# US 10,501,332 B2 · Structured zirconium solutions

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- Number: US 10,501,332 B2
- Document ID: US10501332B2
- Status: Granted
- Kind: B2
- Application number: 15/770,070
- Filed: 2016-10-27
- Published: 2018-11-08
- Granted: 2019-12-10
- Earliest claimed: 2015-10-27
- Assignees: Magnesium Elektron Limited
- Applicants: Magnesium Elektron Limited
- Inventors: David Alastair Scapens
- Web page: https://patentgrep.com/patent/US10501332B2

## CPC

- C01G 25/02: Oxides
- B01D 53/945: {characterised by a specific catalyst}
- B01J 13/0021: {containing a solid organic phase}
- B01J 13/0047: {containing a metal oxide}
- B01J 21/066: {Zirconium or hafnium; Oxides or hydroxides thereof}
- B01J 23/002: {Mixed oxides other than spinels, e.g. perovskite}
- B01J 23/10: of rare earths
- B01J 27/053: Sulfates
- B01J 35/613: {10-100 m2/g}
- B01J 35/633: {less than 0.5 ml/g}
- B01J 35/635: {0.5-1.0 ml/g}
- B01J 35/647: {2-50 nm}
- B01J 35/651: {50-500 nm}
- B01J 37/03: Precipitation; Co-precipitation
- B01J 37/031: {Precipitation}
- B01J 37/036: {to form a gel or a cogel}
- B01J 37/04: Mixing {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/06: Washing {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/10: in the presence of water, e.g. steam
- B01J 37/20: Sulfiding
- C01F 17/32: oxide or hydroxide being the only anion, e.g. NaCeO2 or MgxCayEuO
- C01G 25/006: {Compounds containing zirconium, with or without oxygen or hydrogen, and containing two or more other elements}
- B01D 2255/407: Zr-Ce mixed oxides
- B01J 23/20: Vanadium, niobium or tantalum
- B01J 23/28: Molybdenum
- B01J 23/30: Tungsten
- B01J 35/30: characterised by their physical properties
- B01J 2235/00: Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
- B01J 2523/00: Constitutive chemical elements of heterogeneous catalysts
- C01P 2002/52: containing elements as dopants
- C01P 2002/60: Compounds characterised by their crystallite size
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C01P 2002/88: by thermal analysis data, e.g. TGA, DTA, DSC
- C01P 2006/12: Surface area
- C01P 2006/13: thermal stability thereof at high temperatures
- C01P 2006/14: Pore volume
- C01P 2006/16: Pore diameter
- C01P 2006/17: Pore diameter distribution
- Y02A 50/20: Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
- Y02T 10/12: Improving ICE efficiencies
- 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)
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C01F: COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts of peroxyacids C01B15/00; sulfides or polysulfides of magnesium, calcium, strontium, or barium C01B17/42; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds other than ammonia or cyanogen containing nitrogen and non-metals and optionally metals C01B21/082; amides or imides of silicon C01B21/087}; metal {imides or} amides C01B21/092, {C01B21/0923}; 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 cyanic acid C01C3/14; salts of cyanamide C01C3/16; thiocyanates C01C3/20; {double sulfates of magnesium with sodium or potassium C01D5/12; with other alkali metals C01D15/00, C01D17/00})
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- Y02A: TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02T: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION

## Abstract

This invention relates to a zirconium solution or sol comprising: (a) zirconium, (b) nitrate, acetate and/or chloride ions, and (c) one or more complexing agents being an organic compound comprising at least one of the following functional groups: an amine, an organosulphate, a sulphonate, a hydroxyl, an ether or a carboxylic acid group, wherein the molar ratio of components (a):(b) is 1:0.7 to 1:4.0, the molar ratio of components (a):(c) is 1:0.0005 to 1:0.1, and the pH of the zirconium solution or sol is less than 5. The invention also relates to a process for preparing a zirconium solution or sol, the process comprising the steps of: (a) dissolving a zirconium salt in nitric, acetic and/or hydrochloric acid, and (b) adding one or more complexing agents to the resulting solution, the one or more complexing agents being an organic compound comprising at least one of the following functional groups: an amine, an organosulphate, a sulphonate, a hydroxyl, an ether or a carboxylic acid group, and (c) heating the solution or sol to a temperature of at least 75° C. In addition, the invention relates to products formed from the zirconium solution or sol or obtainable by the process.

## Claims

### Claim 1

A zirconium solution or sol comprising:
(a) zirconium,
(b) nitrate, acetate and/or chloride ions, and
(c) one or more complexing agents being an organic compound comprising at least one of the following functional groups: an amine, an organosulfate, a sulfonate, a hydroxyl, a dicarboxylic acid or an alpha hydroxycarboxylic acid,
wherein the molar ratio of components (a):(b) is 1:0.7 to 1:4.0, the molar ratio of components (a):(c) is 1:0.0005 to 1:0.1, and the pH of the zirconium solution or sol is less than 5.

### Claim 2 (depends on 1)

A zirconium solution or sol as claimed in claim 1 wherein when the solution or sol comprises nitrate ions as component (b), the molar ratio of components (a):(b) is 1:0.8 to 1:2.0; when the solution or sol comprises acetate ions as component (b), the molar ratio of components (a):(b) is 1:1.5 to 1:4.0; and when the solution or sol comprises chloride ions as component (b), the molar ratio of components (a):(b) is 1:0.7 to 1:2.2.

### Claim 3 (depends on 1)

A zirconium solution or sol as claimed in claim 1, comprising nitrate ions as component (b).

### Claim 4 (depends on 3)

A zirconium solution or sol as claimed in claim 3, wherein there is an increase in size of the absorbance peak at 361 nm as measured by UV-Vis spectroscopy by a factor of 2.7 after the solution is heated to a temperature of 94° C. at a heating rate of 1° C./min, with a dwell time of 2 hours.

### Claim 5 (depends on 1)

A zirconium solution or sol as claimed in claim 1 having a refractive index of at least 1.34.

### Claim 6 (depends on 1)

A zirconium solution or sol as claimed in claim 1, wherein the conductivity in mS/cm is at least 10% higher after being heated to a temperature of 94° C. at a heating rate of 1° C./min, with a dwell time of 2 hours.

### Claim 7 (depends on 1)

A zirconium solution or sol as claimed in claim 1, wherein component (a) is zirconium basic sulfate.

### Claim 8 (depends on 1)

A zirconium solution or sol as claimed in claim 1, wherein the solution or sol comprises zirconium in an amount of 5-30% by weight based on ZrO2 equivalent.

### Claim 9

A process for preparing a zirconium solution or sol, the process comprising the steps of:
(a) dissolving a zirconium salt in nitric, acetic and/or hydrochloric acid, and
(b) adding one or more complexing agents to the resulting solution, the one or more complexing agents being an organic compound comprising at least one of the following functional groups: an amine, an organosulfate, a sulfonate, a hydroxyl, a dicarboxylic acid or an alpha hydroxycarboxylic acid, and
(c) heating the solution or sol to a temperature of at least 75° C.

### Claim 10 (depends on 9)

A process as claimed in claim 9, wherein the zirconium salt is zirconium basic carbonate.

### Claim 11 (depends on 9)

A process as claimed in claim 9, wherein in step (a) the solution or sol is heated to a temperature of at least 40° C.

### Claim 12 (depends on 9)

A process as claimed in claim 9, wherein the method comprises the step of increasing the pH of the solution or sol by adding a base.

### Claim 13 (depends on 9)

A process as claimed in claim 9, wherein in step (c) the heating comprises heating the solution or sol to a temperature of at least 80° C.

### Claim 14 (depends on 9)

A process as claimed in claim 9, wherein in step (c) the solution is maintained at that temperature for 1-5 hours.

### Claim 15 (depends on 9)

A process as claimed in claim 9 comprising, after step (c), the step of:
(d) adding sulfate ions.

### Claim 16 (depends on 9)

A process as claimed in claim 9, wherein the solution or sol comprises zirconium in an amount of 5-30% by weight based on ZrO2 equivalent.

### Claim 17 (depends on 1)

A mixed metal hydroxide, mixed metal oxide, crosslinker, or functional or non-functional binder, formed from a zirconium solution or sol as claimed in claim 1.

### Claim 18 (depends on 15)

A zirconium basic sulfate obtainable by the process of claim 15.