Antimony removal

Fischer, J. Lusk, L. Hinkley, D. Dowd, M. Boske, G. Plott, M. Mofiitt, J. Reliability assessment of antimony removal from Sn-Pb solders. Proc. Natl. Electron. Packag. Prod. Conf. 1992, 2, 1056. 

Crude lead contains traces of a number of metals. The desilvering of lead is considered later under silver (Chapter 14). Other metallic impurities are removed by remelting under controlled conditions when arsenic and antimony form a scum of lead(II) arsenate and antimonate on the surface while copper forms an infusible alloy which also takes up any sulphur, and also appears on the surface. The removal of bismuth, a valuable by-product, from lead is accomplished by making the crude lead the anode in an electrolytic bath consisting of a solution of lead in fluorosilicic acid. Gelatin is added so that a smooth coherent deposit of lead is obtained on the pure lead cathode when the current is passed. The impurities here (i.e. all other metals) form a sludge in the electrolytic bath and are not deposited on the cathode. 

The gas is washed with water to remove any hydrogen chloride. Since iron(II) sulphide is a non-stoichiometric compound and always contains some free iron, the hydrogen sulphide always contains some hydrogen, liberated by the action of the iron on the acid. A sample of hydrogen sulphide of better purity can be obtained if antimony(III) sulphide, (stibnite) SbjSj, is warmed with concentrated hydrochloric acid ... 

Properties. Antimony pentafluoride [7783-70-2], SbF, is a colorless, hygroscopic, very viscous liquid that fumes ia air. Its viscosity at 20°C is 460 mPa-s(=cP) which is very close to the value for glycerol. The polymerization of high purity SbF at ambient temperature can be prevented by addition of 1% anhydrous hydrogen fluoride, which can be removed by distillation prior to the use of SbF. The pure product melts at 7°C (11), boils at 142.7°C,... 

Ethylene glycol esterification of BHET is driven to completion by heating and removal of the water formed. PET is also formed using the same chemistry starting with dimethyl terephthalate [120-61-6] and ethylene glycol to form BHET also using an antimony oxide catalyst. 

Commercial Stabilizers. The performance of the antimony stabilizers is significantly enhanced by adding polyhydroxybenzene compounds, eg, catechol, to the PVC (36). In commercial practice, about 5—10% catechol is formulated with the antimony mercaptide stabilizer products. The antimony mercaptides are normally prepared by heating antimony oxide with the appropriate mercaptan, normally isooctyl thioglycolate, under conditions to remove water. 

Two methods are used to measure pH electrometric and chemical indicator (1 7). The most common is electrometric and uses the commercial pH meter with a glass electrode. This procedure is based on the measurement of the difference between the pH of an unknown or test solution and that of a standard solution. The instmment measures the emf developed between the glass electrode and a reference electrode of constant potential. The difference in emf when the electrodes are removed from the standard solution and placed in the test solution is converted to a difference in pH. Electrodes based on metal—metal oxides, eg, antimony—antimony oxide (see Antimony AND ANTIMONY ALLOYS Antimony COMPOUNDS), have also found use as pH sensors (8), especially for industrial appHcations where superior mechanical stabiUty is needed (see Sensors). However, because of the presence of the metallic element, these electrodes suffer from interferences by oxidation—reduction systems in the test solution. 

If antimony and arsenic are present ia the feed, copper and iron react to form the respective antimonides and arsenides known as speiss (specific gravity 6.0). If it is preferred to remove copper ia a speiss layer, the sulfur ia the siater must be reduced and the addition of scrap iron may be necessary to encourage speiss formation. Matte and speiss are usually sent to a copper smelter for recovery of the metals. 

Removal by Oxidation. The oxidizing process used to remove antimony, arsenic, and tin has been termed softening because lowering these impurities results in a readily detectable softening of the lead. 

The softening of a high hardness charge (3% or greater) follows the same procedure, except that after the first slag is removed, Htharge, ie, PbO, is added to hasten the reduction of the hardness to 0.5%. The bath is then blown with air to a concentration of 0.03% antimony. 

The niter and fresh caustic soda, required to maintain the fluidity of the salt bath in the reactor chamber, are added gradually. When the color of the saturated salts turns from a dark gray to white, the impurity metals are at their highest state of oxidation, and the lead content of the spent salts is very low. In a modification, the arsenic and tin are selectively removed as sodium arsenate and sodium stannate, followed by the removal of antimony as sodium antimonate. 

After firing, the powder is washed in water typically with a small amount of complexing agent such as ethylenediarninetetraacetic acid (EDTA), sodium EDTA, or a weak acid such as citric acid to remove the excess chloride, volatile antimony oxychlorides which have recondensed on the phosphor during cooling, and manganese compounds which are not incorporated in the halophosphate lattice. The powder is then ready for suspension. 

Metals less noble than copper, such as iron, nickel, and lead, dissolve from the anode. The lead precipitates as lead sulfate in the slimes. Other impurities such as arsenic, antimony, and bismuth remain partiy as insoluble compounds in the slimes and partiy as soluble complexes in the electrolyte. Precious metals, such as gold and silver, remain as metals in the anode slimes. The bulk of the slimes consist of particles of copper falling from the anode, and insoluble sulfides, selenides, or teUurides. These slimes are processed further for the recovery of the various constituents. Metals less noble than copper do not deposit but accumulate in solution. This requires periodic purification of the electrolyte to remove nickel sulfate, arsenic, and other impurities. 

In metallurgical practice, sodium uses include preparation of powdered metals removal of antimony, tin, and sulfur from lead modification of the stmcture of siHcon—aluminum alloys appHcation of diffusion alloy coatings to substrate metals (162,163) cleaning and desulfurizing alloy steels via NaH (164) nodularization of graphite in cast iron deoxidation of molten metals heat treatment and the coating of steel using aluminum or zinc. 

Purification. Tellurium can be purified by distillation at ambient pressure in a hydrogen atmosphere. However, because of its high boiling point, tellurium is also distilled at low pressures. Heavy metal (iron, tin, lead, antimony, and bismuth) impurities remain in the still residue, although selenium is effectively removed if hydrogen distillation is used (21). 

In hquidation, tin is heated on the sloping hearth of a small reverberatory furnace to just above its melting point. The tin mns into a so-called poling ketde, and metals that melt sufficiently higher than tin remain in the dross. Most of the iron is removed in this manner. Lead and bismuth remain, but arsenic, antimony, and copper are partly removed as dross. 

Iron, copper, arsenic, and antimony can be readily removed by the above pyrometaHurgical processes or variations of these (3). However, for the removal of large quantities of lead or bismuth, either separately or together, conventional electrolysis or a newly developed vacuum-refining process is used. The latter is now in use in Austraha, BoHvia, Mexico, and the CIS (5). 

AHoy scrap containing tin is handled by secondary smelters as part of their production of primary metals and alloys lead refineries accept solder, tin drosses, babbitt, and type metal. This type of scrap is remelted, impurities such as iron, copper, antimony, and zinc are removed, and the scrap is returned to the market as binary or ternary alloy. The dross obtained by cleaning up the scrap metal is returned to the primary refining process. 

The standard chemical and biological methods of analysis are those accepted by the JnitedStates Pharmacopeia XXIII as well as the ones accepted by the AO AC in 1995 (81—84). The USP method involves saponification of the sample (dry concentrate, premix, powder, capsule, tablet, or aqueous suspension) with aqueous alcohoHc KOH solvent extraction solvent removal chromatographic separation of vitamin D from extraneous ingredients and colormetric deterrnination with antimony trichloride and comparison with a solution of USP cholecalciferol reference standard. 

The AO AC (978.42) recognizes a similar procedure, except that the unsap onitiable material is treated with maleic anhydride to remove the trans-isomer which may possibly be present (83). The antimony trichloride colorimetric assay is performed on the trans-isomer-free material. This procedure cannot be used to distinguish certain inactive isomers, eg, isotachysterol if present, these are included in the result, giving rise to a falsely high analysis. A test must therefore be performed to check for the presence of isotachysterol. 

Copper sulfate, in small amounts, activates the zinc dust by forming zinc—copper couples. Arsenic(III) and antimony(TTT) oxides are used to remove cobalt and nickel they activate the zinc and form intermetaUic compounds such as CoAs (49). Antimony is less toxic than arsenic and its hydride, stibine, is less stable than arsine and does not form as readily. Hydrogen, formed in the purification tanks, may give these hydrides and venting and surveillance is mandatory. The reverse antimony procedure gives a good separation of cadmium and cobalt. 

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