JPH07121804B2 - Multi-metal columnar intercalated clay product and manufacturing method thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the production of pillared intercalated clays obtainable by the reaction of smectite-based clays with polymeric cationic polymetallic complexes. The pillar intercalated clay of the present invention has an internal microstructure that can be created by introducing discrete discrete inorganic oxide particles or pillars of length 6-16Å between clay layers. Such pillars serve to retain the cavities between the expanded clay layers after removal of the entrapped water, and also provide an interconnected microporous structure throughout the inner layer, with the majority of the pores being about 30Å. Helps construct the structure with a diameter less than.

The present invention relates to thermally stable columnar intercalated clay having interlayer voids of up to 16 liters, the columnar containing more than one metal atom. This intercalated clay product is a polymeric cationic hydroxy poly-compound produced by reacting naturally occurring or synthetic smectite clay with certain metal-containing compounds and materials such as aluminum chlorohydroxide complexes (chlorohydrols). It can be prepared by heating a polymer complex that reacts with and hydrolyzes a metal complex to convert it to an inorganic multi-metal oxide. Of course, polymer cationic hydroxy polymetallic complex,
It can also be prepared by various other methods, for example, by introducing an addition metal into the initial acidic aluminum solution used for polymer synthesis.

Description of the Preferred Embodiments The following general procedures can be used to obtain the novel pillar intercalated clay products of the present invention: (1) Johansen [Acta.chem.Scan.
d., Vol. 14 (1960), p. 771], the cations of the type believed to be [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ with a spherical structure. The polymer is reacted with the fourth, fifth or sixth period transition metal in an aqueous solution. The metal is mainly from Group VB, VIB, VIIB and VIII of the Periodic Table. The base polymetallic complex is considered to be of the following type: [Al ^iv Al ▲ ^vi ₁₂ ▼ O ₄ (OH ₂₄ )] ⁺⁷ One or more of the above elements are either iv or vi coordination sites. Either or both may be substituted. The general formula of this substitution molecule can be represented as: N ^iv (Al _12-X M _X ) ^vi O ₄ (OH) ₂₄ ^{+ a} where N is Al ³⁺ , Si ⁴⁺ , Ga ³⁺ , Ge ⁴⁺ , As ⁵⁺ , P ⁵⁺ , C
It may be r ³⁺ , Fe ³⁺ , V ⁵⁺ , Ru ³⁺ , Ru ⁴⁺ , Ni ³⁺ , M is VB group of the 4th, 5th or 6th period in the periodic table, V
It can be one or more of Group IB, VIIB and VIII elements, the value of "x" can be from about 1 to about 6, and the value of "a" depends on the type of substitution metal. Representative polymetallic cationic polymer complexes include: [Fe ^iv (Al ₁₀ Cr ₂ ) ^viO ₄ (OH) ₂₄ ] ⁷⁺ [Al ^iv (Al ₉ Fe ₃ ) ^viO ₄ ( OH) ₂₄ ] ⁷⁺ [Al ^iv (Al ₁₀ Ni ₂ ) ^viO ₄ (OH) ₂₄ ] ⁵⁺ Obviously, such substituents can change the charge of the polymer molecule. Vaughan, etc. [Proc. 5th Intl. Zeolite Con
f. (1980, p. 94], such polymetallic molecules can hydrolyze depending on the pH of the solution.

Another method for producing (Al ₁₃ ) ⁷⁺ is described below. Such a method can be used as an alternative to starting with a lower aluminum chlorohydrol commercial liquor.

(2) Smectite clay is mixed with an aqueous solution of the polymer cationic hydroxypolymetal complex formed in step (1) in an amount such that the weight ratio of clay to metal complex solution is 1: 2 to 1,000. The metal complex solution preferably comprises 1-40% by weight solids in a suitable liquid medium such as water.

(3) Hold the mixture of clay and metal complex at a temperature of 5 ° C to 200 ° C for 0.1 to 4.0 hours.

(4) Collect the reacted clay solids, 200 ℃ ~ 700 ℃
The metal complex hydrolyzed by heating at the temperature of
Decomposes into columnar substance which seems to be multi-metal oxide or hydroxide.

Clays suitable for use as starting materials in the present invention are the group of minerals known as smectites and are those outlined above in the Background of the Invention. A detailed description of such materials is given in "Crystal Structure of Clay Materials and Their X-Ray Identification (Crystal Structur Identification), edited by GW Brindley et al.
es of Clay materials and Their X−Ray Identificati
on) "(Mineralogical Soc.), 1980.

The inorganic metal polymer used as a starting material for the production of the multi-metal polymer is generally known as a basic aluminum complex formed by hydrolysis of an aluminum salt.
Indeed, although there is some discrepancy in the type of species present in the hydrolyzed metal complex solution (or suspension), generally speaking, these mixtures are complexed by some metal ions. It is thought to contain a highly charged cation complex.

Hydrolysis of the cation gives rise to the polymer via a process called oarization. CL Rollinson describes this process for aluminum as "Chemistry of the Coordination.
Compounds) ”(edited by JC Bailar, Reinhold Publishing
Corp. New York, (1956)].

In this process, OH between Al ions between ^- the single bridge or Nijubashi may be formed. At lower acid solutions, larger polymers are formed by the process and crosslinked OH
^- it can be added to crosslink O ^-2 (oxo configuration). It should be noted that the double OH bridged complex is a pair of edge-sharing octahedra, which means that the boehmite AlOOH in which the OH ^- groups are shared by two AlO ₆ octahedra each at the surface of the layer. The same type of structure found in. Gibbs stone Al (OH)
^In the case of ^a3 , all oxygen is also shared between the two AlO ₆ octahedra. The various methods used to make Al polymers are described in US Pat. No. 4,176,090.

However, mixtures of aluminum salts and transition metal salts are used to make the novel substituted clays of the present invention.

The metal ions can be added to a solution already containing the polymer (Al ₁₃ ) ⁷⁺ or to the solution in which the polymer is forming. Both methods appear to produce similar mixed metal polymers. This work involves only the transition metal cation substituted form of (Al ₁₃ ) ⁺⁷ having the general formula N ^iv (Al _12-X M _X ) ^vi O ₄ (OH) ₂₄ ^{+ a} . In the above formula, N is Al ³⁺ , Si ⁴⁺ , Ga ³⁺ , Ge ⁴⁺ ,
As ⁵⁺ , P ⁵⁺ , Cr ³⁺ , Fe ³⁺ , V ⁵⁺ , Ru ³⁺ , Ru ⁴⁺ , Ni ³⁺ or a mixture thereof, and M is the 4th or the 4th element in the periodic table. VB group, VIB group, VIIB group in the 5th or 6th period and
It may be one or more elements selected from Group VIII. These metals include V, Cr, Mn, Fe, Co, Ni, Nb, M
o, Tc, Ru, Rh, Pd, Ta, W, Re, Os, Ir and Pt. The value of "x" can be about 1-6. The value of "a" depends on the substitution metal.

Preferred are materials where M is V, Cr, Mn, Fe, Co, Ni or mixtures thereof when N is a1 or A1 and Ru.

The polymer is exchanged into smectite clay by cation exchange or other swelling methods to form swollen clay. Typically, the clay is comminuted and slurried in excess water. A large amount of the polymetallic polymer of this clay slurry is added. The mixture is then aged for a period of time sufficient to introduce the polymer in position between the host clay platelets.

Referring to the drawings, FIG. 1 shows a repeating distance (a) of 16-24Å treated with a polymetallic complex polymer according to the teachings of the present invention.
3 shows a typical smectite with. The interlayer distance (b) is in the range of 6 to 16Å. The height (b) of the pillar is
The temperature of the columnar polymetallic complex polymer inserted between the clay platelets
Established when decomposed by burning in the range of 200 ℃ -700 ℃. The distances shown in the figure are easily obtained from the X-ray diffraction patterns for various products and represent the primary fundamental reflection parameter or 001.

It should be understood that the layers are not uniform within a given clay structure,
It is that the composition of one layer constitutes a heterogeneous chemical mixture that may differ somewhat from that of its adjacent layers. This is likely to result in slight charge fluctuations between the layers, and therefore in small differences in polymer exchange between different layers. Since the dimension of the polymetallic polymer is a controlling factor when setting the interlayer distance, the charge inhomogeneity on the layers is only dependent on the number of polymer species between layers (ie not on the size of the pillars). Affect.

Generally speaking, the ware of the present invention has an interlayer distance of 6 to 16Å, a nitrogen BET surface area of 150 to 600 m ² / g, and 0.1 to 0.6 cc / g.
It has a nitrogen pore volume of. Also, the novel multimetallic columnar intercalated clay composition possesses a substantially internal microporous structure. This is evidenced by nitrogen pore size distribution analysis, which shows that most of the pores are in the <25Å range. The pillars themselves may certainly contain some aluminum as they are formed by heating the polymetallic polymer as described above. Thus, a part of aluminum can be replaced by various metals or metalloids as described above. That is,
In the cationic multi-metal polymer, N ^iv is Al, Si, Ga, G
It may be one or more of e, As, P, Cr, Fe, V, Ru or Ni. In addition, a considerable part of the metal compound in the pillar is V, Cr, Mn, Fe, Co, Ni, Nb, Mo,
It must be at least one of Tc, Ru, Rh, Pd, Ta, W, Re, Os, Ir or Pt. The Mx component of the polymer intermediate is the source of these metals. The compound in the column is
After firing, it is primarily a single or complex type oxide. However, some hydroxide may remain.

Such intercalated products are useful as absorbents, catalyst supports and often catalysts. The intercalated clay product is also contemplated for use with other inorganic oxide absorbents or catalysts such as silica, alumina, silica-magnesia, silica-alumina, hydrogels, natural or synthetic zeolites and clays. Such compositions are useful in the manufacture of catalysts containing matrix components such as silica, alumina and silica-alumina hydrogels, and other active or stabilizing metals such as platinum, palladium, cobalt, molybdenum, nickel, tungsten, rare earths and the like. Can be. The resulting catalysts can be used in conventional petroleum conversion processes such as molecular sieve separation, catalytic cracking, hydrocracking, hydrotreating, isomerization, reforming, polymerization and other petrochemistry. In addition, these compositions are for producing a dual-function catalyst in which the first metal catalyst is introduced into clay by ion exchange and the second functional catalyst substance is mixed into the pillar as a part of the multi-metal pillar. It is contemplated that can be particularly useful in

Having described the basic features of the present invention, the following specific examples are given for the purpose of illustrating preferred specific embodiments.

Example 1 In this example, aluminum chlorohydrol Al ₁₃ O ₄ (OH)
_{In a 24} Cl ₇ (“chlorohydrol”) solution, the composition Al ₁₁ Cr ₂ O ₄
Sufficient Cr ³⁺ was added to obtain a pure columnar (OH) ₂₄ Cl ₇ .

50% by weight aqueous chlorohydrol solution (Reheis Chemica
(Company l) 0.5 g of CrCl ₃ .6H ₂ O was dissolved in 20 g at room temperature. The solution was stirred at 22 ° C for 16 hours and then heated at 100 ° C for 2 hours. Bentolite L smectite (Geo
rgia Kaolin) 10g, the resulting slurry at 95 ℃
Stir for 75 minutes. The mixture was passed and the blue-grey filter cake was dried in the freeze dryer for 16 hours. According to X-ray diffraction analysis, about 30% of the clay swelled to 18.8Å (001)
It was shown that there was a layer spacing. In contrast, Cr
A similar sample of clay that can only be exchanged with a solution of Cl ₃ (0
01) gave a green-grey product with reflection 15.1Å. 55
After calcination at 0 ° C., the polymer-treated clay was a light tan color, while the Cr ³⁺ exchanged clay was a grey-brown color.

Example 2 0.5 g of CrCl ₃ .6H ₂ O was dissolved in 10 g of H ₂ O and mixed with 20 g of chlorohydrol (same as in example 1). After aging at 22 ° C for 16 hours, the polymer solution was thermally aged at 95 ° C for 75 minutes. Bentrite L smectite (10 g) was added, and the resulting slurry was mixed at 95 ° C
Stir for 0 minutes. Clay to obtain a liquid having a color similar to that of a blue-grey filter cake. The exchanged clay was freeze-dried for 16 hours, and the clay powder had an X-ray diffraction (001) interval of 18.2Å (60
%) And 15.2Å (25%) (this indicates only H ₂ O mutual firing, and 9.8Å indicates no swelling). After baking, the sample turned a light tan to cream color.

Example 3 In this example, Ni ²⁺ is substituted into the columnar body.

0.5 g of NiCl ₂ 6 · 6H ₂ O was dissolved in 20 g of H ₂ O and added to 20 g of a 50 wt% chlorohydrol solution (Reheis Chemical Co.).
The resulting mixture was stirred at room temperature for 10 minutes. Bentrite L Mori Morillonite 10 g sample was added and the whole was stirred at 23 ° C. for 16 hours. After the filtration, the filter cake was freeze-dried. X-ray diffraction showed the sample to have strong reflections at 21.7Å and 11.8Å. After baking this material for 1 hour at 450 ° C., the sample was placed on a saturated solution of CaCl _{2 at} a relative humidity of 8
Equilibrated at 8%. As a result of thermogravimetric analysis of this sample, the total weight loss was 26% by weight, and 23% by weight at a temperature below 450 ° C.
Was lost. In X-ray diffraction, the sample is strong at 18.2Å (00
1) It was shown to have reflection. Absorption of n-hexane showed an increase of 3.8% by weight. After baking in air at 650 ° C for 2 hours and re-equilibration with 88% water for 2 hours, the sample absorbed 9 wt% H ₂ O. If in this experiment two N
If i ²⁺ replaces two Al ³⁺ , the insertion polymer has the formula [Al ₁₁ Ni ₂ O ₄ (OH) ₂₄ ] ⁵⁺ .

While the invention has been illustrated and some examples of its practice have been shown, it is obvious that various equivalents will be obvious to those skilled in the art and that they fall within the scope of the following claims.

[Brief description of drawings]

FIG. 1 shows a schematic cross-sectional view of the texture structure of a typical smectite-type clay treated with a polymer cationic hydroxypolymetallic complex so as to form columnar interlayers between clay layers.

Claims (10)

[Claims] 1. A smectite clay product containing pillars having substantially separated layers, wherein the interlayer distance is substantially larger than the precursor of the same clay except unisolated, and the pillars contained in the product are aluminum compounds. And at least one metal compound, wherein the metal of the compound is V, Cr, M
n, Fe, Co, Ni, Nb, Mo, Tc, Ru, Rh, Pd, Ta, W, R
A smectite clay product selected from e, Os, Ir, Pt or mixtures thereof and wherein the pillars separate the layers. 2. The columnar material has the formula: N (Al _12-X M _X ) O ₄ (OH) ₂₄ ^{+ a} (where N is Al, Si, Ga, Ge, As, P, Cr, Fe, V, Ru or
Ni or a mixture thereof, M is V, Cr, Mn, Fe, Co, Ni, Nb, Mo, Tc, Ru, Rh, P
d, Ta, W, Re, Os, Ir, Pt or a mixture thereof, x is 1 to 6, and a is a cationic polymer complex of) depending on the selection of M and N). Products in the range 1 3. A product according to claim 1 wherein M is selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Ru and mixtures thereof. 4. A product according to claim 1, wherein the pillars are substantially oxides. 5. A product according to claim 1 wherein the smectite is selected from the group consisting of hectorite, chlorite, bentonite, montmorillonite, beidellite and mixtures thereof. 6. (a) Formula: N (Al _12-X M _X ) O ₄ (OH) ₂₄ ^{+ a} (where N is Al, Si, Ga, Ge, As, P, Cr, Fe, V, Ru or
Ni or a mixture thereof, M is V, Cr, Mn, Fe, Co, Ni, Nb, Mo, Tc, Ru, Rh, P
d, Ta, W, Re, Os, Ir, Pt or mixtures thereof, x is 1 to 6 and a is dependent on the selection of M and N) Aqueous containing polymeric cationic hydroxy polymetallic complex A method of making a multi-metal intercalated smectite clay product, comprising reacting the composition with smectite to form an intercalated smectite product, and (b) separating the intercalated smectite product from the mixture. 7. The method of claim 6 wherein M is selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Ru and mixtures thereof. 8. The method according to claim 6, wherein the mixture is reacted at a temperature of 5 ° C. to 200 ° C. for 0.1 to 4 hours. 9. Intercalated smectite product is 200 ℃ ~ 700 ℃
The method according to claim 6, wherein the reaction is carried out at the temperature of. 10. A metal complex of 0 to 1 part by weight of smectite.
The method according to claim 6, wherein 05 to 2.0 parts by weight are mixed.