Preparation of borohydride salts

Abstract

A method for preparing a metal borohydride salt, M(BH4)n, where n is 1 or 2, from a slurry of sodium borohydride and a sodium alkoxide in a liquid hydrocarbon, wherein M is Li, K, Rb, Cs, Mg, Ca, Sr or Ba.

Description

DETAILED DESCRIPTION

Unless otherwise specified, all percentages herein are stated as weight percentages and temperatures are in 0° C.

In one embodiment of the invention, the metal, M, is Li, K, Ca, Sr or Ba. In a preferred embodiment of the invention, M is K. In one embodiment of the invention, the anion, X, in the metal salt is alkoxide, chloride, bromide or iodide. In a preferred embodiment of the invention, X is chloride or alkoxide. Particularly preferred metal salts include potassium methoxide, potassium chloride, calcium chloride, strontium chloride and barium chloride.

The liquid hydrocarbon used in the present invention is any hydrocarbon which is liquid at 25° C. Suitable hydrocarbons include alkanes, e.g., mineral oil; and aromatics. Mineral oil is particularly preferred. Preferably, the amount of liquid hydrocarbon is from 0.01 L/g NaBH₄ to 10 L/g NaBH₄, alternatively from 0.2 L/g NaBH₄ to 1 L/g NaBH₄.

In one embodiment of the invention in which X is an alkoxide, the alkoxide is a C₁-C₁₂ alkoxide, alternatively a C₁-C₈ alkoxide, alternatively a C₁-C₄ alkoxide. In one preferred embodiment, the alkoxide is methoxide, ethoxide, isopropoxide or t-butoxide. Methoxide is particularly preferred. Alkoxides can be generated from hydroxides and alcohols.

In one embodiment of the invention, the amount of metal salt used is from 0.995 to 1.005 equivalents with respect to the amount of sodium borohydride in the slurry, alternatively about one equivalent. In one embodiment of the invention, the sodium alkoxide and sodium borohydride in the slurry are in a molar ratio of about 3:1, alkoxide:borohydride.

For the case where M is a monovalent metal (n=1), and sodium alkoxide and sodium borohydride in the slurry are in a molar ratio of about 3:1, alkoxide:borohydride, an equation describing the reaction is as follows:

3NaOR+NaBH₄+MX→MBH₄+NaX+3NaOR

MBH₄ is insoluble in the methanol/hydrocarbon reaction medium, and thus will form a precipitate. NaX may also be insoluble, depending on the nature of X. In cases where NaX is soluble, the MBH₄ can be isolated by filtration, with the filtrate containing a hydrocarbon phase, and a methanol/NaX phase. When M is divalent (n=2) and X is chloro, the reaction is as follows:

6NaOR+2NaBH₄+MCl₂→M(BH₄)₂+2NaCl+6NaOR

In this case, both M(BH₄)₂ and NaCl are insoluble. NaCl can be removed from the metal borohydride by washing the solids with water.

Preferably, the reaction temperature is from 0° C. to 50° C., alternatively from 15° C. to 40° C. Preferably, the amount of methanol added is from 10 g/g NaBH₄ to 50 g/g NaBH₄, alternatively from 12 g/g NaBH₄ to 30 g/g NaBH₄.

EXAMPLES

Preparation of KBH₄ (KBH)—A two liter three neck flask equipped with an overhead stirrer, thermometer, liquid addition funnel and nitrogen purge was charged with 658.2 grams of a mineral oil slurry containing 20.2% NaOCH₃ and 4.6% NaBH₄. The addition funnel was charged with a solution of 49.01 g of solid KOH and 406.1 g of methanol. This material was added to the stirred slurry at a rate such that the reaction temperature of the slurry did not rise above 40° C. The consistency of the reaction slurry changed from a free flowing slurry to a clumpy dough material to a partial three-phase system. An addition 400 g of methanol was added, resulting in a three-phase system having two liquid phases and a white powdery solid in the top layer.

This three-phase slurry was initially filtered through a grade “B” ultra-coarse glass frit (70-100 μm) but no solids were caught by the filter. The slurry was then passed through a grade “E” extra-fine glass frit (2 to 8 μm). This filtration was done under a dynamic oil pump vacuum. The resulting solid was washed multiple times with 742 grams of hexane and the resulting solid was dried under vacuum at room temperature. The resulting two liquids were separated using a separatory funnel. T

he two liquids and solids were analyzed for % NaOCH₃ (NaOMe), % KBH, % NaOH, % oil and by ICP analysis.

TABLE 1
Analysis of product from KOH in methanol
			CH3OH
	Solids g,	Oil Layer	Layer g,
	(yield)	g (yield)	(yield)	Recovery
Wt	46.31	525.24	658.2
sample(g)
% KBH	86.21, 86.25	0.0	0.35, 0.34
ICP, Na	4.34%	29 ppm	10.14%
ICP, K	61.46	2.6 ppm	967 ppm
ICP, B	19.42	4.4 ppm	937 ppm
% NaOMe/	N/A	0.0	26.19.26.13
total
alkalinity
% NaOH	7.52, 7.52
% Oil	1964 ppm	N/A	1184 ppm
Grams KBH	39.82		2.30 g	42.12/48.50 =
	(82.1%)			86.85
Grams Oil		525.24		525.24/553 =
				94.89
Grams	4.63		172.11	176.74/198.94 =
NaOMe/total			( 86.5%)	89.26
alkalinity

These results demonstrate that KBH and NaOMe both can be isolated with good purity and yield, especially with regard to K contamination in NaOMe.

TABLE 2
Analysis of product from KOCH3/methanol
			CH3OH
	Solids g,	Oil Layer g	Layer g,
	(yield)	(yield)	(yield)	Recovery
Wt sample(g)	55.44	408.82	700.51
% KBH	75.422	0.014	0.341
ICP, Na	—	—	—
ICP, K	—	—	—
ICP, B	—	—	—
% NaOMe/		0	23.060
total
alkalinity
% NaOH	16.403	0
% Oil	—	N/A	—
Grams KBH	41.814	0	2.38	44.19/46.75 =
	(89.43%)			94.52
Grams Oil		530.82		530.82/533.76 =
				99.45
Grams	9.31		165.32	174.63/191.55 =
NaOMe/total			(86.30%)	91.17
alkalinity

Claims

1. A method for producing a metal borohydride, M(BH4)n, where n is 1 or 2, from a slurry of sodium borohydride and a sodium alkoxide in a liquid hydrocarbon; said method comprising steps of: (a) combining said slurry with 0.99 to 1.01 equivalents of a metal salt, M(X)n, and methanol, wherein M is Li, K, Rb, Cs, Mg, Ca, Sr or Ba; and X is halide, alkoxide or acetate;(b) filtering to collect M(BH4)n; and(c) separating oil and methanol liquid phases to obtain sodium methoxide in methanol solution.

2. The method of claim 1 in which M is K.

3. The method of claim 2 in which X is alkoxide.

4. The method of claim 3 in which alkoxide is C1-C4 alkoxide.

5. The method of claim 4 in which the liquid hydrocarbon is mineral oil.

6. The method of claim 1 in which X is alkoxide.

7. The method of claim 6 in which M is K.

8. The method of claim 1 in which X is Cl, Br or I.

9. The method of claim 8 in which M is K and X is Cl.

10. The method of claim 9 in which the liquid hydrocarbon is mineral oil.