Imperial Gals.) 15-Water Requirements for AERO Xanthate Solutions

(U.S. Gals.) ... .. .. . .. . .. 30

INTRODUCTION

The information in this bulletin is provided mainly toassist customers in the application and handling of bulkand drum shipments of AERO Xanthate products.

AERO Xanthate products for American Cyanamid Com-pany, Cyanamid International, and Cyanamid CanadaInc., are now manufactured by Cyanamid Canada Inc., inNiagara Falls, Ontario, Canada. The original plant beganproduction in Niagara Falls in 1957.

Since 1917, Cyanamid has supplied chemicals and tech-nical knowledge to mineral processors throughout theworld. Research chemists and engineers at the miningchemicals research laboratory, Stamford, Connecticut,maintain a continuing quest for new and improvedchemicals and processes for the mining industry. ATechnical Service Group. staffed with qualified metallur-gists. provides customers with recommendations andinformation pertaining to ores and mill samplessubmittedfor evaluation. At this laboratory. information gatheredfrom Cyanamid representatives is carefully assessed andadded to a vast store of knowledge of mining andmetallurgy. In addition, Cyanamid field engineers andtechnical representatives. skilled in mineral processingtechnology and trained to advise and assist, are located inmining districts throughout the world (see back page foraddresses).

1

USES ANDSPECIAL APPLICATIONS

AERO. Xanthates, under suitable conditions, are excellent col-lectors for all sulfide minerals. In the absence of modifyingagents, they are essentially non-selective in their action. Generallytheir effectiveness as collectors increases with an increase in thecarbon chain length and conversely they become less selectivewith an increase in carbon chain length. Thus, ethyl xanthate isthe weakest and most selective xanthate, and amyl xanthates arethe most powerful and least selective collectors. In conjunctionwith a sulfidizing agent, such as sodium sulfide, or sodiumhydrosulfide, they are good collectors in the flotation of oxidizedlead and copper ores. For this application, isopropyl and amylxanthates are most frequently used.

Cyanamid produces xanthates in easily handled. pelletized form.The pelletized products have a higher bulk density than competi-tive powdered products. However. the pellets are small enough sothat the rate of solubility is not unduly hindered.

The xanthates at present offered by Cyanamid are AERO 317,325. 343. 350. and 355 Xanthates.

AERO 325 Xanthate - Sodium ethyl xanthate

This xanthate is essentially similar in action to flotationcollectors; and being the shortest carbon chain xanthate,has found use particularly where maximum selectivity isdesired. It can be used alone or in combination with one ormore of the AEROFLOA T* Promoters.

"Registered Trademark of American Cyanamid Company

2

AERO 317 Xanthate - Sodium isobutyl xanthate

This is a strong, non-selective collector for all sulfidemi nerals. AERO 317 Xanthate is considered the best xanthatefor the flotation of pyrite in natural circuits, that is, in circuitswhere the pH has not been adjusted with either lime or acid.

AERO 343 Xanthate - Sodium isopropyl xanthate

Because of its lower cost, AERO 343 Xanthate is chosen bymill operators for wide application in copper, lead and zincsulfide flotation.

AERO 350 Xanthate - Potassium amyl xanthate

This is the most powerful of the AERO Xanthates. It is mostuseful in operations where a strong, non-selective sulfidecollector is desired, and as the collector in "scavenger"flotation operations. AERO 350 Xanthate is chosen in theflotation of copper, copper-lead and copper-nickel minerals,where a strong collector is desired. Because of its non-selectivity, it is frequently the principal collector in theflotation of pentlandite and pyrrhotite minerals.

AERO 350 Xanthate is the preferred xanthate for therecovery of oxide lead and copper minerals after sulfidiza-tion, although AERO 343 Xanthate is also used for thispurpose.

AERO 355 Xanthate - Sodium amyl xanthate

This addition to the xanthate group of products is, like itscounterpart AERO 350 Xanthate, a very powerful non-selective sulfide mineral collector. It can be substituted forAERO 350 Xanthate under all conditions of flotation. Fieldtesting of this product has indicated, in specific instances,superior performance over AERO 350 Xanthate at lowerdosages resulting in cost savings.

"[

3

PHYSICAL AND CHEMICALPROPERTIES OF

XANTHATE SOLUTIONS

A. Specific Gravity

The specific gravities for AERO Xanthate solutions are givenin Figures 1-4 and in Table 1. The data were derived fromtesting solutions of three known concentrations at threetemperature levels, 50°F (15°C), 68°F (20°C), and 77°F(25°C), using a hydrometer calibrated @ 60°F/60°F. Onlythe values for 68° F were plotted in the Figures, sincespecific gravity does not change significantly with temper-ature.

This information can be used: 1) to determine the rate ofsolution during the unloading of sparger cars 2) to controlthe concentration of xanthate solutions in storage and inprocess and 3) to determine the solution storage require-ments for bulk shipments. An example of the latter is asfollows:

Determination of the final volume of a 25% by wt. real AERO343 Xanthate solution, to be prepared by dissolving a 20,000lb. (as received) bulk shipment. From Figures 14 and 15, it isseen that 20,000 lb. of AERO 343 Xanthate, as received, willrequire 6,122 U.S.G. (5,100 i.g.) or 51,000 lb. of water tomake a 25% by weight real xanthate solution; from Figure 3,page 9, it is seen that the specific gravity of this solutionwill be 1.101 at 68°F (20°C).

The final volume @ 680 F (200 C) can then be calculated

Final volume. gallons =Wt. xanthate (as received) lb. + wt. water required, lb.

Ib/gal X specific gravity @ 680 F (200 C)

4

20,000 + 51,000Final volume, U.S.G. = ;.!i,':: = 7,742 gal.

8.33 X 1..101

Final volume, i.g. = i, = 6,449 gal.,,_.. - --120,000+ 51,000

"Note: i.g. = IMPERIAL GALLONU.S.G. = UNITED STATES GALLON

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FIGURE 1AERO 317 Xanthate

SPECIFIC GRAVITY @ 68°F (20°C)VS. SOLUTION STRENGTH

36

32

28

24

20

16

12

8

4

0

c7

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FIGURE 2

AERO 325 XanthateSPECIFIC GRAVITY @ 68°F (20°C)

VS. SOLUTION STRENGTH

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20

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10

B. Solubility

The solubility of AERO Xanthate solutions in water is givenin Figures 5-8. Crystal points. taken from the Figures. aregiven in Table I. For a given concentration, storage at anytemperature below the curves in Figures 5-8 will result insolids formation. It is evident from the Figures that evendilute solutions should not be stored outside in winter.

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FIGURE 5

SOLUBILITYOF

AERO 317 Xanthate

12

FIGURE 6

SOLUBILITYOF

AERO 325 Xanthate

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FIGURE 7

SOLUBILITYOF

AERO 343 Xanthate

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% Xanthate (grams Xanthate per 100 grams Sotution)

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FIGURE 8

SOLUBILITYOF

AERO 350 Xanthate

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15

10

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. 15

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C. Stability

1. General

The decomposition of xanthate solutions occurs mainly byhydrolysis and is temperature dependent. It is also acceler-ated by low pH; this would only be a factor if acid wereaccidentally added to a xanthate solution.

Table 1 gives the average percent loss of real xanthate perday. This is based on total xanthate content and it is not thesame as numerical drop in assay. Thus a 25% solution ofAERO 343 Xanthate stored at 200 C. with an average percentloss per day of 0.2% would have a 0.05% numerical drop per

day initially.

The Figures 9-12 show the numerical drop of 100/0 and 25%solutions with time (or rate of decomposition).

2. Products of Decomposition

The mechanism by which xanthate decomposes is asfollows:

2X2CS3Carbon

Disulfide

+6 ROH +Alcohol

SII

6 R-O-C-SX + 3H20 ~Xanthate Water

X2CO3 + 3C52Carbonate Trithiocarbonate

(where X is sodium or potassium)

The decomposition products are alcohols, carbonate andtrithiocarbonate salts and the flammable carbon disulfide.The latter is very hazardous if formed in sufficient quantity(see Safety Discussion, p. 31).

16

The amount of carbon disulfide released by decompositionhas not been measured. but an estimate can be made usingthe preceding reaction equation which shows that threemoles of carbon disulfide form when six moles of xanthatedecompose. For example. in the case of AERO 343 Xanthate

lb. carbon disulfide released

lb. xanthate decomposed

3 X molecular wt. carbon disulfide

6 X molecular wt. xanthate

3 X 76

6 X 158=0.24-

If a mill had an inventory of 1,000 i.g. (1200 U.S.G.) gals. ofa10% sol ution of this xanthate, the amount of carbon dis ulfidereleased at a decomposition rate of 0.3% per day would be:

0.3 lb. decomposedX 1,000 i.g. sol'n,"",;!'cr"-~.'.=

(100 lb. xanthate) (day)

10.4 lb. sol'n.

i.g.IX .. ..

0.10 lb. xanthate

024 lb. carbon disulfide" )( (. i"),!,,,,""ii~' ,O;, '..'::

lb. decomposed

= 0.7 carbon disulfide per day

Table 2 summarizes the maximum amount of carbon disul-fide released per day by 10% and 25% solutions of xanthateproducts. On forming. some of the carbon disulfide willdecompose to carbonate and thiocarbonate salts. Some ofthe remainder will evaporate and the rest will buildup in thexanthate solution until its solubility is exceeded when it willform a separate layer. This layer could also contain somexanthate and some alcohol. anotherdecomposition product.

17

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The separate layer will form below the xanthate solution inAERO 325. and 343 Xanthates. It may accumulate in deadspaces such as the bottom of a storage tank or. with theproper piping arrangement. it can be purged continuouslyinto the flotation circuit. However. the separate layer willform above the xanthate solution in AERO 317.350. and 355Xanthates. and present a serious fire hazard unless thestorage tank is properly vented (see Safety Precautions.page 31).

18

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DECOMPOSITION OFAERO 317 Xanthate

SOLUTIONS

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FIGURE 11


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FIGURE 12


SOLUTIONS

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20

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0

23

D. Determination of Active Xanthate in XanthateSolutions by the Acetone Method

1. Apparatus

Fisher Vacuum Filtrator (tall-form) equipped with a longstem funnel and Witt plate

A source of heat maintained between 45° C and 55° C(hot plate or water bath)

1-25-ml. Pipette2-50-ml. Burettes1 - 2So-ml. Erlenmeyer Flask with Stopper1 - 250-ml. Volumetric Flask2-150-ml. Beakers1 - Transfer FunnelGlass Stirring Rods

2. Reagents

Hydrochloric Acid-O.1N StandardSodium Hydroxide - O. 1 N StandardAcetone (Dry)Methyl Red Indicator-O.2% AqueousAqueous slurry of long fiber asbestos

3. Procedure

Weigh an 8-gram sample to the nearest milligram. Keepingthe volume to approximately 10Q-ml., wash the sample into a250-ml. Erlenmeyer flask with acetone. Stopper the flaskand shake and allow the sample to stand for at least fiveminutes.

In the meantime, prepare an asbestos pad on the Witt plateof the filtrator funnel. Carefully wash the asbestos first withdistilled water and then with acetone under vacuum. Discardall washings.

The same asbestos pad can be reused several times bywashing with hot water and then with acetone after eachtest.

24

Filter the sample into a clean, dry 2So-ml. volumetric flaskunder vacuum in the filtrator assembly. Rinse the sides ofthe Erlenmeyer flask and funnel and the Witt plate withacetone, allowing the filtrate to mix with the sample solution.Dilute to mark with acetone and mix thoroughly.

Add 35-ml. O.1N HCI to each of two 150-ml. beakers.

Pipette a 25-ml. aliquot of the sample solution to one of thebeakers. Place both beakers in a bath maintained between45°C-55°C for 15 minutes. with occasional agitation.Remove the beakers and allow the contents to cool to roomtemperature. Add 2 to 3 drops of methyl red indicator andtitrate to an orange-yellow endpoint with O.1N sodiumhydroxide.

4. Calculations

Net Titer = mi. of 0.1 N NaOH required for blank0.1 N NaOH required for sample

mi. of

Net Titer X N of NaOH X M.W. X 100

Sample Weight% Xanthate =X 25 X 1000

250

Molecular Weights of Xanthates

172.3 for AERO 317 Xanthate144.2 for AERO 325 Xanthate158.2 for AERO 343 Xanthate202.4 for AERO 350 Xanthate

25

HANDLING SHIPMENTS

Equipment Required for Handling SpargerCar/Truck Shipments of Solid Xanthates

A.

The solid xanthate is shipped in tank cars or tank trucks. Thecars usually contain two compartments with 40M lb. percompartment or four compartments with 20M. lb. percompartment. Tank truck shipments can contain up to 40Mlb.

For dissolution of the xanthate in the shipment, the follow-ing equipment is required.

.1 storage tank (for size required see page 4)

1 pump (SRL centrifugal pump 2" x 3" is satisfactory)

water supply

low pressure steam supply to maintain dissolution tem-perature in winter

flexible hose with quick coupling connections.

Carbon steel is adequate for the storage tank, all piping andthe pump. The flexible hose can be made of rubber. Copperand brass are not recommended for xanthate service.

26

Procedure for DissolutionB.

1. With the tank carltruck connected up as in Figure 13. addthe required amount of water to the storage tank. Therequired amount of water to make 10% and 25% solutionstrengths can be obtained from Figure 14. All xanthatesabsorb heat during dissolution so, to achieve rapiddissolution, the water used should be preheated. However.high temperatures (>210 C) should be avoided to limitdecomposition. The sodium xanthates heat up in thepresence of small quantities of water due to the formationof hydrates and some decomposition could occur; thiscan be avoided by adding the water for dissolution rapidly.

2. Pump water into the tank car/truck and overflow back tothe storage tank. The tank car/truck is now under pressure(see note below).

3. Recirculate until xanthate is all dissolved, which can bechecked by specific gravity measurements in tankcar/truck and storage tank.

It is imperative that the safety valve on the tankcompartment be in working order when the xan-thate is being dissolved and that pressure setting ofthis valve not be over 15 p.s.i.g. Normally, while thetank car/truck is in transit, the safety valve isinactivated and must be reactivated before thedissolving operation is commenced.

NOTE:

Procedure for Final Unloading

Connect the tank car/truck drain nozzle to the pum p suction(Figure 13) and pump the solution into the storage tank.

.

.

. 27

FIGURE 13

EQUIPMENT SETUP FOR DISSOLVING & UNLOADINGBULK XANTHATES

Water

RECIRCULATION AND DISSOLVING

UNLOADING

28

FIGURE 14

WATER REQUIRED TO PREPARE 10%AND 25% AERO Xanthate SOLUTIONS

80

70

60

50

40

30

20

10

. 0

40 50 6010 20 30

29

FIGURE 15

WATER REQUIRED TO PREPARE10% and 25% AERO Xanthate SOLUTIONS

80

70

60

10%25%

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10 Water RequiredU.S. Gallons in Thousands

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30

..."CC~~0

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SAFETY DISCUSSION

A. General

Solid xanthates are stable for months when kept cool anddry. The ignition temperature of dry solid xanthates is in the250°C range. However, upon exposure to moisture and/orheat, decomposition results and spontaneous combustioncan occur. Heat generated by hydration and/ordecomposi-tion may raise the temperature to the auto-ignition point ofthe decomposition product, carbon disulfide (100°C).Occasionally, material in punctured drums has ignited dueto circulation of moist air through the pelletized mass. In theevent of ignition, the fire may be extinguished with water.

Freshly-prepared xanthate solutions do not normally exhibita flash point by standard methods until heated to a point,well above room temperature, where decomposition israpid. However, since xanthates decompose in solution,even at room temperature, hazards develop with aging. Themain hazards are due to the decomposition product carbondisulfide (see page 16).

Pertinent properties and characteristics of carbon disulfideare:

Liquid100°C1% to 50% by volume in air-30° CClear, ColorlessOdorless when pure0.210

Physical StateAuto-Ignition TemperatureFlammable LimitsFlash PointColorOdorSolubility in water, % C~

in water @ 20° CSpecific Gravity

@ 20°C/4°CVapor Pressure @ 28° C

1.263

400 mm Hg (about 4 timeshigher than acetone)

20 ppm or 60 mg/M3Threshold limit

a

~31

I

Safety Precautions in HandlingB.

To avoid any problems with xanthate and its decompositionproducts, the following precautions are recommended.

1. Keep solid xanthates dry and reasonably cool.

2. Limit xanthate dusting as much as possible.

3. Maintain xanthate solutions at as Iowa temperature as

practical.

4. Before pumping xanthate solution from one vessel toanother. make sure that all vessels and equipment areproperly grounded or bonded to avoid buildup of staticelectricity.

5. Add the water as quickly as possible when dissolvingsolid xanthate.

6. When draining the tank car/truck, drain from the lowestpoint. This will allow continuous drainage of any separatecarbon disulfide layer below the xanthate solution. Forthe same reason, the solution storage, mixing and millhead tanks should have sloping bottoms and should bedrained from their lowest points. If the latter is notpossible a syphon should be installed to remove anyseparate layer. Unless the layer is continuously removedinto the flotation circuit it must be collected under ablanket of water.

7. The vapor space in a storage tank should have a forcedexhaust or purge to atmosphere to prevent any buildupof carbon disulfide to the explosive limits (1% to 50% inair). If possible. the vapor space should be checkedregularly with an explosimeter.

8. Before returning the empty truck, flush out any remaining

32

xanthate solution with water. Allow enough space in thexanthate storage tank to take care of the water flush.

9. The xanthate storage tank and immediate area must befree from any source of ignition. as contact of carbondisulfide vapors with any surface above 1000 C. will causeignition. Only explosion proof classified light fixtures,conduit, and motors should be used. Smoking must beprohibited and non-sparking tools should be used whenopening drums or working on a tank or tank/truck inxanthate service.

10. No maintenance work should be performed on a xanthatestorage tank or pipe lines leading to or from the tankwithout first thoroughly washing the tank and pipe linesto remove any sludge. This applies especially to all hotwork including soldering, brazing, welding, heating andburning. An explosive test must be taken prior to any hotwork.

11. Wear eye protection (goggles and face shield) whenworking directly with xanthate solution. Rubber glovesshould also be worn when working with these solutions.

12. Solutions of xanthate in sufficient quantity and concen-tration may be harmful to fish and other aquatic life.Therefore, no solutions of xanthate should be dischargedinto any well, lake. river, pond, spring, reservoir. or otherwatercourse.

33

C. Medical Management

Solutions of xanthate may cause a mild to severe irritation ofskin and eye. Prolonged or repeated skin contact andsplashes of the product near or into the eyes should beavoided.

I n case of contact of solutions with the eyes, the eyes shouldbe flushed immediately with plenty of water for at least 15minutes, and a physician should be called. Spills on the skinshould be washed off promptly with water.

34

VANCOUVER, B.C.602 West Hastings StV68 1P2(604) 682-3891

CYANAMID CANADA, INC.ONT ARlO2255 Sheppard Ave. EastWillowdaleM2) 4Y5(416) 498-9405

SALES OFFICES

MONTREAL TORONTO19,400 Trans-Canada 2031 Kennedy Road

Highway Scarborough,Baie d'Urfe, Quebec Onto M1P 2M4H9X 3N7 (416) 293-8181(514) 457-2110

AMERICAN CYANAMID COMPANY

INDUSTRIAL PRODUCTS DIVISION

MINING CHEMICALS

WAYNE, NEW JERSEY 07470One Cyanamid Plaza(201) 831-2000

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TUCSON, ARIZONA 857452002 N. Forbes Blvd.,Suite 103(602) 624-0496

CYANAMID INTERNATIONAL DIVISIONS

CHEMICALS DEPARTMENTONE CYANAMID PLAZA

WA YNE. NEW JERSEY 07470

SALES OFFICES

CYANAMID AMERICAS/FAR EAST CYANAMID (F~r East) ltd.

CYANAMID AUSTRALIA PTY. LW. Office of the RepresentativeP.O. Box 584 l/F., Inchcape HouseCrows Nest 450 Alexandra RoadNSW 2065, Australia Pasir Panjang

Singapore 0511

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klMBROS CO.C.P.O. Box 3483Seoul, Korea

f UROPf/MIDfAST / AiR ICACYANAMID TAIWAN CORPORATION

P.O. Box 1057Taipei, TaiwanRepublic of China

CYANAMID s.A.74, Rue 0' Arcueil, Silic 27594578 Rungis Cedex, France

SOUTH AFRICAN CYANAMID PTY. LW.P.O. Box 7552Johannesburg 2{XK)Republic of South Africa

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CYANAMID DE ARGENTINA, s.A.Charcas 5051-63Buenos Aires, Argentina

CYANAMID QUIMICA DO BRASILLWA.Caixa Postal 10392O.<XX> Rio de JaneiroR.J., Brazil

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CYANAMID NORDISKA ABArchimedesvagen 45-161 70 Bromma, Sweden

CYANAMID INTERNATIONAL CORP.Zurichstrasse 12CH-8134 AdliswilSwitzerland

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This information is not to be taken as a warranty or representation forwhich we assume legal responsibility nor as permission. inducement orrecommendation to practice any patented invention without a license.The information is offered solely for your consideration, investigationand verification.

MC1 206 Rev. 3/82MC42A 215113/82PrWited in U.S.A.

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AERO XANTHATE PRODUCTS