CA1165535A - Transition metal aluminates - Google Patents

Abstract

ABSTRACT
Crystalline transition metal aluminates having to the formula MA?Z??nA1(OH)3?mH2O
where M is a transition metal having a valence of +2 selected from Cu, Zn, Mn, Fe, Co, and Ni, where AZ
represents negative valence ions or radicals, v is a valence of -1, -2, or -3, n is a value to provide a mol ratio of Al/M of at least 1/1, and m is an integer of from zero to the maximum for waters of hydration, with (va)+(vb) equal to 2, are prepared in alkaline aqueous medium wherein transition metal compounds to form adducts with amorphous hydrous alumina, Al(OH)3, said adducts forming crystals when heated, said aluminates being useful as ion exchangers and as spinel precursors.

Description

5 3 ~i 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~

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 ~ ~

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~

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 3 ~

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-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.

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 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 ~ ~

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 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 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 ~

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~

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 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 ~ ~

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-~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-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--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 ~ ~

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 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~

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-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~

Claims (13)

1. Crystalline transition metal aluminates conforming generally to the formula MA?Z??nAl(OH)3?mH2O

where M 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, with (va)+(vb) equal to 2, and with m being a value of zero or more.

2. The aluminate of Claim 1, wherein the crystallinity is identifiable by x-ray diffraction as being hexagonal having an a-axis cell constant in the range of 5.2-5.5 (direct) and a c-axis cell constant in the range of 20-50 (direct).

3. The aluminate of Claim 1 wherein the radical(s) or anion(s) (AZ) are selected from the groups consisting of hydroxyl, halide, organic and inorganic acid moieties having valences of from one to three, inclusive.

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4. The aluminate of Claim 1 wherein the transition metal is only one metal selected from the group consisting of Cu, Zn, Mn, Fe, Co, and Ni.

5. The aluminate of Claim 1 where n is an integer to provide an Al/M ratio in the range of 1/1 to 4/1, and m is an integer in the range of zero to maximum for waters of hydration.

6. The aluminate of Claim 1 when supported on a polymeric substrate having ion exchange function-alities.

7. The aluminate of Claim 1 when supported on or within a cation exchange resin.

8. The aluminate of Claim 1 when supported on or within an anion exchange resin.

9. The aluminate of Claim 1 when supported on or within a reticular ion exchange resin.

10. A method for preparing the aluminates of Claim 1, said method comprising: mixing amorphous hydrous alumina in an alkaline aqueous medium with the requisite transition metal compound, thus forming an adduct of the transition metal compound with the amor-phous hydrous alumina, Al(OH)3; heating the so-farmed adduct to crystallization at a temperature in the range of 50°C to 150°C for a period of time from 1 hour to 100 hours; and recovering the so-formed transition metal aluminate.
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11. The method of Claim 10 wherein there is supplied in the aqueous medium a substrate upon which the adduct is formed.

12. The method of Claim 11 wherein the substrate is an ion exchange resin.

13. 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 transition metal aluminate being defi-cient in said transition metal ion at the outset;
continuing said reaction until the said transition metal aluminate has become substantially enriched by transition metal ions from the said aqueous solution.

28,147-F -26-