Note: Descriptions are shown in the official language in which they were submitted.
5 3 ~i
--1--
TRANSITION METAL ALUMINATES PREPARED BY
REACTING TRANSITION METAL COMPOlnNDS WITH
AMORPHOUS HYDROUS ALUMINA
It is disclosed in U.S. Patents 4,116,858 and
U.S. 4,159,311 (both by Bauman and Lee) that novel
crystalline compounds are formed, especially in certain
reticular ion exchange resins, by contacting aqueous
solutions of Li halides with hydrous alumina, Al(OH)3,
to form LiX ~Al(OH)3 crystals, where X is halide, which
are useful in selectively removing Li ions from a~ueous
solutionsA Prepara-tion of LiOH 2Al(OH)3 is also
disclosed. .
In U.S. Patents 4jll6,857 and U.S. 4,183,900
(both by Bauman and Lee) it is disclosed that
MgX2 2Al(OH)3, where X is halide, is prepared by react-
ing Mg halide with hydrous alumin~ in an ion exchange
resi~ and that the so-formed aluminate is useful in
selectively removing Mg ions from aqueous solution.
Maksimovic, in Compt. Rend. Soc. Serbe Geol.
Ann 1955, reported on x-ray diffraction studies of
Takovite, a natural mineral from Takova, Serbia which
he identified as nickel alumin~m oxide hydroxide hydrate,
Ni5Al4O2(OH)l~o6~2o-
28,147-F
~ ~553~
--2--
Gallezot, in Compt. Rend. 268B, 323-31 (1969),
reported on x-ray diffraction studies of he~agonal
nickel aluminum oxide hydra-te, identi:Eied as
Ni5Al~0ll 18H~O and as 2A1203 5NiO 18~I20.
It has been found, unexpectedly, that novel
and useful transition metal aluminates are formed by
reacting compounds of certain transition metals with
hydrous alumina, e.g. Al(OH)3, to form certain transi-
tion metal aluminates which are crystallizable by
hçating. The aluminates so-formed are useful, e.g., as
ion exchangers and as precursors to spinels among other
things; they may be supported by a substrate or may be
unsupported.
The present invention is crystalline transi-
tion metal aluminates conforming generally to theformula
MAVaZb~nAl(OH)~ mE20
where ~ is at least one divalent transition
metal selected from the group comprising Cu, Zn, Mn,
Fe, Co, and Ni,
where AZ represents negative valence ions or
radicals,
n is a value of from about 1 to about 4,
v is a negative valence of 1, 2, or 3,
a and b are each values of from zero to 2,
wi~h (va)+~vb~ equal to 2, and
with m being a value of zero or more.
The present invention is also directed to a
method for preparing the aluminates, said method compris-
ing, mixing amorphous hydrous alumina in an alkaline
28,147-F -2-
.
5-5 ~ ~
3--
aqueous medium with the requisite transition metal
compound, thus forming an adduct of the transition
metal compound with the amorphous hydrous alumina,
Al(OH)3, heating the so-formed adduct to crystalli-
zation at a temperature in the range of 50C to 150Cfor a period of time from 1 hour to 100 hours, and
recovering the so-formed transition metal aluminate.
The present invention also embraces a process
for removing transition metal ions from aqueous solution,
said transition metal ions being selected from the
group consisting of Cu, Zn, Mn, Fe, Co, and Ni, said
process comprising reacting said aqueous solution with
a transition metal aluminate of Claim 1 wherein the
transition metal in the aluminate structure corresponds
to the transition metal in said solution, said transi-
tion metal aluminate being deficient in said transition
metal ion at the outse.t, continuing said reaction until
the said transition metal aluminate has become substan-
tially enriched by transition metal ions from the said
a~ueous Folution.
The transition metals within the purview of
this invention comprise one or more of the group com-
prising Cu, Zn, Mn, Fe, Co, and Ni, all in their diva-
lent form. The starting transition metal compounds are
referred to herein as "MAZ" compounds, where M is the
transition metal and AZ represents the negative
radical(s~ or anion(s). Each "A" and "Z" may be the
same as, or different from, the other.
The hydrous aluminas within the scope of this
invention are amorphous and conform essentially to the
formula Al(OH)3 along with whatever waters of hydration
28,147 F ~3-
.
.
~ ~55~
--4--
are present. The waters of hydration will depend, to
some extent, on the methods of prepar~tion and the pH,
temperature, and environment in which the hydrous
alumina is formed or dispersed. Preferably the amor-
phous hydrous alumina is freshly formed in agueousmedium by precipitation of a dissolved Al compound,
such as AlCl~, by the action of a non--interfering
transient base, such as N~3. Other bases, e.g. alkal
metal hydroxide/ or alkaline earth metal hydroxides
form corresponding aluminates which are not directly
useful in forming the aluminates of the present inven-
tion. Crystalline Al~OH)3, e.g., Gibbsite, Bayerite,
or Norstrandite/ is usually converted to Boehmite
(crystalline AlOOH) when heated.
The amorphous Al(OH)3 may be a neat (unsup-
ported~ dispersion of the Al~OH)3 in aqueous medium or
may be supported on and/or within a substrate. Non-porous .
or reticular inorganic or organic substrates may be
used to support the Al(OH)3/ so long as the substrates
do not substantially interfere with the desired formation
of the subject crystalline aluminates. The precipitated
Al(O~)3 is usually a suspension of small gel particles.
There are/ of course/ substrates which permit
the formation of the crystalline transition metal
aluminates/ but which offer certain reactivities of
their own during subseguènt use of the said supported
crystalline aluminates, such as ion exchange resin
substrates. If it is desired to heat the suppoxted
aluminate to very high temperature/ then the choice of
substrates is considerably narrowed. The subject
aluminates are generally prepared in situ on the sub-
strate when a substrate is used/ but may also be
28/147 F -4-
3 ~
-5
prepared as an aqueous dispersion and then deposited on
or within a substrate.
As mentioned, supra, it is preferred that the
amorphous Al(O~)~ be freshly preparecl, such as by
precipitating Al(OH)3 by the action of NH3 or NH~OH on
a solution of an Al salt, such as AlCl3. Contacting of
the MAZ compound with the Al(QH)3 may be done simul-
taneously with, or subsequent to, the Al(OH)3 formation.
Since elevated temperature and/or long periods of
standing can cause the Al(OH)3 to become at least
partially crystallized to forms such as Boehmite or
Norstrandite, it is best to avoid using elevated
temperatures until the MAZ has been added to the
Al(OH)3. After ~he MAZ compound has been mixed with
the Al(OH)3 to form an adduct, the adduct is then
heated to crystallize it to the subjec-t
MAVaZbV nAl~OH~3m~20. The following descriptions
generally illustrate the preparations.
Preparation of Unsupported Aluminates
An alkaline aqueous dispersion of hydrous
alumina (which is preferably freshly prepared) is mixed
well with at least one MAZ compound to form an adduct
or complex which, when heated to a temperature in the
range of about 50C to about 150C for a period of time
of from about 1 hour to about 100 hours, yields the
subject crystalline MAVa2b-nAl(OH) 3 mH2 compounds. The
average particle size of the neatly prepared (i.e.
unsupported) crystals is generally in the range of
about 0.01 microns to about 1 microns, probably de-
pending somewhat on the alkalinity and/or other surfac-
tants or micelles i~the aqueous solution.
28,147-F ~5
5 ~ ~
--6~
Preparation of Aluminates on Inert, Non-Porous Substrates
Hydrous alumina is precipitated in aqueous
medium on-to the surfaces of substantially inert,
non-porous substrates or is mixed with said substrates
in aqueous medium and reacted with at least one MAZ
compound in the aqueous medium to form the subject
crystalline compounds. By "non-porousl' it is meant
here that there are no po~es visible to the naked eye,
though the surface as ~iewed under high magni~ication
is likely to appear rough or irregular. Surfaces which
appear mirror-smooth, even under magnification, are not
likely to hold well to an appreciable amount of the
coating. The affinity of the surfaces o~ the substrate
for receiving the reactant compounds (hydrous alumina
and MAZ compounds) may be enhanced or improved by
roughening the surfaces. The substrates may be organic
~e.g. polymers) or inorganic ~e.g. stable oxides), or
metallic (e.g. metal particles, screens, or sheets).
Natural or resinous type su~strates (e.g. cellulosic,
wood, etc.) may be used as the substrate. Mixing of
said hydrous alumina and MA~ compounds in a substrate-
-containing aqueous medium in a hall-mill, tumbler or
other mixing device is contemplated, said mixing being
done prior, during, or subsequent to the step of heating
to obtain the subject crystals.
Pre2~ tion of Alum nates on Inert, Reticular Substrates
The use of substantially inert, reticular
substrates is contemplated. Such substrates are employed
in substantially the same manner as with the non-porous
substrates. The term "reticular" is used herein to
refer to the presence of holes, voids, channels, cracks,
indentations or other physical features which permit
the reactant compounds to enter the physical structure
28,147--F -6-
-7-
of the substrate rather than merely coat the outer
surfaces. For optimum penetration into the substrate,
it is best if substrate imbibes an aqueous solution of
a soluble Al compound (e.g. AlCl3) before the pH is
increased (e.g. with NH3 or NH4OH) to precipitate
hydrous alumina (Al(OH)3). The soluble MAZ compound
may then also penetrate the substrate to substantially
react with the Al(OH)3 and, upon heating, the subject
crystals are formed in and on the substrate.
Preparation of Aluminates in Reticular Ion
Exchange Resins
The use of reticular ion exchange resins as
substrates is carried out in substantially the same
manner as with other reticular substrates, including
the optimum loading of the crystals on and into the
exchange resin by the in situ precipitation of hydrous
alumina from a soluble Al compound that has permeated
the resin. The ion exchange resin may be substantially
of the anionic or cationic, or mixed cation-anion
variety. Once the subject crystals are formed on or
within the ion exchange resin one may use the composite
to alternately, or simultaneously, utilize the ion
exchange capabilities of the subject aluminate crystals
and of the resin.
The MAZ Compounds
The anions or negative radicals which may be
employed as a compound with the transition metal to
form the subject aluminates, MAZ?nAl(OH)3, may have a
valence of 1, 2, or 3. The transition metal compound
is preferably water-soluble and/or alkali soluble, but
may also be a compound which, when added to alkaline
water, will react to form water-soluble compounds.
-7-
28,147-F
~ ~5~
Transitlon metal compounds containing more ~han one of
the subject transition metals may be used. The A2 may
represent two monovalent ions or radi.cals or one divalent
ion or radical or two-thirds of a tri.valent ion or
radical.
Examples of monovalent, di~alent, and txi
valent anions and negative radicals contemplated for
the present invention to be used in the generic formula
MAVZb ~Al(OH~3 mH20 are as follows:
halide (esp. Cl , Br , I
hydroxy (OH )
dihydrophosphate (H2PO4)
sulfate ( S04
hydrocarbonic (HCO3 )
hydrophosphate (EPO~ )
nitrate (NO3 )
chromate (~CrO4)
trichloroacetic (Cl3C~COO 3
other inorganic acid radicals
and organic acid radicals of monobasic,
dibasic, and tribasic carboxylic acids having
l to about 8 carbon atoms, with the valence
o~ 1, 2, or 3 corresponding to the number
of carboxyl groups present in the organic
acid moiety.
In the generic formula MAaZb nAl~OH)3 mH20
the value o n should be enough to provide a mole ratio
of Al/M of at least 1/1, preferably at least about
1.5/1, most preferably at least about 2/l. At Al/M
ratios of less than 1/l in the process of preparing the
crystalline subject aluminates, other forms o crystals
28,147 F -8-
,, .
~9~
may be formed which are not part of the present inven-
tion. During the formation process to obtain the
desired crystals, i-t is best if the Al/M ratio is at
least about 1/1, preferably about 1.5/1 to about 2/1.
Once the crystal is formed, the MAZ portion of the
aluminate may be substantially depleted by use of an
aqueous elution step without destroying the aluminate
crystal, so long as there remains enough of the MAZ
moiety present within the three-layered structure to
retain integrity of the crystal. Generally, one may
substantially retain the three-layered hexagonal
expanded crystal structure so long as there remains
enough MAZ moiety so tha~ the A1/M ratio does no-t
e2ceed about 4/1. When the crystal structure has a
reduced amount of MAZ moiety, there is available space
within the three--layers of the unit cell of the hexa~
gonal crystal lattice to take up additional MAZ moie~
ties until the crystal becomes essentially packed or
loaded at an Al/M ratio in the range of about 1.5/1 to
2/1. The three layers of the unit cell compxise three
layers of the Al (OH)3 complexed with intercalated
layers of the MAZ moiety. The unit cell layered struc-
ture may be graphically illustr~ted for discussion
purposes as:
Al-O
MAZ:
Al~O
MAZ _
Al-O__
MAZ
Also in the above generic formula the value
of m for the waters of hydration may be from zero ~when
the crystal has been dehydrated by heating) to as much
28,147-F 9
5 3 5
--10--
as 6 or more depending on the particular MAZ moiety in
the crystal and on the temperature, p~, and conditions
o the preparation. Though th~xe may be more than ~
waters of hydration in the crystal, it is believed that
most of the crystals within the scope of this invention
will be less -than 6 and mos-t often less than about 4.
As discussed supra, the transition metal
aluminate crystals of the present invention are three-
-layered, hexagonal with intermediate ~or intercalated)
layers of the MAZ moiety between layers of the hydrated
alumina. The crystals are further identifiable by
a~axis cell constants typically in the range of about
.2-5.5 (direct) and c-axis cell constants typically in
the range of about 20-50 (direct). It will be under-
stood, of course, that the a-axis and c-axis cell
measurements will vary to some degree according to the
particular MAZ compound and amount of MAZ compound in
the crystal when formed~
In a given crystal, the MAZ may be eluted
with an aqueous wash, taking care not to remove all the
MAZ; then the crystal which is unloaded with respect to
MAZ may be used in selectively takin~ up more o~ the
same MAZ from agueous solution. This property makes it
possible to make a crystal to remove from solution any
one compound of a transition metal selected from the
group consisting of Cu, Zn, Mn, Fe, Co, and Ni. This
property is demonstrated by example hereinafter and is
particularly applicable when the crystal is deposited
within the matrices of a reticular (esp. a microporous)
ion exchange resin in bead or particulate form.
28,147~F 10-
Furthermore, the negative radical ~or anion)
in a given crystal structure may be exchanged with a
different negative radical ~or anion) in aqueous solu-
tion, thus yielding a~ditional or alternate novel forms
of the transition metal aluminate structure. For
example a crystalline NiC12 2Al(OH)3 may undergo anion
exchange with different anions in aqueous solution,
such as NO3 , to form Ni(No3)2 2Al~OE[)3 and/or
NiCl(NO3) 2Al(OH)3, depending on the concentration of
each in the agueous medium.
Exam~le 1 ~Nickel Alumlnates)
For this example, the substrate employed is a
macroporous anion exchange resin. It is a porous bead
form of a cross-linked styrene-divinylbenzene polymer
network having amine groups attached to the benzene
rings and is in its chloride form (though the OH form
is usable). The resin has a porosity of about 30 per-
cent and a surface area of about 40-50 m2/g.
The resin beads are saturated with an excess
of 32 percent AlCl3 aqueous solution. The beads are
~hen subjected to a flow of inert gas (~iz. N2) to
remove excess AlC13 solution until the resin is sub-
stantially dry and free-flowing. A 75-g portion of the
beads is treated with 200 ml of 30 percent aqueous N~3
for about 15 minutes at ambient room temperature; this
converts the AlCl3 to amorphous Al(OH)3 and forms
soluble NH~Cl in the a~ueous phase. The product is
washed well with water to remove solubles and 98 ml of
the resin, containing Al(OH)3, is obtained. The resin
is added to a 250 ml aqueous solution containing 25.5 g
NiC12-6H20 and 34 g of N~4Cl. The resultant slurry is
refluged at atmospheric (ambient) pressure for 16 hours
28,147-F 11-
5 ~ ~
-12-
and 130 ml of resin composite is obtained; the gain in
volume of the beads indicates that they are swelled.
The product is identified by x-ray diffraction analysls
as a hexagonal, three-layered, crystalline
NiCl2 ~Al(OH)3 mH20 with the NiCl2 being the interme-
diate layer, expanding the crystallinle Al~OH)3 structure.
About 120 ml of the resin is loaded into a
jacketed glass column and washed with de-ionized water
~downflow) at 23 ml/min. and 50C, sampling the ef-
fluent in 50-ml cuts for Ni + analysis, as follows:
Cut ~o. Ni Conc.(g/l~
1 ~ 0.965
2 1.503
3 2.850
4 3.420
1.905
6 1.~50
7 1O033
8 0.830
9 0.652
0.499
~1 0.355
The above wash substantially unloads the
NiCl2 from the resin, but not to the extent of allowing
the Al (0~3 lattice to collapse and destroy the vacan
cies in the three-layer crystal.
The column is then operated downflow with
26 percent NaCl brine containing 0.5 g/l Ni (as
NiCl2).at 23 ml/min. and 50C. Cuts of 10 ml each are
taken of the effluent for Ni analysis. Cuts 1-14
28,147-F ~12~
i5~5
-13-
inclusive show zero Ni + content which indicates the
Ni in the brine is being retained in the crystal.
Ni breakthrough is cletected in cut 15 (100 ml) as
follows:
Cut No. ~ Ni (g~l~
100 0.070
16 100 0.100
17 lO0 0.430
18 100 0.390
19 100 0.390
The column is -then operated again on water
elution downflow at a rate of 23 ml/min. at 50C. The
effluent is cut into 25-ml segments and each is analyzed
for Ni content, as follows:
Cu-t No. Ni (~/1)
1 0.390
2 ~,~390
3 0.~88
4 0.41
2.37
6 4.725
7 2.700
8 2.300
9 1.675
~0 1.280
11 1 . 100
The demons-trated ability of the crystal Ni
aluminate to give up much of its Ni values and then
selectively re absorb Ni values is ~ound in other
28,147 F -13-
-
-
.
3 ~
-14-
aqueous solutions, such as brines containing other
salts, e.g., CaCl2, MgCl2, KCl, and SrCl2. Recovery
of, e.g., NiSo4 values ~rom mine wastes or ore smelters
or other mineral sources operates substantially in the
same manner.
Whereas it is possible to prepare a large
variety of concentrations of Al/Ni in the crystal and
of Al/(amine nitrogen~ of the crystal in the resin, the
usual range appears to be about 1 to 2 moles for Al/Ni
and about 0.5 to 3.0 moles for Al/(amine nitrogen).
In place of NiCl2 values in the crystal
described supra, one may also utilize NiSo~ r Ni~NO3)2,
Ni-acetate, Ni-(citrate)++/ + and a wide variety of
anion or negative radicals having a valence of 1, 2, or
3 and to use such Ni -deficient crystals to absorb
such other Ni compounds.
Exam~le 2 (Cobalt Aluminates)
A cobalt alwminat~ crystalline material is
prepared and tested as an absorber for Co values
substantially in accordance with the procedure shown in
E~ample 1 for Ni aluminates.
The ion-exchange resin (the same as used in
Example 1) is treated with excess 31 percent AlCl3
solution and the excess blown ou-t with N2 to substan-
tial dryness. An 85-g portion is added to 200 ml of
30 percent aqueous NH3 and allowed to react for about
15 minutes, thus obtaining Al(OH)3 in the resin; and
the so-formed composite is washed well with water, ob-
taining about 112 ml of still-wet composite. This is
added to an aqueous solution containing 30 g C~C126H20
28,147~F Q14
~ .
;5~
-15
and 30 g NH4C1 in 250 ml H20 and refluxed at ambient
pressure for 16 hours. The final pH is about 5.57 and
tlle resin is found to be swelled to about a 145-ml
volume. .X-ray diffraction analysis shows the t~pical
hexagonal, three-layered crystal.
A 116-ml portion of the so-formed resin com-
posite is placed in a jacketed glass column and washed
well with water to substantially reduce the CQC12 con-
tent of the crystal. A 26 percent NaCl brine contain-
ing 0.48 g Co /liter is downflowed through the resinbed at 22 ml/min. and 50C. The effluent is taken in
100-ml cuts (20 cuts in all), with analysis of some of
the samples as follows:
Cut No. Co (~m/l)
15 7 0.05
12 0.15
16 0.28
17 0.2g
18 0.29
The column is eluted with H20 downflow at 22
ml/min. and 50C with effluent taken in 25-ml cuts
which are analyzed for Co as follows:
28,147;F -15
55~5
-16-
Cut No. Co ~g~l~
1 0.233
~ 0.250
3 0.250
4 0.280
3.48
~ 5.4
7 4.8
8 4.44
g 3.36
2.80
11 2.36
12 2.08
13 1.84
The chloride ion may.be exchanged for other
anions or negative radicals, e.g., Br , SO4 , NO3 ,
acetate, chloroacetate, oxala-te, or citrate without
altering the hexagonal configuration.
. ..
The crystalline CoAZ"nAl(OH)3 mH20 iS useful
as a spinel precursor, as a source of Co+~ ion for use
with agueous medium containing Co++ ores, Co+~ minerals,
Co + waste streams, or Co + containing brines, by
washing Co++ values from the crystals, thus leaving
vacancies in the crystals for taking up more Co~+
values.
Exam~ Zinc Aluminates)
For this example, the substrate employed is
the same anion exchange resin used in Examples 1 and 2,
28,147-F -16-
.
5 ~ ~
-17-
except it is in the OH' form. The resin-zinc aluminate
preparation is carried out by loading 90 ml of resin
with l mmole of ~l(OH)3/ml by equilibration with 30 per-
cent AlC13 solution, drying until free flowing, react-
ing with excess 30 percent aqueous NH3, heating with
M~4Cl added and ~itrating with 135 me~. of HCl to pH 5.
The volume of resin composite at -the end poin-t is 139
ml. The resin is rinsed with 300 ml of H2O containing
60 g of zinc acetate dihydrate and heated in a 95C
oven for 4 days. Analysis by x-ray shows desirable Zn
aluminate in acetate form along with some Bayerite
and/or Norstrandite (this indicates that too much
heating before the addition of zinc acetate, can prema-
turely transform some of the amorphous alumina hydrate
to crystalline forms). The resin is washed, suspended
in NaCl brine and titrated with 100 meq of NaOH as pH
is kept below pH 7Ø The zinc hydrate precipitated
outside the resin is washed out, 50 g o Zn acetate
dihydrate is added, then the composite is heated in a
95C oven. X ray diffraction analysis indicates good
crystals of the zinc acetate aluminate hydrate.
A 120-ml portion of the composite is placed
in a glass column fitted for a jacket temperature con-
trol and the column is held at 65C. A synthetic brine
of 1 g Zn/liter is prepared by dissolving ZnCl2 in
25 percent NaCl. This brine is pumped at 10 ml/min.
through the column. The resin shows 3.5 percent shrink-
age but the column is filled again. This shrinkage
occurs twice and the column is again filled. After 800
ml o the 0.0306 N Zn brine, the flow is changed to
water ak the same rate. Samples are collected for each
and Zn content e~tablished by titration.
28,147-F ~17-
3 S
~18-
Brine Wa-ter
Flow cc Zn(~Elution_ c ~n~g/l) or Normallty
1-100* ~ 50 0.032Normal
2-100 0.005 N2~25 0.036 y/l
3-100 0.00653-25 0.032 g/l
4-100 0.01~94-25 0.130 g/l
5-100 0.01705 25 0.~28 g/l
6-100 0.01956-25 0.240 ~/1
6-100 0.02757~25 0.224 g/l
8-100 0.03158-25 0.228 g/l
9-25 0.214 g/l
10~25 0.198 g/l
* discarded
The crystalline zinc aluminate in its chlo-
ride form has been identified by x-ray diffraction and
its hexagonal structure has been closely defined. The
chemical constitution is variable; a
(ZnCl~x[Al(OH)3]m - water wash will remove a portion of
the ZnCl2 - and the Cl may be e~changed for other
anions without altering the crystal character.
Example 4 (Cu_Aluminates)
130 Ml of the same resin used in Example 1 is
rinsed, dried and added to excess 30 percent AlCl3
solution. The excess AlC13 is removed at 87C and the
resin is dried to 98.73 g in a stream of N2. The resin
is treated with excess 30 percent aqueous NH3 a~d then
washed with water. The basi~ resin is added to a
solution of 83 g Na2S04 in 300-ml H2O, heated to 50-55C,
28,147~F -18-
-19-
and 35 g CuS04 5H20 iS slowly added with the pH held at
4O0-4.5. Finally it is heated at 100C with the pH
dropping to 3.8.
110 Ml of this resin is placed in a jacketed
glass column and satura-ted with Cu + by flowing a
solution of 25 percent NaCl containing 1.0 g/l of Cu
~added as CuSO~ 5H2O) at 10 ml/min and 70C. The Cu
is eluted wi.th water at 10 ml/min and 70C. The efflu-
ent is sampled and analyzed for Cu++l as shown in the
following table:
Sample No. Volume (mll Cu ln q/1
6 50 0.65
7 25 0.95
8 23 7O4
9 25 11.2
5.6
11 ~5 3,0
12 2S 2.2
13 25 1.6
The crystalline copper aluminate in its sul-
fate form has been identified by x-ray diffraction and
its hexagonal structure has been closely deined. The
chemical constitution is variable, a (CuS04 )X[Al(OH)3]m -
water wash will remove a portion of ~he CUSO4 - and the
S04 may be exchanged for other anions without altering
the crystal character.
.
This microcrystalline copper aluminate is
formed within the pores of a macroporous anion exchan~e
resin. The anion exchange resin is a cross-linked
styrene-divinyl benzene polymer network to which is
affixed -CH2N(CH3)2 groups or
28,147-F ~19-
-20-
-CH2N(CH3)3
OH
grou~s. These macroporous resins normally contain
about 30-40 percent porosity and have a surface area of
40-50 m2/g-
Such resin composites usually contain 0.8-3.0
moles Al/mole N and about 0.5 1.0 moles Cu/mole ~l.
Example 5 (Mn Alumlnates)
90 ~1 of a macroporous anion exchange resin,
which has been treated once with saturated AlCl3, dried
and then added to 30 percent a~ueous NH3 to precipitate
the Al(OH)3 within the pores of the resin, is wet with
water under vacuum to displace all air, and then is
titrated in the presence of NH4 Cl with 130 me~ of HCl
to pH 5 at 80C. Yield is 134 ml of the chloride form
of the resin + Al(0~)3. In about 300 ml total volume
50 g MnCl2-4E20 is added at 30C, to pH 5.6. All is
heated to 80C and one normal NaOH is dripped in at
constant pEI 600. After 39.5 meq of NaOH a brown precipi-
tate is ob~erved. Then are added 10 meq HCl to pH 5.4
at 78C. All of the dark precipitate does not dissolve
and the sample is put into a 95C oven overnight. By
x-ray analysis there is found a small amount of
~5 MnCl2-nAl(OH)3 a~d Bayerite or Norstrandite. After
three days it is washed, excess NH40H added, then
washed again; then is added NaCl plus e~cess MhCl2, and
heated to 75C, with a resulting pH of 5.7. After 95C
oven heating overnight it gives good crystals of the
aluminate in the resin.
28,147-F -20-
.
5 ~ ~
-21-
In a glass-jacketed column is placed 110 ml
of the resin and, at 65C, pump first brine, then water
at 10 ml/min.
The synthetic brine is pxepared by dissolving
3.6024 g MnCl2/4H2O, 295 g NaCl in 885 g H2O to yield
one liter containing 1.O g Mn/liter. Samples are
collected and analyzed for Mn.
Brine CutVol cc q Mn/liter
100 --
2 100 0.8
3 50 0.6
4 50 0.65
0.75
6 50 0.75
7 50 __
8 50 __
9 50 0.75
To W_ter
o.go
11 25 1.50
12 25 7.70
13 25 16.00
14 25 15.00
13.20
~5 16 2~ 12.50
The crystalline manganese aluminate in its
chloride form has been identified by x-ray diffraction
and its hexagonal structure has been closely defined.
The chemical constitution is variable; a (MnCl2)~Al(OH~3]
water wash will xemove a portion of the ~nCl2 - and the
Cl may be exchanged fox other anions withou-t altering
the crystal character.
28,147-F -21-
I l~S~
-22-
This microcrystalline manganese aluminate is
formed within the pores of a macroporous anio~ exchange
resin. The anion exchange resin is a cross-linked
styrene-divinyl benzene polymer network to whlch is
affixed -CH2N(CH3)3 groups or
-cH2N~cH3)3
OH
groups.
The resin composites prepared usually contain
0.8-3.0 moles Al/mole N and about 0.5-1.0 moles Mn/mole
Al.
Example 6 ~Fe Al m_nates)
A sample of macroporous anion exchange resin
is equilibrated with 30 percen~ AlC13 solution, dried
to free flowing, then added to excess aqueous 30 percent
NH3. After washing, 115 ml of the product is further
treatedO
A large amount of NH4Cl is added and the
whole slurry is titrated with 50 meq HCl at 35C to
pH 7. About 300 cc of deionized H20 and 69.5 g
FeSO47H20 are added and the sample placed into a 95C
oven. After 24 hours, and after cooling to 25C the pH
is 4.5. Some crystalline FeSO4 nA-l(OH)3 is found by
x-ray. The resin composite is washed with H20, slurried
in excess NH4 OH and washed again. The wet resin with~
300 ml H20 and 69~5 g FeSO4 7H20, is again placed in a
95 ovenO ~fter an additional 24 hours, the resin is
again washed with N~40H, then returned with 20.0 g
FeSO4 7H20 to the 95C oven ~or another 24 hours. The
product is now well crystallized.
28,147~F -22-
-23-
llO Ml of the product are placed in a jacketed
temperature controlled column, and sy:nthetic brine and
water are pumped through at 10 ml/min and 65C. Samples
are collected and titra-ted for Fe(+2). Feed brine is
prepared by adding Fe(+2) to 1 g/lite:r in 25 percent NaCl
~0.035 N Fe(+2~].
Brlne CutVol ccNormality, in Fe
1 100 Discarded
2 100 0.0015
3 100 0.0030
4 100 0.0030
100 0.0120
~ lO0 0.020
7 100 0.023
8 ~00 0.02~
9 100 0.0275
0.0282
~20
1 50 0.029
2 50 0.134
3 25 0.236
4 25 0.188
0.150
6 25 0.128
7 25 0.112
8 25 0.102
9 25 0.092
1~ 25 0.08
; 28,147-F -23~
