Title of Invention

"A SOLID COMPOSITION"

Abstract A solid composition comprising: (a) from 50% to 98% of at least one borohydride compound; and (b) from 2% to 50% of at least one base
Full Text BOROHYDRIDE FUEL FORMULATION
'"This invention relates to a solid borohydride-containing formulation useful
for hydrogen generation in fuel cells,
Borohydride-containing compositions are known as hydrogen sources for
hydrogen fuel cells, usually in the form of aqueous solutions. Solid borohydridecontaining
compositions also have been used. For example, U.S. Pub. No.
2005/0238573 discloses the use of solid sodium borohydride, which is combined
with aqueous acid to produce hydrogen. However, the problem of rapid
dissolution of borohydride is not addressed by this reference.
The problem addressed by this invention is to find a solid formulation of
borohydride that dissolves at least as quickly as pure borohydride salts.
STATEMENT OF INVENTION
The present invention provides a solid composition comprising: (a) from
50% to 98% of at least one borohydride compound; and (b) from 2% to 50% of at
least one base.
DETAILED DESCRIPTION
Percentages are weight percentages and temperatures are in °C, unless
specified otherwise. A "base" is a compound with a pKa>8 which is solid at 40°C.
A "borohydride compound" is a compound containing the borohydride anion,
BH4'.
In one embodiment, the amount of borohydride compound(s) is at least
75%, alternatively at least 83%, alternatively at least 85%, alternatively at least
86%, alternatively at least 87%; the amount of base(s) is no more than 25%,
alternatively no more than 17%, alternatively no more than 15%, alternatively
no more than 14%, alternatively no more than 13%. In one embodiment of the
invention, the amount of base is at least 2.5%, alternatively at least 3%,
alternatively at least 5%; the amount of borohydride compound is no more than
97.5%, alternatively no more than 97%, alternatively no more than 95%.
Preferably, the borohydride compound is a metal salt which has a metal cation
from groups 1, 2, 4, 5, 7, 11, 12 or 13 of the periodic table, or a mixture thereof.
In one embodiment, the borohydride compound is an alkali metal borohydride or
combination thereof, alternatively it comprises sodium borohydride (SBH) or
potassium borohydride or a mixture thereof, alternatively sodium borohydride.
Preferably, the base is an alkali metal hydroxide or combination thereof, alkali
metal alkoxide or alkaline earth alkoxide or combination thereof; alternatively it
is an alkali metal hydroxide or sodium or potassium methoxide, or mixture

thereof; alternatively sodium, lithium or potassium hydroxide or sodium or
potassium methoxide, or a mixture thereof; alternatively sodium hydroxide or
potassium hydroxide; alternatively sodium hydroxide. More than one alkali
metal borohydride and more than one base may be present.
The present invention is also directed to a method for rapid production of
an aqueous borohydride solution. Adding to water a sufficient amount of the
borohydride/base composition described above to form a 1% to 40% solids
solution produces a maximum dissolution rate. In one embodiment of the
invention, the solution has at least 5% solids, alternatively at least 10%; the
solution has no more than 35% solids, alternatively no more than 30%. The
water may contain small amounts of additives, e.g., anti-foaming agents,
surfactants, etc.
The present invention is further directed to a method for improving flow of
powdered metal borohydride salts, and to a solid composition having improved
flow. Addition of at least 2.5% of at least one base to at least one metal
borohydride prevents clumping and caking of the solid. In one embodiment of
the invention, at least 3% of a base is added, alternatively at least 5%. In one
embodiment of the invention, no more than 40% of a base is added, alternatively
no more than 20%, alternatively no more than 17%, alternatively no more than
15%, alternatively no more than 14%, alternatively no more than 13.5%.
Preferably, the metal borohydride compound is an alkali metal borohydride;
alternatively it comprises sodium borohydride or potassium borohydride,
alternatively sodium borohydride. Preferably, the base is an alkali metal
hydroxide or sodium or potassium methoxide, or mixture thereof; alternatively
lithium, sodium or potassium hydroxide or sodium or potassium methoxide, or a
mixture thereof; alternatively sodium hydroxide or potassium hydroxide;
alternatively sodium hydroxide. More than one alkali metal borohydride and
more than one base may be present.
The solid composition of this invention may be in any convenient form.
Examples of suitable solid forms include powder, granules, and compressed solid
material. Preferably, powders have an average particle size less than 80 mesh
(177 um). Preferably, granules have an average particle size from 10 mesh (2000
um) to 40 mesh (425 um). Compressed solid material may have a size and shape
determined by the equipment comprising the hydrogen generation system. In
one embodiment of the invention, compressed solid material is in the form of a
typical caplet used in other fields. The compaction pressure used to form
compressed solid material is not critical.
In one embodiment of the invention, the solid composition is substantially
free of substances that catalyze hydrolysis of borohydride, e.g., salts of transition
metals such as Co, Ru, Ni, Fe, Rh, Pd, Os, Ir, Ft, or mixtures thereof; and borides
of Co and/or Ni.
Preferably, the water content of the solid composition is no more than
0.5%, alternatively no more than 0.2%, alternatively no more than 0.1%.
Preferably, the solid composition contains less than 20% of anything other than
the borohydride compound and the base, alternatively less than 15%,
alternatively less than 10%, alternatively less than 5%. Other possible
constituents of the solid composition include, e.g., catalysts, acids, anti-foam
agents and surfactants.The solid composition of this invention also may be used in the fields of
synthesis and metal recovery.
EXAMPLES
Example I- Effect of NaOH on SBH Dissolution Rate
SBH powders were formulated with different NaOH contents. The
preweighed solid mixtures were blended by mixing in a coffee grinder for about
two minutes, and the resulting powder sieved through an 80 mesh (177 urn)
sieve. The sieved powders were placed in water to make 10 mL of a 30% solution
(% based on SBH+NaOH) and allowed to dissolve with slow stirring with a
magnetic stir bar. Average complete dissolution times for 2 runs are displayed
These results show that the dissolution time per gram of SBH begins to decrease
at 2% NaOH and then begins to increase again at about 15-20% NaOH, with a
marked increase beyond 25% NaOH.
Example 2'- Dissolution Time for Caplets
Caplets were formed under a pressure of 10,000 psi (68.9 kPa), and
dissolved as described in Example 1. Results are presented below in Tables 3
The data demonstrate that when a larger amount of solution is prepared, the
difference between SBH and the NaOH formulation increases. Therefore, the
advantage of including NaOH in the formulation increases with solution size.
Example 4'- Dissolution Time vs. Weight % of Solids
Caplets, granule and powdered forms of SBH and of a formulation of 87%
SBH/13% NaOH were dissolved as described in Example 1 to form solutions
having different percentages of dissolved solids (Wt. %). The results are
presented below in Table 6. Times are reported in seconds.
The dissolution times show that the difference in dissolution times between SBH
and the NaOH formulation increases with the weight percent solids of the
solution being prepared. Therefore, the advantage of adding NaOH to the
formulation increases with the concentration of the solution being prepared.
7
Example 5- Test of Flowability of Borohydride/Hydroxide Composition
Mixtures of SBH and NaOH were pulverized in a coffee grinder for 2
minutes and then placed into 100 mL polypropylene bottles. The samples were
then left on a lab bench for 2 months, at which time each sample was lightly
tapped and checked for its ability to flow. Results are reported below.








We claim:
1. A solid composition comprising:
(a) from 50% to 98% of at least one borohydride compound; and
(b) from 2% to 50% of at least one base.
2. The composition as claimed in claim 1 in which said at least one borohydride compound
is sodium borohydride, potassium borohydride or a combination thereof, and said at least one
base is sodium, lithium or potassium hydroxide, sodium or potassium methoxide, or a
combination thereof.
3. The composition as claimed in claim 2 having at least 2.5% of said at least one base and
no more than 97.5% sodium or potassium borohydride.
4. The composition as claimed in claim 3 in which the borohydride compound is sodium borohydride and the base is sodium hydroxide.
5. The composition as claimed in claim 4 having from 3% to 17% sodium hydroxide and from 83% to 97% sodium borohydride.
6. The composition as claimed in claim 5 having 15% sodium hydroxide and at least 85% sodium borohydride.
7. A method for rapid production of an aqueous borohydride solution comprising a step of
adding the composition as claimed in claim 1 to water in an amount sufficient to produce a
solution having from 1% to 40% solids.
8. The method as claimed in claim 7 in which the solution has from 5% to 35% solids.

Documents:

267-DEL-2007-Abstract-(13-12-2010).pdf

267-del-2007-abstract.pdf

267-DEL-2007-Claims-(13-12-2010).pdf

267-del-2007-claims.pdf

267-del-2007-correspondence-others 1.pdf

267-DEL-2007-Correspondence-Others-(13-12-2010).pdf

267-DEL-2007-Correspondence-Others.pdf

267-del-2007-description (complete).pdf

267-DEL-2007-Form-1-(13-12-2010).pdf

267-del-2007-form-1.pdf

267-del-2007-form-18.pdf

267-DEL-2007-Form-2-(13-12-2010).pdf

267-del-2007-form-2.pdf

267-DEL-2007-Form-3-(13-12-2010).pdf

267-DEL-2007-Form-3.pdf

267-del-2007-form-5.pdf

267-DEL-2007-GPA-(13-12-2010).pdf

267-del-2007-gpa.pdf

267-DEL-2007-Petition 137-(13-12-2010).pdf


Patent Number 245822
Indian Patent Application Number 267/DEL/2007
PG Journal Number 05/2011
Publication Date 04-Feb-2011
Grant Date 02-Feb-2011
Date of Filing 09-Feb-2007
Name of Patentee ROHM AND HAAS COMPANY
Applicant Address 100 INDEPENDENCE MALL WEST, PHILADELPHIA, PENNSYLVANIA 19106-2399, U.S.A.
Inventors:
# Inventor's Name Inventor's Address
1 JOHN HIROSHI YAMAMOTO 129 SUMMER STREET, ANDOVER, MA 01810, U.S.A.
PCT International Classification Number H05B3/10
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 60/774,253 2006-02-16 U.S.A.