# US 4,392,980 A · Transition metal aluminates

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- Number: US 4,392,980 A
- Document ID: US4392980A
- Status: Granted
- Kind: A
- Application number: 06/362,690
- Filed: 1982-03-29
- Granted: 1983-07-12
- Earliest claimed: 1977-07-05
- Assignees: The Dow Chemical Company
- Inventors: John M. Lee; William C. Bauman
- Web page: https://patentgrep.com/patent/US4392980A

## CPC

- C01G 45/22: Compounds containing manganese, with or without oxygen or hydrogen, and containing two or more other elements
- B01J 41/10: Inorganic material
- C01G 3/006: {Compounds containing copper, with or without oxygen or hydrogen, and containing two or more other elements}
- C01G 9/006: {Compounds containing zinc, with or without oxygen or hydrogen, and containing two or more other elements}
- C01G 49/009: {Compounds containing iron, with or without oxygen or hydrogen, and containing two or more other elements}
- C01G 51/82: Compounds containing cobalt, with or without oxygen or hydrogen, and containing two or more other elements
- C01G 53/82: Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
- C22B 3/42: by ion-exchange extraction
- C01P 2002/77: by unit-cell parameters, atom positions or structure diagrams
- Y02P 10/20: Recycling
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C22B: PRODUCTION AND REFINING OF METALS (electrolytic C25); PRETREATMENT OF RAW MATERIALS
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Crystalline transition metal aluminates conforming generally to the formula MA.sub.a.sup.v Z.sub.b.sup.v.nAl(OH).sub.3.mH.sub.2 O where M is a transition metal having a valence charge of +2 selected from the group consisting of Cu, Zn, Mn, Fe, Co, and Ni, where AZ represents negative valence ions or radicals, v is a negative valence of 1, 2, or 3, n is a value to provide a mol ratio of Al/M of at least 1/1, preferably at least 1.5/1, 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 are caused to form adducts with amorphous hydrous alumina, Al(OH).sub.3, said adducts forming crystals when heated, said aluminates being useful, e.g., as ion exchangers and as spinel precursors among other things.

## Claims

### Claim 1

Crystalline transition metal aluminates conforming generally to the formula
MA.sub.a.sup.v Z.sub.b.sup.v.nAl(OH).sub.3.mH.sub.2 O
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.

### Claim 2 (depends on 1)

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 about 5.2-5.5 (direct) and a c-axis cell constant in the range of about 20-50 (direct).

### Claim 3 (depends on 1)

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.

### Claim 4 (depends on 1)

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.

### Claim 5 (depends on 1)

The aluminate of claim 1 wherein the radical(s) or anion(s) are selected from the group consisting of OH.sup.-, halide.sup.-, sulfate.sup.--, carbonic.sup.--, hydrocarbonic.sup.-, formate.sup.-, hydrophosphate.sup.--, acetate.sup.-, nitrate.sup.-, citrate.sup.---, chromate.sup.-, ascorbic.sup.-, oxalate.sup.--, and trichloracetic.sup.-.

### Claim 6 (depends on 1)

The aluminate of claim 1 when in crystalline form identifiable by x-ray diffraction as being hexagonal having a-axis of about 5.2-5.5 (direct) and c-axis of about 20-50 (direct), where M is at least one metal selected from the group consisting of Cu, Zn, Mn, Fe, Co, and Ni.
where AZ is at least one anion selected from the groups consisting of halo, sulfate, nitrate, hydrophosphate, carbonate, hydrocarbonate, formate, acetate, citrate, hydroxy, chlorate, perchlorate, sulfite, borate, and nitrate.
where n is an integer to provide an Al/M ratio in the range of about 1/1 to about 4/1, and
m is an integer in the range of zero to maximum for waters of hydration.

### Claim 7 (depends on 1)

The aluminate of claim 1 when unsupported by a substrate.

### Claim 8 (depends on 1)

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 amorphous hydrous alumina, Al(OH).sub.3,
heating the so-formed adduct to crystallization at a temperature in the range of about 50.degree. C. to about 150.degree. C. for a period of time from about 1 hour to about 100 hours, and
recovering the so-formed transition metal aluminate.

### Claim 9 (depends on 8)

The method of claim 8 wherein there is supplied in the aqueous medium a substrate upon which the adduct is formed.

### Claim 10 (depends on 9)

The method of claim 9 wherein the substrate is an ion exchange resin.

### Claim 11 (depends on 10)

The method of claim 10 wherein the ion exchange resin is reticular.

### Claim 12 (depends on 10, 11)

The method of claim 10 or 11 wherein the ion exchange resin is a cation exchange resin.

### Claim 13 (depends on 10, 11)

The method of claim 10 or 11 wherein the ion exchange resin is an anion exchange resin.

### Claim 14 (depends on 9)

The method of claim 9 wherein the substrate is at least one selected from the group consisting of natural inorganic, natural organic, metallic, synthetic polymers, synthetic resins, and synthetic inorganics.