Boron extraction

This element is widely employed in the production of glass and glass fibers, fluxes, antiseptics, and other products. Boron compounds are also widely used in nuclear technology [264]. Boron is an element that occurs at a relatively high concentration level in seawater (4.5 mg/L). Yet, economically acceptable processes for boron extraction from the sea do not exist, despite the fact that methods for its recovery from highly mineralized brines have been available since the beginning of the 1960s [253]. With the development of such methods, attempts were made to determine the lowest concentration levels of the element, at which economical processes could be developed [256, 266]. This critical concentration of boron was at that time estimated to be around 20 mg/L. Currently, the critical concentration of boron is estimated to be 15 mg/L or even somewhat less. 

In this chapter, we review the achievements in the area of extractions with boron extractants accomplished in the last five years. The literature on extraction with cobalt bis(dicarbollide) and synergist, the UNEX process, and new boron-selective extractants is ample, and other connected science, such as ion-selective electrodes with boron anions, boron anion room-temperature ionic liquids, modeling of the mechanism of the extraction, IR studies on extracts, the state of CD in water solutions, or a description of some of the new ideas on solvation, resolvation theory, and so on, could not be covered here. 

Brine and Product Analyses of a Boron Extraction Process with Lithium Chloride Crystallization (Brown... 

Boron extraction with four parts of 20% isooctanol in kerosene to one part of brine, and four mixer-settler stages. 

Figure 1.70 Second view of SQM s lithium carbonate plant. Processing building to the right boron extraction to the left (courtesy of SQM SA).

Isotherms at 25°C for Boron Extraction from Salar de Atacama Brine, and Re-extraction in Water... 

Figure 1.71 The rate of extraction and solvent washing, and the density and viscosity of strong lithium chloride brine before and after boron extraction (Orrego et al, 1994 reprinted courtesy of Nucleotecnica).

A solution of 6-bromoindole (O.lOmol) in toluene (200 ml) was treated with Pd(PPh3)4 (5mol%) and stirred for 30 min. A solution of 4-fluorophenyl-boronic acid (0.25 M, 0.15 mol) in abs. EtOH was added, followed immediately by sal aq. NaHCOj (10 eq.). The biphasic mixture was refluxed for several hours and then cooled to room temperature. The reaction mixture was poured into sat. aq. NaCl (200 ml) and the layers separated. The aq. layer was extracted with additional EtOAc (200 ml) and the combined organic layers dried (Na2S04), filtered and concentrated in vacuo. The solution was filtered through silica gel using hexane-CHjCl -hexanc for elution and evaporated. Final purification by recrystallization gave the product (19 g, 90%). 

The chain-growth catalyst is prepared by dissolving two moles of nickel chloride per mole of bidentate ligand (BDL) (diphenylphosphinobenzoic acid in 1,4-butanediol). The mixture is pressurized with ethylene to 8.8 MPa (87 atm) at 40°C. Boron hydride, probably in the form of sodium borohydride, is added at a molar ratio of two borohydrides per one atom of nickel. The nickel concentration is 0.001—0.005%. The 1,4-butanediol is used to solvent-extract the nickel catalyst after the reaction. 

Occurrence. Brine found in Seades Lake, California is the only brine source where boron is produced commercially. Other brine bodies such as the Great Salt Lake or brine from thermal weUs at the Salton Sea have been considered but have not been exploited. Brines at the Salar de Atacama in Chile also contain boron, but it is not presently extracted. 

Recovery Process. Boron values are recovered from brine of Seades Lake by North American Chemicals Corp. In one process the brine is heated to remove some water and burkeite. The remaining brine is cooled to remove potassium chloride. This cooled brine is then transferred to another crystallizer where borax pentahydrate, Na2B40y 5H20, precipitates (18). In a separate process, boron is removed by Hquid—Hquid extraction followed by stripping with dilute sulfuric acid (19). Evaporator-crystallizers are used to recover boric acid [10043-35-3] H BO. In a third process, borax is recovered by refrigerating a carbonated brine. 

Homoallyl alcohol (3) Metalation of (E) butene (1 05 equiv) with n BuLI (t equiv) and KOtBu (1 equiv) in THF at SO C for 15 mm followed by treatment of (E)-crotyl potassum salt with B(OiPr)3 at 79°C gave after quenching with 1 N HCI and extraction with EtjO containing 1 equiv of diisopropyl tartarate. the crotyl boronate 2 A solution of decanall (156 mg 1 mmol) was added to a toluene solution of 2 (1 1 15 equiv) (0 2 M) at 78 C containing 4A molecular sieves (15-20 mg/L) After 3 h at -78°1 N NaOH was added, followed by extraction and chromatography to afford 208 mg of 3 (90%), anti syn 99 1... 

Core damage can result most likely from heat imbalance. Figure 6.3-3 is an example from the Indian Point PRA that uses heat imbalance to approach completeness. This diagram shows that cote damage may result from either a loss of cooling or excess power (or both). The direct causes of insufficient heat removal may be loss of flow, makeup water, steam flow, or heat extraction by the turbine. Indirect causes are reactor trip or steam line break inside or outside of containment. Cau.ses of excess power production are rod withdrawal, boron removal, and cold water injection. 

A suspension of lithium aluminum deuteride (1.6 g) in dry tetrahydrofuran (60 ml) is added dropwise to a stirred and cooled (with ice-salt bath) solution of 5a-androst-l4-ene-3j3,17j3-diol (179, 1.6 g) and boron trifluoride-etherate (13.3 g) in dry tetrahydrofuran (60 ml). The addition is carried out in a dry nitrogen atmosphere, over a period of 30 min. After an additional 30 min of cooling the stirring is continued at room temperature for 2 hr. The cooling is resumed in a dry ice-acetone bath and the excess deuteriodiborane is destroyed by the cautious addition of propionic acid. The tetrahydrofuran is then evaporated and the residue is dissolved in propionic acid and heated under reflux in a nitrogen atmosphere for 8 hr. After cooling, water is added and the product extracted with ether. The ether... 

Bromo-4-methoxy-A-homo-estra-2,4,5(10)-trien-17-one (44 0. 2g), is dissolved in formic acid, 2 ml of boron trifluoride etherate is added and the mixture is stirred vigorously at 0° for 2 hr. A brown mass ca. 0.12 g) is obtained after evaporation of the solvents at reduced pressure. This material is diluted with water and extracted with chloroform. The chloroform extracts are washed successively with water and saturated salt solution, dried over anhydrous magnesium sulfate and evaporated at reduced pressure to give 95 mg of a product which is purified by filtration through a column of neutral alumina and crystallization of the residue after evaporation of the solvent from ethyl acetate-petroleum ether. The resulting A-homo-estra-l(10),2,4a-triene-4,17-dione (45), mp 143-146°, is identical to the tropone (45) prepared from monoadduct 17-ketone (43a). 

The usefulness of the bond density surface is more apparent in the following model o diborane. The surface shows that diborane is not flat. It also shows that there is relatively little electron density between the two borons. Apparently there is no boron-boron bonr in this molecule. This is information that we can extract from the bond density surfact model. We do not have to assume this information in order to construct a model. We would need it in order to construct a conventional model. 

A solution of 3 g of the nitrile, water (5 moles per mole of nitrile), and 20 g of boron trifluoride-acetic acid complex is heated (mantle or oil bath) at 115-120° for 10 minutes. The solution is cooled in an ice bath with stirring and is carefully made alkaline by the slow addition of 6 A sodium hydroxide (about 100 ml). The mixture is then extracted three times with 100-ml portions of 1 1 ether-ethyl acetate, the extracts are dried over anhydrous sodium sulfate, and the solvent is evaporated on a rotary evaporator to yield the desired amide. The product may be recrystallized from water or aqueous methanol. Examples are given in Table 7.1. 

Step 1 1-(p-Chlorophenyl)-3-Ethoxy-1 H-lsoindole - Crystalline triethyloxonium boron-tetrafluoride (21 g) (prepared from 23 g of borontrifluoride etherate and 11 g of epichlorohydrin) is dissolved in 100 ml of absolute methylenechloride. 3-(p-Chlorophenyl) phthalimidine (21 g) is added and the reaction mixture is stirred overnight at room temperature. The resulting solution is poured onto 50 ml of saturated Sodium carbonate, extracted with 500 ml of ether and dried. Upon evaporation of the solvent there is obtained crude material which is recrystallized from methylene chloride/hexane (1 1) to yield l-(p-chlorophenyl)-3-ethoxy-1 H-isoindole MP 102° to 103°C. 

The following procedure is given in U.S. Patent 3,458,528 78 grams (0.675 mol) of 5-nitroimidazole is dissolved in 1,500 ml of acetic acid upon the addition of 72 ml (0.57 mol) of boron trifluoride etherate. 175 ml (3.5 mols) of ethylene oxide in 175 ml of hexane, in a dropping funnel topped with a cold finger, is added slowly over 1 hour to the above solution maintained at 32° to 35°C with a water cooling bath. The mixture is concentrated under high vacuum to 100 to 150 ml volume. The residue is diluted with 500 ml of water, neutralized to pH 7 with aqueous sodium hydroxide, and extracted with 1.5 liters of ethyl acetate. The extract is dried and evaporated to yield 1-(2 -hydroxyethyl)-5-nitroimidazole. 

Ethyl-2-methyl-3-(10,11) -dihydro-5H-dibenzo [a,d] cycloheptene-5-ylidene)-1 -pyrrolinium iodide (4.7 g) was dissolved in 7 cc of methanol. To this solution there were added 1.4 g of sodium boron hydride within about 80 minutes with stirring and stirring of the solution was continued for two hours to complete the reaction. The reaction mixture was acidified with 10% aqueous hydrochloric acid solution and then the methanol was distilled off. The residual solution was alkalized with 20% aqueous sodium hydroxide solution and extracted with ether. The ether layer was dried over magnesium sulfate and the ether was distilled off. The resulting residue was further distilled under reduced pressure to yield 2.0 g of 1-ethyl-2-methyl-3-(10,11 ) dihydro-5H-dibenzo[a,d]cycloheptene-5-ylidene)pyrrolidine (boiling point 167°C/4 mm Hg.). 

Discussion. The method is based upon the complexation of boron as the bis(salicylato)borate(III) anion (A), (borodisalicylate), and the solvent extraction into chloroform of the ion-association complex formed with the ferroin. 

The intensity of the colour of the extract due to ferroin is observed spectrophotometrically and may be related by calibration to the boron content of the sample. 

The method has been applied to the determination of boron in river water and sewage,16 the chief sources of interference being copper(II) and zinc ions, and anionic detergents. The latter interfere by forming ion-association complexes with ferroin which are extracted by chloroform this property... 

To a stirred — 78 C solution of 5.85 mL (62.5 mmol) of 3-methoxy-l-prnpene in 25 mL of THf- are added 43.1 mL (50 mmol) of 1.16 M. vcc-butyllithium in cyclohexane over a 20-25 min period. The mixture is stirred at — 78 °C for an additional 10 min, and diisopinocampheyl(methoxy)borane [50 mmol prepared from (+ )-a-pinene] in 50 mL of THF is added. This mixture is stirred for 1 h, then 8.17 mL (66.5 mmol) of boron trifluoride diethyl etherate complex are added dropwise to give a solution of diisopiuocampheyl[(Z)-3-inethoxy-2-propenyl]borane. Immediately. 2.8 mL (50 mmol) of acetaldehyde are added and the mixture is stirred for 3 h at — 78 rC and then allowed to warm to r.t. All volatile components are removed in vacuo, then the residue is dissolved in pentane. The insoluble fraction is washed with additional pentane. The combined pentane extracts are cooled to 0 JC and treated with 3.0 mL (50 mmol) of ethanolamine. The mixture is stirred for 2 h at 0rC and is then seeded with a crystal of the diisopinocampheylborane-ethanolaminc complex. The resulting crystals arc filtered and washed with cold pentane. The filtrate is carefully distilled yield 5.6 g (57%) d.r. (synjanti) >99 1 (2/ ,37 )-isomer 90% ee bp 119-120 C/745 Torr. 

IA solution of the allylsilane (2 mmol) in chloroform (2 ml) was added all at lonce to boron trifluoride-acetic acid complex (2.2 mmol) with vigorous Ishaking until a single phase resulted. After 5 min, the solution was poured linto saturated sodium hydrogen carbonate solution (10ml) and extracted... 

---