P.O. Box 6, Clifton Junction, Swinton, Manchester M27 8LS, England.

Magnesium Elektron Inc., 500 Point Breeze Rd, Flemington, NJ 08822, USA Nikkei-MEL, 4025-1, Shimizu-Miho, Shizuoka City, Shizuoka Prefecture, 424-0901, Japan. A Luxfer Group Company

Hydrotalcites
Hazel Stephenson, Heather Bradshaw, MEL Chemicals, Clifton Junction, Swinton, Manchester M27 8LS, England.

Introduction
In 2006 we began development on a range of hydrotalcites. To date we have been focusing our development on products primarily for use as carbon dioxide sorbants to complement our melsorb product range, however there are a wide variety of applications that can use hydrotalcites, examples include: Additives for polymers Anion exchange Antacids Catalysts Catalyst supports Nuclear waste treatment Sorbants Water purification Hydrotalcites are formed in nature by the weathering of basalts or from precipitation in saline water sources, they are of the general formula:

gentle calcination, the double layered hydroxide structure can be regenerated by exposure to anions, hence use as regenerable CO2 sorbants. The mixed oxides resulting from calcinations of hydrotalcites can be useful in catalytic applications, due to their high surface area and large pores, but also the distribution of metals on the surface.

Figure 4: SEM of XZO 1679/01

Summary
Hydrotalcites can be used in a variety of applications. Modifying the structure by addition of zirconia and / or alternative metals gives us the ability to tailor the product properties to suit the specific application. Tuneable properties include: Activity of supported metal Basisity Capacity Kinetics: sorption/ion exchange Particle size Selectivity Surface area

Products
Using our experience in the preparation of mixed oxides we have been working on process improvements to the standard preparation techniques, aiming to give improved impurity removal, increased surface area stability and particle size control. We have developed a product called XZO 1679/01 which has a Mg : Al : Zr 2.5 of 3:0.78 0.14. ratio

Characterisation 2.0
Wt% CO2

[M2+1-x M3+x(OH)2x]x+ (An- )x/n.mH2O M2+ is typically Mg but can be Ni, Zn, Cu. M3+ is typically Al but can be Cr, Mn, Co, Fe. A is any anion.
Anions Water molecules OH-

Calcination 1.5 condition (C / hrs) 1.0 Dried

0.5

Surface Area (m2/g) 67 225

Total pore volume (ml / g) 0.27 0.60

250 0.66 300

Samples
Laboratory samples of XZO 1679/01 up to 500g and pilot plant samples up to 5kg are available on request. For larger quantities, or information on other compositions that are available please contact: melchemsales@melchemicals.com or our agents O.C. Lugo, at info@oclugo.com.

400/2
0.0 0 450/2 50 100

M2+ or M3+

200 Time (mins)

150 193

500/2 700/2
1.2

177 157

0.58 0.73

Hydrotalcites are useful in such a variety of applications due to their layered double hydroxide structure (LDH). The cations create an overall positive charge in the layers, which is balanced by the presence of anions in the interlayer. These anions in the interlayer can be exchanged, the order of preference typically being: NO3- < Br- < Cl- < F- < OH- < SO42< CrO42- < HAsO42- < HPO42- < CO32-

Figure 1: Table of data for XZO 1679/01

2.5 1.0
Wt% CO2 Wt% CO 2

Acknowledgments
MEL Chemicals / MEI would like to thank Dr Alexei Lapkin (a.lapkin@bath.ac.uk) and Alina Iwan at Bath University for their help measuring CO2 sorption, SEM and continued support in CO2 sorption projects.

2.0 0.8
0.6 1.5 0.4 1.0 0.2 0.5 0.0

References
0 5 10 15 Time (mins) 100 150 200 250 Time (mins) 20

0.0

Counts Wt% CO2

M+ and M4+ metals can be used to part substitute M2+ or M3+, this enables fine Figure 2: Uptake of CO2 at 25C for XZO 1679/01 tuning of the product to suit specific applications by reducing or increasing the 5000 overall positive charge, and thus the capacity 1.2 Aged 0700/2 for anions, basisity and catalytic activity. 4000 1.0 Aged 0500/2 Another interesting property of hydrotalcites 3000 is their memory effect, after relatively 0.8 Aged 0450/2
2000 0.6 1000 0.4 0 0.2 10 20 30 Aged 0400/2 As Received 40 2 Theta 50 60 70

50

300

0.0 0 5

1679/01 Figure 3: XRD of XZO Time (mins)

10

15

20

1. Tsuji, M. et al. Hydrotalcites with an extended Al3+ substitution: Synthesis, simultaneous TG-DTA-MS study, and their CO2 adsorption behaviors. J. Mater. Res.,1993 8(5). 2. Velu, S. Ramaswamy, V. Ramani, A. New hydrotalcite-like anionic clays containing Zr4+ in the layers. Chem. Commun,. 1997, 2107. 3. Tichit, D et al, Preparation of Zr containing Layered Double Hydroxides and characterization of the acido-basic properties of their mixed oxides, Chem. Mater. 2002, 14, 1530-1538. 4. Braterman, P.S. Xu, Z.P, Yarberry, F. Layered Double Hydroxides. (LDHs) Handbook of Layered Materials. 5. Das, N.N. et Al, Adsorption of Cr(VI) and Se(IV) from their aqueous solutions onto Zr4+ substituted ZnAl/Mg/Al-layered double hydroxides: effect of Zr4+ substitution. Colloid and interface science 2004 1-8. 6. Velu. S. et al. Selective production of hydrogen from fuel cells via oxidative steam reforming of methanol over CuZrAl(Zr) oxide catalysts. Applied Cat. 2001, 213 47.

5000 Aged 0700/2 4000

Counts

Aged 0500/2 3000 Aged 0450/2 2000 Aged 0400/2 1000 As Received 0 10 20 30 40 2 Theta 50 60 70