Catalyst – solid sorbent – or support therefor: product or process – Zeolite or clay – including gallium analogs – Clay
Reexamination Certificate
2002-03-15
2004-11-09
Nguyen, Cam N. (Department: 1754)
Catalyst, solid sorbent, or support therefor: product or process
Zeolite or clay, including gallium analogs
Clay
C502S073000, C502S084000, C501S108000, C501S118000, C501S119000, C501S120000, C501S125000, C501S127000, C501S128000, C501S129000, C501S141000
Reexamination Certificate
active
06815389
ABSTRACT:
BACKGROUND OF THE INVENTION
This invention involves the preparation of anionic clays and the preparation of Mg—Al solid solutions by heat-treatment of the anionic clay. Anionic clays have a crystal structure which consists of positively charged layers built up of specific combinations of metal hydroxides between which there are anions and water molecules. Hydrotalcite is an example of a naturally occurring anionic clay, in which carbonate is the predominant anion present. Meixnerite is an anionic clay wherein hydroxyl is the predominant anion present.
In hydrotalcite-like anionic clays the brucite-like main layers are built up of octahedral alternating with interlayers in which water molecules and anions, more particularly carbonate ions, are distributed. The interlayers may contain anions such as NO
3
−
, OH, Cl
−
, Br
−
, I
−
, SO
4
2−
, SiO
3
2−
, CrO
4
2−
, BO
3
2−
, MnO
4
−
, HGaO
3
2−
, HVO
4
2−
, ClO
4
−
, BO
3
2−
, pillaring anions such as V
10
O
28
−6
and Mo
7
O
24
6−
, monocarboxylates such as acetate, dicarboxylates such as oxalate, and alkyl sulphonates such as laurylsulphonate.
It should be noted that a variety of terms are used to describe the material which is referred to herein as an anionic clay. Hydrotalcite-like and layered double hydroxide are interchangeably used by those skilled in the art. Herein, the materials are referred to as anionic clays, comprising within that term hydrotalcite-like and layered double hydroxide materials.
The preparation of anionic clays has been described in many prior art publications.
Recently, two major reviews of anionic clay chemistry were published in which the synthesis methods available for anionic clay synthesis have been summarized, F. Cavani et al., “Hydrotalcite-type anionic clays: Preparation, Properties and Applications,”
Catalysis Today”,
11 (1991) Elsevier Science Publishers B. V. Amsterdam.
J P Bessee and others, “
Anionic clays: trends in pillary chemistry, its synthesis and microporous solids
” (1992), 2, 108, editors: M. I. Occelli, H. E. Robson, Van Nostrand Reinhold, N.Y.
In these reviews the authors state that a characteristic of anionic clays is that mild calcinations at 500° C. results in the formation of a disordered MgO-like product. The disordered MgO-like product is distinguishable from spinel (which results upon severe calcination) and from anionic clays. Herein, the disordered MgO-like materials are referred to as Mg—Al solid solutions. Furthermore, these Mg—Al solid solutions contain a well-known memory effect whereby the exposure to water of such calcined materials results in the reformation of the anionic clay structure.
For work on anionic clays, reference is given to the following articles:
Helv Chim. Acta,
25, 106-137 and 555-569 (1942)
J Am. Ceram. Soc.,
42, no. 3, 121 (1959)
Chemistry Letters (Japan),
843 (1973)
Clays and Clay Minerals,
23, 369 (1975)
Clays and Clay Minerals,
28, 50 (1980)
Clays and Clay Minerals,
34, 507 (1996)
Materials Chemistry and Physics,
14, 569 (1986).
In addition there is an extensive amount of patent literature on the use of anionic clays and processes for their preparation.
European Patent Application 0 536 879 describes a method for introducing pH-dependent anions into the clay. The clay is prepared by the addition of a solution of Al(NO
3
)
3
and Mg(NO
3
)
2
to a basic solution containing borate anions. The product is then filtered, washed repeatedly with water, and dried overnight. Additionally mixtures of Zn/Mg are used.
In U.S. Pat. No. 3,796,792 by Miyata entitled “Composite Metal Hydroxides” a range of materials is prepared into which an extensive range of cations is incorporated, including Sc, La, Th, In, etc. In the examples given solutions of the divalent and trivalent cations are prepared and mixed with base to cause co-precipitation. The resulting products are filtered, washed with water, and dried at 80° C. Example 1 refers to Mg and Al and Example 2 to Mg and Bi. Other examples are given, and in each case soluble salts are used to make solutions prior to precipitation of the anionic clay at high pH.
In U.S. Pat. No. 3,879,523 by Miyata entitled “Composite Metal Hydroxides” also a large number of preparation examples is outlined. The underlying chemistry, however, is again based on the co-precipitation of soluble salts followed by washing and drying. It is important to emphasize that washing is a necessary part of such preparations, because to create a basic environment for co-precipitation of the metal ions a basic solution is needed and this is provided by NaOH/Na
2
CO
3
solutions. Residual sodium, for example, can have a significant deleterious effect on the subsequent performance of the product as a catalyst or oxide support.
In U.S. Pat. No. 3,879,525 (Miyata) very similar procedures are again described.
In U.S. Pat. No. 4,351,814 to Miyata et al. a method for making fibrous hydrotalcite is described. Such materials differ in structure from the normal plate-like morphology. The synthesis again involves soluble salts. For example, an aqueous solution of a mixture of MgCl
2
and CaCl
2
is prepared and suitably aged. From this a needle-like product Mg
2
(OH)
3
Cl.4H
2
O precipitates. A separate solution of sodium aluminate is then reacted in an autoclave with the solid Mg
2
(OH)
3
Cl.4H
2
O and the product is again filtered, washed with water, and dried.
In U.S. Pat. No. 4,458,026 to Reichle, in which heat-treated anionic clays are described as catalysts for aldol condensation reactions, again use is made of magnesium and aluminum nitrate salt solutions. Such solutions being added to a second solution of NAOH and Na
2
CO
3
. After precipitation the slurry is filtered and washed twice with distilled water before drying at 125° C.
In U.S. Pat. No. 4,656,156 to Misra the preparation of a novel absorbent based on mixing activated alumina and hydrotalcite is described. The hydrotalcite is made by reacting activated MgO (prepared by activating a magnesium compound such as magnesium carbonate or magnesium hydroxide) with aqueous solutions containing aluminate, carbonate and hydroxyl ions. As an example the solution is made from NAOH Na
2
CO
3
and Al
2
O
3
. In particular, the synthesis involves the use of industrial Bayer liquor as the source of Al. The resulting products are washed and filtered before drying at 105° C.
In U.S. Pat. No. 4,904,457 to Misra a method is described for producing hydrotalcites in high yield by reacting activated magnesia with an aqueous solution containing aluminate, carbonate, and hydroxyl ions.
The methodology is repeated in U.S. Pat. No. 4,656,156.
In U.S. Pat. No. 5,507,980 to Kelkar et al. a process is described for making novel catalysts, catalyst supports, and absorbers comprising synthetic hydrotalcite-like binders. The synthesis of the typical sheet hydrotalcite involves reacting pseudo-boehmite to which acetic acid has been added to peptize the pseudo-boehmite. This is then mixed with magnesia. More importantly, the patent summary states clearly that the invention uses mono carboxylic organic acids such as formic, propionic and isobutyric acid. In this patent the conventional approaches to preparing hydrotalcite are presented.
In U.S. Pat. No. 5,439,861 a process is disclosed for preparing a catalyst for synthesis gas production based on hydrotalcite. The method of preparation is again based, on the co-precipitation of soluble salts by mixing with base, for example, by the addition of a solution of RhCl
3
, Mg(NO
3
)
2
and Al(NO
3
)
3
to a solution of Na
2
CO
3
and NaOH.
Also in U.S. Pat. No. 5,399,537 to Bhattacharyya in the preparation of nickel-containing catalysts based on hydrotalcite use is made of the co-precipitation of soluble magnesium and aluminum salts.
In U.S. Pat. No. 5,591,418 to Bhattacharyya a catalyst for removing sulfur oxides or nitrogen oxides from a gaseous mixture is made by calcining an anionic clay, the anionic clay having been prepared by co-precipitation of a solution of Mg(NO
3
)
2
,
Brady Michael F.
Jones William
Kooli Fathi
Stamires Dennis
Akzo Nobel NV
Nguyen Cam N.
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