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Mesoporous silicoaluminate products and production thereof by controlled acid extraction of aluminum from calcium bentonite clay


Disclosed is a process of making mesoporous silico-aluminates from calcium bentonite by controlled extraction of octahedral aluminum under mild condition, by acid, preferably phosphoric acid. The mesoporous silicoaluminates contain only tetrahedral aluminum as the residual aluminum. As the result of the selective removal of the octahedral aluminum, the mesoporous silico-aluminates have several unprecedented properties compared to products produced by conventional processes either by mild acid-activation or by a removal of all the aluminum.


What is claimed:

1. A method for producing an amorphous mesoporous silicoaluminate containing at least 0.5 weight percent aluminum from a calcium bentonite clay mineral containing octahedral and tetrahedral aluminum in the framework of the mineral, which comprises mixing said calcium bentonite clay with sufficient acid to leach substantially all of said octahedral aluminum without removing tetrahedral aluminum as determined by using .sup.27 Al NMR to determine that tetrahedral aluminum has not been removed.

2. The method of claim 1, wherein the acid is a mineral or organic acid.

3. The method of claim 1, wherein the acid is phosphoric.

4. The method of claim 3, wherein the concentration of said phosphoric acid is in the range of 1 to 6M.

5. The method of claim 1, wherein aluminum is leached at a temperature of to C.

6. The method of claim 3, wherein the residue of phosphoric acid after leaching is washed with sufficient water to reduce the level of phosphorous to below 1.0 wt %, expressed as P205.

7. The method of claim 1, wherein the calcium bentonite prior to leaching contains less than 2.0 wt % of iron, expressed as Fe.sub.2 O.sub.3, and after leaching has a BET surface area in the range of 600-730 m.sup.2 /g, a pore volume in the range 0.4 to 0.8 cc/g, and pore diameter in the range of 30-60 .ANG. unit.

8. The method of claim 1, wherein the calcium bentonite prior to leaching contains more than 5.0 wt % of iron, expressed as Fe.sub.2 O.sub.3 , and the leached clay has a BET surface area in the range of 300 to 500 m.sup.2 /g, a pore volume in the range of 0.4 to 0.8 cc/g, and pore diameter in the range of 50 to 80 .ANG..

9. A mesoporous silicoaluminate residue of calcium bentonite clay having a BET surface area in the range of 600 to 730 m.sup.2 /g and a pore volume in the range of 0.4 to 0.8 cc/g, a pore diameter in the range of 30-60 .ANG. units, said residue containing tetrahedral aluminum but no octahedral aluminum.

10. The composition of claim 9 obtained from a Cheto bentonite clay.

11. A mesoporous silicoaluminate residue of calcium bentonite clay having a BET surface area in the range of 300 to 500 m.sup.2 /g, a pore volume in the range of 0.4 to 0.8 cc/g and a pore diameter in the range of 50 to 80 .ANG. units, said residue containing tetrahedral aluminum but no octahedral aluminum.

12. The composition of claim 11 obtained from Fowlkes clay.



This invention relates to novel mesoporous silico-aluminate products and to a process for making such products by controlled extraction of octahedral aluminum from a calcium bentonite clay by an acid, preferably phosphoric acid, leaving mesoporous silicoaluminate containing tetrahedral aluminum in the solid residue.


Calcium bentonite clays, i.e., clay in which the principal exchangeable cation is a calcium ion, are also referred to as sub-bentonites, calcium montomorillonites or calcium smectites. Generally, these are hydrated aluminosilicate crystalline minerals. Usually, magnesium proxies for some of the aluminum in the crystals of the clay. Iron content varies with clays from different deposits.

For many years, selected bentonite source clays have been treated on a commercial scale with acids to leach aluminum from the structure. The acid leaching has been practiced to produce bleaching earths, cracking catalysts and reactive pigments for carbonless copying paper, among other commercial applications. See for example, patents and publications cited in U.S. Pat. Nos. 5,008,226 and 5,008,227.

The starting clays which are used to produce known forms of acid leached bentonites typically contain approximately 20% alumina (based on the dry weight). The aluminum in bentonites are in octahedral and tetrahedral bonding structures. Acid dosages of about 40-50 gm of 96% H.sub.2 SO.sub.4 /100 gm clay are typically used. Alkaline earth and alkali metals are removed. The clays are usually leached to a residual aluminum content in the range of about 10-15 wt. %. The extent of leaching varies inter alia with the intended use of the leached clay. However, in general practice, both octahedral and tetrahedral aluminum remain in the solid residue which, when studied by XRD, exhibits lines characteristic of the clay crystals. The acid treated clay is invariably washed to remove soluble salts and entrained acid. While sulfuric acid is usually the acid of choice, other acids such as phosphoric and citric acids have been proposed.

It is known that repeated sulfuric acid leaches, resulting in extractions in excess of those used in the typical commercial prior art practice, can produce siliceous residues with essentially no aluminum. The porosity (surface area and pore volume) can be severely destroyed by such practice. This may explain why exhaustive leaching to remove virtually all aluminum has not been practiced commercially.

Acid-activated bentonites have been used as reactive pigments for several decades for paper products, in particular for use as a porous pigment in carbonless copy paper manufacture. The acid-leached bentonite was used with normally colorless leuco dyes to develop colored images. In the case of U.S. Pat. No. 4,405,371, Sugahara et al., proposed to use a relatively highly leached bentonite. The bentonite was leached by H.sub.2 SO.sub.4 or HCl to such degree that SiO.sub.2 content was about 82-96.5 wt %, preferably 85-95 wt %. The acid-leached bentonite was characterized by its loss of X-ray crystallinity, regardless of its aluminum content or structure. However, it was noted that the acid-leached bentonite had a relatively low BET surface area, about 180 m.sup.2 /g.

The use of acid-activated bentonite as petroleum cracking catalysts was proposed in the 1930s. The mild acid-leaching, usually using H.sub.2 SO.sub.4 or HCl, generated porosity and acidity which were required for the catalysis. After the acid-leaching, part of the clay crystallinity was maintained, and most aluminum still remained in the structure, about 10-15 wt. % expressed as Al.sub.2 O.sub.3. It was found that the catalytic activity was reduced after more aluminum was removed.

The following references are nonlimiting examples of references that relate to the preparation of acid-leached bentonites and to their use in catalytic cracking applications:

R. E. Grim, "Applied Clay Mineralogy", McGraw-Hill, New York, 1962, p. 307-332.

G. R. Bond, "Acid-treated clay catalyst for cracking hydrocarbons", U.S. Pat. No. 2,551,580 (1951).

A. Grenall, "Montomorillonite cracking catalyst, X-ray diffraction", Ind. Eng. Chem., 40 (1948) 2148-2151.

U.S. Pat. No. 3,944,482, Bruce R. Mitchell et al., "Process for the Cracking of High Metals Content Feedstocks".

Since the discovery of zeolites in the 1960s, the role of acid-activated bentonite in refinery cracking has substantially decreased except for some uses such as a matrix constituent. For example, in Mitchell et al patent (U.S. Pat. No. 3,944,482) acid-leached bentonite was used as matrix for high metals tolerant resid catalysts. Mitchell et al found that the acid-activated bentonite matrix must meet two requirements: (1) it must have a high aluminum content above 20 wt %, and (2) its average pore diameter must be larger than 100 A.


One aspect of the present invention comprises a method for manufacturing mesoporous particulate silico-aluminate from calcium bentonite clay minerals containing octahedral and tetrahedral aluminum in the framework of the mineral. The process comprises mixing the calcium bentonite mineral with sufficient acid, preferably phosphoric acid, to leach substantially all of the octahedral aluminum while leaving at least a predominating amount, preferably all, of the tetrahedral aluminum.

The term "mesoporous" as used herein refers to a pore diameter (volume average) of about 20-100 .ANG., measured by N.sub.2 adsorption.

The concentration of the acid is in the range of 0.5 to 8M, preferably at least 1.0M and less than 6.0M, and, most preferably in the range of 2.0 to 4.0M. Expressed in wt %, the acid concentration is in the range of 5 to 86 wt %, preferably at least 10 and less than 60 and, most preferably in the range of 20 to 40 wt %. Temperature is preferably in the range of to C., most preferably to C.

The leached silicoaluminate residue is washed, preferably with water, until the residual acid is below 1.0% weight, expressed as P.sub.2 O.sub.5, (based on the anhydrous weight of the solid). After leaching, the resulting mesoporous residues contain 4.0 to 0.5 weight % Al.sub.2 O.sub.3 (based on the anhydrous weight) and have surface areas from 300 to 730 m.sup.2 /g, depending on the starting clays.

Preferably, the characteristic XRD lines of bentonite are absent in the silicoaluminate product. Only two broad peaks at about 2.theta.=2.2 and are observable, which are due to the amorphous mesoporous silicoaluminates.


FIG. 1 displays small-angle XRD powder patterns of fresh and H.sub.3 PO.sub.4 -leached Cheto clay. Notice the disappearance of clay peaks and the formation of the mesoporous silicoaluminate (MEPSA) peaks as leaching time increases.

FIG. 2 shows .sup.29 Si MAS NMR of fresh and H.sub.3 PO.sub.4 -leached Cheto clay. Notice the disappearance of the clay Si--O--Al bond and the formation of MEPSA Si--O--Si and Si--O--OH bonds as leaching time increases.

FIG. 3 shows water adsorption isotherms of MEPSAs at C. All products have very high water adsorption capacity.

FIG. 4 displays .sup.27 Al MAS NMR of Fowlke clay and the fresh and steamed MEPSA-3 obtained therefrom. For the starting clay, most aluminum is octahedral. H.sub.3 PO.sub.4 leaching removes almost all the octahedral Al and keeps the tetrahedral Al intact. The tetrahedral Al has very high hydrothermal stability.


In one embodiment of this invention novel silico-aluminate products are produced. These products have a remarkably high hydrothermal stability and a high BET surface area, typically about 300-500 m.sup.2 /g, a pore volume in the range of 0.4 to 0.8 cc/g, and a pore diameter in the range of 30-80 .ANG. units. Suitable source clays for these ultra highly stable products are commercially available as Mississippi or Fowlkes clay. These stable mesoporous silicoaluminates material can be used both as a cracking catalyst and a matrix for a zeolitic resid cracking catalyst.

Such porous materials are used to improve the gasoline yield and increase the bottoms upgrading, but at no significant penalty of hydrogen and coke. They also tolerate high metal content in the feedstock. This is achieved by the extensive, but controlled acid-leaching, which generates much higher porosity and removes all the octahedral aluminum, but keep all the tetrahedral aluminum.

In other preferred embodiments of the invention, the products are mesoporous silicoaluminates with ultra high surface area (up to 730 m.sup.2 /g) and brightness (typically about 90% using the TAPPI procedure). The mesoporous silicoaluminates may find many applications such as reactive pigments for carbonless copy paper and ink-jet printing as well as desiccants and adsorbents. Mesoporous silicoaluminates derived from bentonite, such as the calcium bentonites known as Cheto (Arizona) clays, can be processed to provide materials that are not only ultra highly porous and bright, but also have favorable water adsorption isotherms for use as desiccants. Surface areas of such products are typically about 600 to 730 m.sup.2 /g; pore volume in the range of 0.4 to 0.8 cc/g and pore diameter in the range of 30-60 Angstrom units.

In practice of this invention, the range of phosphoric acid concentration is preferably 1-6M when producing high BET surface area products at reasonable leaching time at C. Especially preferred is the use of 2-4M H.sub.3 PO.sub.4 when producing high surface area products using 2-10 hours leaching time at C.

Generally the minimum acid concentration is about 1.0 M; using lower concentration leaching time may be excessive even at C. The maximum concentration is about 6.0M. Use of stronger acid can result in a reaction that is too vigorous to control.

Optimum temperature varies with the concentration of the acid. Preferred leaching temperature is in the range C. Especially preferred are temperatures in the range to C.

Mesoporous silicoaluminate products of the invention may be prepared by batch or continuous operations, preferably employing continuous agitation either by mechanical stirring or by bubbling steam into the system.

After reaction is complete, the mesoporous silico-aluminate is separated from the bulk of the liquid by known means such as filtration or centrifugation. The residues are washed, preferably with deionized water, to reduce H.sub.3 PO.sub.4 residual to below 1.0 wt %, expressed by P.sub.2 O.sub.5.

Before acid-leaching, clays can be processed by drying and crushing into powder. Typically particle size of the powders is about 10-40 micrometer in diameter.

Suitable but nonlimiting sources of clay useful in practice the invention have the following composition (on a dry weight basis):

______________________________________ Source Clay (wt %): Cheto Fowlke (Arizona) (Mississippi) ______________________________________ SiO2 66.7 66.4 Al2O3 19.9 19.4 CaO 3.4 3.6 MgO 6.1 3.6 Fe2O3 1.9 5.7 TiO.sub.2 0.3 0.9 K.sub.2 O 0.2 0.8 Na.sub.2 O 0.1 0.2 ______________________________________

Clay mineralogy: XRD powder diffraction patterns indicate that Fowlkes and Cheto clays are of typical layered montmorillonite smectite structure except that Fowlke has a higher impurity content. The main smectite peaks of as-received clays are located at

______________________________________ 2 Theta (degree) Intensity ______________________________________ 5.8 vs 17.4 w 20.0 s 29.5 w 35.2 s ______________________________________

In one especially preferred embodiment of the invention a mesoporous silicoaluminate material, dubbed MEPSA-1, with high surface areas about 730 m.sup.2 /g, is synthesized. The high surface area can be obtained only when H.sub.3 PO.sub.4 acid and a special smectite clays are used. Such bentonite clays are mined in the Cheto deposit and are supplied under the trade name F2 by Engelhard Corporation. To our knowledge, products obtained by practice of this invention using such clays have the highest surface areas of acid-leached bentonites ever achieved. Both XRD and .sup.29 Si NMR provide evidence that the acid-leaching has fundamentally transformed the layered bentonite into an amorphous silica-like structure. The resulting products, designated MEPSA-1 in the illustration examples is no longer a bentonite. The high surface area is related to the removal of aluminum in the clay. However, a maximum surface area is obtained only when some or all the tetrahedra aluminum (Al.sub.2 O.sub.3 0.5-2.0 wt. %) remains in the structure. A complete removal of aluminum leads to a destruction of some of the porosity.

MEPSA-1 can be made by stirring as-mined (dried and pulverized) F2 bentonite in an aqueous phosphoric acid solution. We found that the same surface area can be obtained by different combinations of the three reaction variables: acid concentration, reaction time, and temperature. After the acid-treatment, the solid is filtered, washed, and dried without further pretreatment. In a typical laboratory procedure a slurry with a F2 clay/3M H.sub.3 PO.sub.4 acid ratio of 1g/10 ml is made, stirred at C. for 2.5 hours, filtered, washed three times with deionized water, and dried at C. overnight.

FIG. 1 shows XRD powder patterns of H.sub.3 PO.sub.4 -leached F2 as a function of reaction time. As the acid-treatment time increases, the signature peaks of bentonite (at about 2.theta.=5.8, 20 and gradually disappear, and a new peak is formed at which corresponds to a very large d-spacing of about 40.5 .ANG.. N.sub.2 adsorption BET surface area (727 m.sup.2 /g) and average pore size (42 .ANG. in diameter) of MEPSA-1 is entirely consistent with the large XRD d-spacing value. Furthermore, as shown in FIG. 2, .sup.29 Si MAS (magic-angle spinning) NMR indicates that the acid-treatment has almost completely changed the local structure of bentonite. Fresh bentonite is characterized by its single silicon peak at about -93 ppm due to silicon sites that are connected to three other Si and one Al (or Mg) atoms through oxygen bridges (FIG. 2-a). After the acid-treatment, shown in FIG. 2-b and -c, the Si--O--Al bond is almost completely replaced either by a Si--O--OH (-103 ppm) bond or a Si--O--Si bond (-113 ppm). Only about 6% of original signal is left. Thus, both XRD and NMR data are definitive that MEPSA-1 is no longer a bentonite. Chemical analysis data also indicate that the acid-treatment has significantly reduced alumina content from 20 to 1.3 wt. % and increased the Si content from 67 to 95 wt. %.

X-ray diffraction evaluations reported herein were performed on a Philips APD 3720 diffractometer. The instrument settings are:

Voltage: 45 K.check mark.

Current: 40 MA

Radiation: Cuk.alpha. 1.5406 .ANG.

Divergency slit: automatic compensator

Receiving slit: 0.2 mm

Monocromator: graphite

Scan range (2.theta.):

Step size

Count time: 2 sec/step

Solid-state nuclear magnetic resonance (NMR) was used to determine the local structure of the starting bentonite clays and the end silica products. This method is particularly useful in determining local atomic bonding structures in the materials. All the high resolution NMR spectra were taken from a Varian Unity-400 MHZ spectrometer at room temperature under a so-called magic angle spinning (MAS) condition.

The aluminum spectra were taken using a Doty 5mm probe with MAS at about 11 kHz spinning speed. The spectra were referenced to a 1.0M aluminum nitrate aqueous solution. In order to further eliminate the quadrupolar broadening associated with .sup.27 Al nucleus, a short RF excitation pulse, 0.5 .mu.s, was used and the samples were moisturized at 80% humidity for at least 24 hours before the analysis. These conditions had been established in literature. Reference is made to the following papers and the references therein:

X. Yang, Structure identification of intermediate aluminum species in USY zeolite using high resolution and spin-lattice relaxation .sup.27 Al NMR, J. Phys. Chem., 99 (1995)1275.

X. Yang and R. Truitt, Observation and study of new tetrahedral Al sites in NH3-treated, steamed zeolites using MAS .sup.27 Al and .sup.15 N NMR, Zeolites, 17 (1996) 249.

The silicon spectra were acquired using a Chemagnetics 7.5 mm probe with MAS at about 5 kHz. A 7.0 .mu.s excitation pulse and 40 s recycle time were used. The spectra were referenced to tetramethyl silane (TMS). The detailed acquisition conditions can be found in the following publication:

X. Yang and P. Blosser, Location and bonding of cations in ETS-10 titanosilicate molecular sieve: A multinuclear NMR investigation, Zeolites, 17 (1996) 237.

The chemical composition analysis was performed with a standard X-ray florescence technique. The elemental composition was based on a volatile free weight basis ( C.). For all the analyzed elements of the clays and the silicon in MEPSA, the accuracy is within .+-.0.1 wt %. For the low aluminum residual in MEPSA, the accuracy is within .+-.0.5 wt %.

The water adsorption isotherms were analyzed using a TGA (thermal gravametric analysis) method. The samples were dried at C. before the analysis. Each measurement point represents the amount of water gained after an equilibrium is reached under the specific relative humidity.

The BET surface area, pore volume, and pore size were determined by nitrogen gas adsorption at liquid nitrogen temperature, using either of two automated instruments: Quantachrome.RTM. Autosorb-6 or Micrometrics.RTM. ASAP2400. The samples were heated at C. under vacuum for at least 6 hours before the analysis. The sample weight was obtained on a dried sample. The surface area was obtained by B.E.T. method with 39 relative pressure points. The pore volume represents the total pore volume with pore radius less than 1000 .ANG..

TAPPI brightness and yellowness were measured using a Technidyne-S4M and Technidyne-MicroTB1C instrument, respectively. The TAPPI brightness is also referred to as GE or Germ brightness. The samples were ground to 325 mesh for the analysis. The instruments were calibrated against the manufacturer's master instruments. A sample of fully calcined kaolin sample supplied by Engelhard Corporation was used as a reference.

The abrasion was measured using an Einlehner abrasion apparatus. An aqueous slurry containing 15 wt % solids and 87,000 revolution of abrasion (equivalent of 40 minutes) were used.

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