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Патент USA US2408616

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2,408,615
Patented Oct. 1, 1946
UNITED‘
2408,6151"
‘
CATION’ EXCHANGE RESINS AND PRODUC- a‘
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TION THEREOFHQ
James R.;Dudley,. Cos Cob, Conn”v assignor to
American Cyanamid Company, New Yorka N. _Y.,
a. corporation of- .Maine
‘ "No Drawing.
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Application March so, 1-944,v ] '
SerialaNo. 5283768
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absorption of cations fromwaterl equivalent to
about 9,600 grains‘ of calcium carbonateperv cubic
foot of resin. The density ofthe material'isabout
This invention relates to cation active mate-j
rials, that is, materials which exchange-'orex
tract, by other means cations from fluid‘ media.
An object of this‘ invention is to provide a sub
13.2 pounds per cubic ioot.‘
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stantially water-insoluble resin having a relatively in
Parts
high capacity for the absorption of cations.
This and other objects are attained by react
ing furfural with mineral acidhalidesand resini<
Sulfuryl chloride (4'.'0’m'ols)'__' ____________ __ 540
fyi'ng to a water-insoluble form.
Furfural (10'.0>mo1s).__~_;__-_-___; _____ “1-. 1010
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Glacial acetic acid_1______;_ _______ ,1 ______ “.840
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The following. examples arefgiven by. way of 10 ‘ As in Ex'ainpl'efl‘ ‘the sulfuryl chlorid‘e‘isr' dis
illustration and not in limitation, The propor
solved in'the acetic acid, this solution-is" cooled
tions‘arei'n-parts byiweight, and the furfural is
in an ice bath; and the’furfural‘ is‘ then, added
95% pure.
‘
slowly with stirring so that the ‘temperature of
Example 1
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the solution does'notexceed 20°C. The solution
15
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‘Parts
is black- when the addition is complete and a
Sulfuryl chloride (4.0 mols‘)l_»_‘__________ ____ __ 540
hard black brittle gel is formed on ‘standing over‘
Glacial acetic acid_.._'_, _____ __. _____ ..; ______ __ 840
night.
Furfural ,(8‘.0 mols) ____ __ ________________ _. 808
The sulfuryl chloride is dissolved in the acetic
acid, and the solution cooled'iin an i‘cebath. The
furfural is thenfadded'slowly with stirring so‘that
the temperature of the solution does ‘not exceed
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The gel is broken into small particles which are
covered with water and allowed to stand over
V20 night.‘ The Water is drained oiT and the resin
driedffor 4.‘ vhours at- 100° C. - The ?nal Product
has’ 'a, capacity for the‘ absorption of, cations iI'Om
fwater equivalent-ttorabout 9,900vgrains of calcium
. 20° C. When the addition is complete the solu¢
tion is black and uponzstanding overnight; a: very 25 carbonate‘per cubic footef resin and the :density
soft black‘gel is formed. After'standing for-an
of thel'materiallis- about 17‘.3=pounds per cubic
foo-t.
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additional day the gel becomes ?rm and hard;
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Example -5
. .
The gel is reduced to particles of‘small size
which are covered with water and allowed .to
I The procedure of Example isiollowed except
stand overnight. The water is then drained off
‘that instead of soaking the gel particles overnight
and the resin dried for 4 hours at 100° v(3'; and
they are suspended in water and the mixture is
evaluated, The ?nal product exhibits a capacity
boiled for 4 hours. The wate‘r’is'the'n ‘drained'off
for the absorption or exchange of: cations from,
and the resin driedforl 4 hours at 100° C. The
water equivalent to about 8,000‘ grains‘ of calcium
carbonate per cubic foot of resimand‘the" density
of the material is‘ about 12.2" pounds per cubic
foot.‘
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?nal product exhibits a‘capacity for the absorp
' 'tion ‘of‘ cations from waterjequivalent' to‘about
15,600 grains of ‘calcium carbonate per cubicifo’ot
pf‘resin and th'e-Tdensitybf ‘the material is about
1
Example}
l5lii'pbiunds per cubic foot‘; ’
Example: 1 is repeated but instead‘ oi. soaking
the small-sized particles of the gel,‘ theyare. sus
pended
hours.» 7
40
.
hours‘? at 145°‘ C.‘ to give aproduct having a capac
. of ‘7.7 pounds. per cubic foot..--,.- *
dot exhibitsja capacity for theabsorption or‘ ex
change of cations from water, equivalent to about 45
1,100 .gr'ains ofcalcium. carbonate per‘ cubic, £00.11 ' ‘
of resin'and the d‘ensity'ofQthe materialisabout
105 pounds ‘per cubic foot;
Eqcaymple, 6
The procedure of Example 4 is iollorvvedexcept
that .instead, of soaking .the gel .particles i-c’v'er
night, dry ‘steam is passed through the resin for 4
‘hours as in‘ Example _'_3_. The resin is then dried
50 for 4 hours at 100° C; and the ?nal product found
s '_ ‘Example 1 is repeated but' instead of soaking - ,
thegel particleslin- water overnight; dry 'steam'is
to have a capacity Viorthe ‘absorption or exchange
of cations from "water equivalent to about 14,100
“grainsof ‘calcium carbonate per cubic foot of resin.
passed through theresin‘for 4 hours. ' After'this
C. and the ?nal'product has?a capacitylmr vthe
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'carbonate'p'er cubic "footbf‘resin'. and a density
The- water; is then drained off and the
- resin dried for 4' hoursat 1.0090.‘ The ?nalrprodr
‘treatment the resin 'isvdried- for 4‘ hours at 100°
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"ity equivalent‘to,abouti12§900 grains‘of calcium
in water and the mixture boiled ,for,4 ‘
Examples ~_ _‘
’
" “ 'ft'er evaluation ‘the "resin is redrie‘d'fori 17
The ‘resin has a density of 16.0 pounds per cubic
65
foot.
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we
2,408,615
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Example 7
Example 12
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Parts
Parts
Sulfuryl chloride (4.0 mols) ______________ _. 540
Phosphorus oxychloride (0.5 mol) ________ __
Glacial acetic acid ______________________ __ 840
Glacial acetic acid ______________________ __ 105
Furfural (12.0 mols)‘ _____________ __y____'___ 1212
Furfural
(1.0 mol) ____ “I _______ __._______ __
77
101
The phosphorus oxychloride is dissolved in the
acetic acid and the solution cooled to about 3° C.
The furfural, cooled to about 5" C., is then added.
The sulfuryl chloride is dissolved in the acetic
acid, the resulting solution cooled in an ice :bath,
and the furfural is then added slowly with stir
ring so that the temperature of the solution does 10V The solution is black and after standing over
night a soft brittle'rubbery black gel is formed.
not exceed 20° C. Upon standing overnight a gel
Upon warming up, an exothermic reaction oc
is formed which is harder and more brittle than
curs in which acetic acid and hydrochloric acid
that of Example 4.
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fumes’ are distilled from the material. Upon
The gel is broken into small-sized particles
which are cured in an oven for 4 hours at 50° C. 15 ‘cooling a very hard brittle gel is obtained.
Small -sized particles of the gel are covered
and then for an additional 4 hours at ‘100° C._
with water and allowed to stand for 4 hours.
The cured resin particles are then covered with
Steamis then bubbled into the mixture for 4
water and allowed to stand overnight. The water
hours, the water is drained o?, and the resin is
is drained oiT and the resin dried for 4 hours at
dried for 4 hours at 100° C. The ?nal product
100° C.
20
has a capacity for the absorption of cations from
The ?nal cured and hydrolyzed product has a
water equivalent to about 16,100 grains of cal
capacity for the absorption or exchange of cations
cium carbonate per cubic foot of resin and the
from water equivalent to about 18,300 grains ‘of
density of the material is about 17.5 pounds per
calcium carbonate per cubic foot of resin and a
cubic foot. _
density of 18.2 pounds per cubic foot.
25
Example '13
Ezcample 8
Parts
Phosphorus oxychloride (0.5 mol) ________ __
77
The procedure of Example 7- is repeated ex
Glacial acetic acid ______________________ _- 105
cept that instead of soaking the cured resin par
ticles overnight they are suspended in water and 30 Furfural (1.5 m0ls)_' ____________________ __ 152
The procedure of Example12 is followed
boiled for 4 hours. Following this the water is
throughout. The brittle black gel, somewhat
drained off and the resin is dried for 4 hours at
100° C. The ?nal product exhibits a capacity.
?rmer than that formed in Example 12, has a
capacity for the absorption of cations from water
forthe absorption or exchange of cations from
water equivalent to about 18,100 grains of cal 35 equivalent to about 17,300 grains of calcium car
bonate per cubic foot of resin. The density of
cium carbonate per cubic foot of resin and has
a density of 18.4 pounds per cubic foot.
the material is about 19.6 pounds per cubic foot.
The mineral acid halides are preferably resin
Example 9
i?ed with furfural alone although a minor por
A hard brittle gel is prepared as described in 40 tion of the furfural may be replaced by other
aldehydes, particularly formaldehyde, a polymer
Example 7. Instead of curing small-sized par
ticles of this gel by heating in an‘cven for a
period of time, they are covered with‘water and
allowed to stand overnight; ' The water is then
drained off and the resin particles dried for 4
hours at 100° C.
i
of formaldehyde or a substance yielding form
aldehyde.
Other aldehydes which may be used
include acetaldehyde, butyraldehyde, heptalde
hyde, crotonaldehyde, acrolein, benzaldehyde,
etc.
The ?nal product has a capacity for the ab
sorption or exchange of cations from water equiv
The resins of the present invention may be
cured by heating at a temperature ranging from
alent to about 11,700 grains of calcium carbonate
room temperature to about 150° C. for from sev
'eral hours to a day.
The reactions of furfural with mineral acid
‘chlorides are necessarily carried out in anhydrous
per cubic foot of resin and a density of 22.2
pounds per cubic foot.
Example 10
Example 7 is repeated except that the curing
step is omitted. The hard brittle gel particles
are suspended in water and boiled for 4 hours.
After draining off the water, the resin is dried
for 4 hours at 100° C. and evaluated. The ?nal
product has a capacity for the absorption of
cations from water equivalent to about 10,800
grains of calcium carbonate per cubic foot and
a density of 23.2 pounds per cubic foot.
Example 11
Example 7 is repeated except that the gel is not
cured but particles thereof instead are treated by
solvents to prevent hydrolysis of the chlorides
before sulfonation or phosphonation takes place.
The reactions involved. in the preparation of
these resins are undoubtedly complex. No at
tempt has been made to determine the mecha
nism andI do not wishto be ‘limited to any par
ticular theory thereof. However, I believe that
the rapidity, and in some cases the violence, of
the reaction in its last stages may be explained
in the following manner. Elimination of water
in all probability takes place during the con
.densation leading to the formation of a resin
from furfural. The water thus liberated will re
act with the acid chlorides (or the furfural acid
chlorides) with the formation of a mineral acid
passing dry steam therethrough for 4 hours as in
and the liberation of heat. The acid thus formed
Example 3, and the resin is then dried for 4 hours
serves to accelerate further condensation and
at 100° C.
70 the heat likewise has the e?ect of accelerating
The ?nal product has a capacity for the ex
thev reactions which are taking place. While the
change of cations in water equivalent to about
rate of reaction may be slow initially, these fac
12,800 grains of calcium carbonate per cubic foot,
tors cause the speed of reaction to increase pro
and the density of the material is about 21.7
gressively until theireaction becomes violent.
pounds per cubic foot.
75
My new resinous materials may be used alone
2,408,615 I
5
or in admixture with other cation active mate
rials. Furthermore, my resins may be applied
before gelation to a suitable carrier such as diato
maceous earth, clays, charcoal, etc. In this Way,
the active resin is spread on the surface of a rela
tively inert material and this enables one to
employ a smaller quantity of resin than other
wise to obtain the same active area.
6
other cations to the metallic state, as well as for
many other reduction purposes.
Obviously many variations in the processes and
compositions described above may be made with
out departing from the spirit and scope of the
invention as de?ned in the appended claims.
I claim:
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1. A granular water-soluble composition of
‘ matter comprising the hydrolyzed product of re
The granular resinous materials prepared ac
action of a mixture including furfural and a min
cording to my invention, and particularly those 10 eral acid halide selected from the group consist
having a particle size less than 8 mesh, are useful
ing of suliuryl chloride and phosphorus oxychlo
in the removal of cations from ?uid media, espe
cially aqueous solutions. The resins may be used
in the hydrogen-activated form to remove cations
from solutions of bases. My resinous cation
active materials may also be employed as ex»
ride and having a particle size of less than about '
8 mesh.
2. A process which comprises condensing fur
iural and a mineral acid halide selected from the
group consisting of sulfuryl chloride and phos
phorus oxychloride, gelling the resulting con
densation product, heating the gel thus obtained
with a sodium salt such as sodium chloride and 20 until it is insoluble in water, and hydrolyzing the
change materials in accordance with the prin
ciples applied to the use of the natural and syn
thetic zeolites. Thus, the resin may be activated
upon contact with a solution containing calcium,
magnesium or other cations, an exchange of the
latter ions for the sodium ions takes place.
The activating solutions or regenerating solu
tions are dilute acid solutions or dilute salt solu
tions, e. g. about 0.2%—l0% of sulfuric acid, hy
drochloric acid, sodium chloride, potassium chlo
water-insolubilized gel.
3. A process which comprises condensing fur
fural and a mineral acid halide selected from the
group consisting of sulfuryl chloride and phos
phorus oxychloride, gelling the resulting con
densation product, hydrolyzing the gel thus ob
tained, and heating the hydrolyzed gel until it is
insoluble in water.
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ride, etc.
4. A granular water-insoluble composition of
To be sufficiently insoluble for practical use in
the art of water puri?cation, a resin should have 30 matter suitable for the removal of cations from
fluid media which comprises the hydrolyzed prod
a sufficiently low solubility that it will not be dis
uct of reaction of a mixture including furfural
solution
to
be
treated.‘
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solved away rapidly by the
and
sulfuryl chloride, and having a particle size
Thus, water should not dissolve more than about
of less than about eight mesh.
one part of resin in 1,000 parts of water when
5. A granular water-insoluble composition of
passed through a bed of resin (after the ?rst cycle
matter
suitable for the removal of cations from
comprising an activation, exhaustion and reacti
fluid media whioh‘comprises the hydrolyzed prod
vation of the resin) .
uct of reaction of a mixture including furfural
My resinous materials are useful for a wide
and phosphorus oxychloride and having a particle
Some
of
the
uses
which
may
variety of purposes.
size
of less than about eight mesh.
40
be mentioned by Way of example are: water puri
6. A process which comprises condensing fur~
?cation; puri?cation of sugar juices; purification
fural and a mineral acid halide selected from the
of water from lead pipes; rem-oval of heavy metal .
group consisting of sulfuryl chloride and phos
ions from food, beverages and pharmaceutical
phorus oxychloride, to produce a reaction prod
products; decolorization of solutions containing
coloring matters, etc. My condensation products 45 uct, gelling said product, hydrolyzing said prod
uct, heating said product until insoluble in water
may also be employed to recover valuable metal
and granulating said product after gelation to a
cations from dilute solutions, e. g., gold from sea
particle size of less than about eight mesh.
water, chromium from chrome tanning liquors,
'7. A process which comprises condensing fur
silver from photographic baths, etc. Another
important application of my materials is in the 50 fural and phosphorus oxychloride, gelling the re
sulting condensation product, hydrolyzing the gel
absorption or adsorption of gases such as am
thus obtained, heating the hydrolyzed gel until-it
monia, amines, e. g., triethyl-amine, methyl
amine, etc., from ?uid media either dissolved
in a liquid or from vapors.
_
is insoluble in water, and granulating said gel to
a particle size less than about eight mesh where
My furfural mineral acid halide condensation 55 by a product is obtained suitable for the removal
of cations from fluid media.
products may be used in reduction processes such
as in reducing ferric ions to ferrous ions, mag
_ nesium ions to a lower degree of oxidation and
JAMES R. DUDLEY.
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