CA1275087A - Multimetallic pillared interlayered clay products and processes of making them - Google Patents
Multimetallic pillared interlayered clay products and processes of making themInfo
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- CA1275087A CA1275087A CA000516085A CA516085A CA1275087A CA 1275087 A CA1275087 A CA 1275087A CA 000516085 A CA000516085 A CA 000516085A CA 516085 A CA516085 A CA 516085A CA 1275087 A CA1275087 A CA 1275087A
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Abstract
ABSTRACT
This invention is a composition of matter made up of an expanded smectite clay having multi-metallic pillars separating the clay layers. The expanded clay may be used as a shape selective catalyst, catalyst support, or as an adsorbent material. More particularly, this invention relates to expanded smectite clays wherein the pillars are made up of aluminum and one or more transition metals.
This invention is a composition of matter made up of an expanded smectite clay having multi-metallic pillars separating the clay layers. The expanded clay may be used as a shape selective catalyst, catalyst support, or as an adsorbent material. More particularly, this invention relates to expanded smectite clays wherein the pillars are made up of aluminum and one or more transition metals.
Description
7~ 37 _MMARY OF THE INVENTION
The present invention reLates to the pre-paration of pillared interlayered clays which may be obtained by reacting smectite type clays witn polymeric cationic multimetal co~,plexes. The pillared inter-layered clays o~ the invention possess an internal microstructure which may be established by introducing discrete and non-continuous inorganic oxide particles or pillars having a length between 6 and 16 ~ between the clay 'ayers. These pillars serve to hold the space between the clay layers open after re~loval of included water and serve to ~orm an internal interconnected icropore structure throughout the inner layer in whicn the majority of the pores are less than about 30 ~ in diameter.
The invention relates to thermally stable interlayered clays having interlayer spacings up to 16 ~ and whose pillars cGntain more than one type of metal atom. T'ne product interlayered clay may be produced by reacting a naturally occurring or synthetic smectite type clay with a polymeric cationic hydroxy multimetal co~lplex, the complex being produced by reacting certain metal-containing compounds with materials such as alu~linun, chlorohydroxide complexes ("chlorohydrol"), and heating to convert the hydrolyzed polyn,er complex into an inorganic ~,ulti~,etal oxide.
The polymeric cationic hydroxy multimetal co~,plex-may be, of cour~e, produced in a variety o~ other ways, including the introduction of the additional metals into the initial acidic aluminum solutions used in polymer synthesis.
\
BRIEF DESCRIPTION OF THE DRAWING
. . _ Figure 1 represents a schematic cross-sectional view of the structure of a typical smectite type clay which has been treated with polymeric cat;onic hydroxy multimetal complex to for~l a pillared interlayer between the clay layers.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
To obtain the novel pillared interlayered clay products of the invention the following general procedure may be used:
(1) a cationic polymer oE the type believed to be (A11304(0H)247+, having a globular structure as Eirst descrioed by Johansen, Acta. Chem. Scand., V. 14 (1960), p. 771, is rea¢ted in aqueous solution with a fourtht fifth or sixth period transition ~etal. These will pri~larily be Ero~ Groups 5B, 6B, 7B and 8 of the Periodic Table. The base ~lultiatomic complex is thought to be of the type:
AliVAllv2O4(OH)24)7~.
One of ~,ore of the noted elements may be substituted into either or both o~ the iv or vi coordinate sites.
The general formula for the substituted molecule ~,ay be represented as:
Nlv(~ll2-xMx)ivo4(OH)24+a where N ~,ay be A13+, Si4~, Ga3~, Ge4~, As5+, P5+, Cr3+, Fe3+, V5+, Ru3+, Ru4+, Ni3+; M ~lay be one or more of the elements of Groups 5B, 6B, 7B and 8 of the 4th, 5th 27~
or 6th Periods of the Periodic Table. The value for "x" may be from about 1 to about 6. The value for "a"
depends upon tne nature of the metal substitutions.
Representative multimetal cationic polymer complexes include:
(FeiV(Allocr2)vio4(oH)24 (AliV(AlgFe3)vio4(OH)247~
(Aliv(AlloNi2)vio4(o~)245 .
Ooviouslyl such substitutions may change the charge on the poly.mer molecule. Depending on the solution pH, such multimetallic molecules ~,ay be hydrolyzed to produce lower charged species as indicated by Vaughan, et al., Proc. 5th Intl. Zeolite Conf., (1980), p. 94.
Other met'nods for producing (A113)7+ are discussed below and may be used as an alternative to beginning with a com~,ercial solution of lower aluminum chlorohydrol.
t2) A smectite clay is mixed with the aqueous solution of polymeric cationlc hydroxy multi-metal complex formed in step (1), in an,ounts so that the weight ratio of clay to metal complex solution is from 1:2 to 1,000. The metal complex solution will preferably contain fro~l l to 40 percent by weight solids in a suitable liquid medium, such as water.
(3) The mixture of clay and metal complex is maintained at a temperature of 5C to 200C Eor a period of 0.1 to 4.0 hours.
9~ Z7~7 (4) The reacted clay solids are xecovered and heated at a temperature of fro~l 200C to 70~C to deco~lpose the hydrolyzed metal co~lplex to a pillar believed to be of multiple metallic oxides or hydroxides.
. The clays which are suitable for use as starting materials in the present invention are the group of minerals known as smectites and are generally described above in the Background of the Invention. An extensive discussion of these materials is given in "Crystal Structures of Clay Materials and Their X-Ray IdentiEication", edited by G. W. Brindley, et al., (Mineralogical Soc.), 19~0.
The inorganic metal polymers that are used as starting material for production of the multi!TIetal poly~lers are generally known as basic alu~linu~l com-plexes which are formed by the hydrolysis of aluminulT, salts. While there is inevitably some disagreement on the nature of the species present in hydrolyzed metal complex solutions (or suspensions), it is generally believed that these ~,ixtures contain highly charged cationic colT,plexes with several ~,etal ions being co~,plexed~
The hydrolysis of cations brings about poly-~,ers through a process called olation. For alu~,inum this process is described by C. L. Rollinson in "Che~,istry of the Coordina~ion Co~,pounds", edited by J. C. Bailar, Reinhold Publishing Corp., New York, (1956) as follows:
,..G.~
OH +~ H20~ +-~
(N2O)~Al~ Al~H20)4 [(~2)4A~ (H2)~] ~2 ~O
O
In this process, single or double OH- hridges can be formed between Al ions. In less acidic solution, larger polymers are formed by the process and the bridging OH- can be converted to a bridging o-2, a process called oxolation. Note that a doubly OH
bridged complex is a pair of edged-sharing octahedra, and this is the same type of structure found in boehmite, AlOOH, where the OH- groups at the surface of the layers are each shared by two A106 octahedra. In hydrargillite, Al(OH)a3, all oxygen are also shared between two A106 octahedra. Various methods that have been used to produce Al polymers are discussed in U. S.
Patent No. 4,176,090.
However, for the purposes of ~laking the novel substituted clays of the invention, mixtures oE
aluminum salts and transition metal salts are used.
The metal ions may eitner be added to a solution already containing (All3)7+ poly~lers or may be added to a solution in which those ~olymers are being formed. Either method appears to produce similar mixed metal polymers. The present work is concerned only with the transition ~,etal cationic substituted forms of (All3)7+ having the general formula:
Niv(All2-xMx)v104(OH)2~
where N ~,ay be Al3~, Si4~, Ga3~, Ge4+, AsS+, p5+, Cr3+, Fe3+, V5+, Ru3+, Ru4+, Ni3+ or a mixture; M may be one or more of the elements selected from Groups 5B, 6B, 7B
and 8 of the 4th, 5th or 6th Periods of tne Periodic Table. Thése ~,etals include V, Cr, Mn, Fe, Co, Ni, Nb, Mo, Tc, Ru, Rh, Pd, Ta, W, Re, Os, Ir and Pt. The value for "x" ~,ay be from about l to 6. The value of "a" depends upon the ~,etal substitutions.
The preferred ~laterial is -that when N is al or ~l and Ru and M is selected fro~, V~ Cr, Mn, Fe, Co, Ni or a mixture of these metals.
The polymers described above ~,ay be exchanged into smectite-type clays by cation exchange or other ~,ethods of imibition to for~, expanded clays.
Typically the clay will be Einely ground and slurried in an excess of water. The ~,ultimetallic polyn,er is also added in a large amount to the clay slurry. The mixture is then aged for a period of time sufEicient to allow introduction of the poly~,er to a position between platelets of the host clay.
~ eferring to the drawing, Figure 1 rep-resents a typical sT,ectite which has been treated with the IT,ulti~letal complex poly~,ers in accordance with the teachinys of this invention and have a repeat distance A of 16 to 24 ~. The distance ~ between layers ranges between 6 and 16 ~. The height of the pillar b is established when the pillared ~lulti~,etal co~T,plex polymer which is inserted between the clay platelets is decolr,posed by calcination at temperatures between 200C
and 700C. The distance as shown in the drawing may be readily obtained from X-ray diffraction pattern for the various products and represent the first-order basal reflection paralrleter~ i.e., 001.
It should be unders-tood that within a given clay structure the layers are not uniform but instead form a heterogeneous chemical mixture in which the exact composition of one layer ~,ay be so~,ewhat dif-feren-t from that adjacent layer. This would be expected to result in slight variations in charge between layers, and, therefore, slight differences in the a~,ount of polymer exchange in different layers.
Since the size of the ~,ultimetal polymer is the con-trolling factor in setting the inner layer distance, charge heterogeneity on the layers would only affect the number of polymer species between the layers, that is to say, the number of pillars but not their size.
In general, calcined products of the inven-tion will have interlayer spacing oE 6 to 16 ~, a nitrogen BET surface area of 150 to 600 lTl2/gram~ and a nitrogen pore volu~,e of from 0.1 to 0.6 cc/g. Further-,ore, the novel pillared multin,etal interlayered claycomposition possess a substantial internal micropore structure, reflected by the nitrogen pore size distri-bution analyses which show a ~,ajor fraction of pores inthe range of less than 25 A. The pillars -themselves, in tha-t they are produced by heating the multimetallic poly~,ers discussed above, must contain so~,e alurninum.
A portion of the alu~inu~, may be replaced by a nu~,ber of semi ~,etals or metals, as discussecl above, i.e., NlV
may be one or more of Al, Si, Ga, Ge, As, P, Cr, Fe, V, Ru or Ni in the cationic multimetal polymer. Further-more, a substantial portion of the metal co~,pound in the pillar ~,ust be at least one or ~,ore of V, Cr, Mn, Fe, Co, Ni, Nb, Mo, Tc, Ru, Rh, Pd, Ta, W, Re, Os, Ir or Pt. The Mx component of the poly~,er intermediate is the source of these metals. The compound in the pillars is believed to be, after calcination, ~lostly an oxide of a si~,ple or co~,plex type. Some hydroxide may remain, however.
These interlayered products are useful as adsorbents, catalytic supports and in many instances as catalysts. Furthermore, it is contemplated that the interlayered clay products ~,ay be combined with other inorganic oxide adsorbents and catalysts, such as silica, alumina, silica-~,agnesia, silica-alumina, hydrogel, natural or synthetic zeolites, and clays.
These co~,positions ~,ay be useful in the preparation of catalysts which contain other active or stabilizing ~,etals, such as platinum, palladium, cobalt, molyb-denu~,, nickel, tungsten, rare-earths and so forth, as well as n,atrix components, such as silica, alumina, and silica-alu~,ina hydrogel. The resulting catalysts may be used in conventional petroleum conversion processes, such as catalytic cracking, hydrocracking, hydrotreat-ing, iso~,erization, re~orming, in polymeriza-tion and other petrochemical processes, as well as in ~,olecular sieve separations. It is contemplated that these com-~ ~5~
positions ~,ay be especially useful in preparing bifunctional catalysts wherein a primary ~.etallic catalyst is introduced into the clay by ion exchange and a secondary functional catalytic material is incor-porated in the pillars as a portion of the multi~etal pillars ~
Having described the basic aspects of the invention, the following specific exa~.ples are given to illustrate the preferred specific embodi~.ents.
Example 1 In this exa~.ple, sufficient Cr3+ was added to an alu~inu.~, chlorohydrol A113O4(OH)24C17 ("chloro-hydrol") solution to give a resulting theoretical pillar having a co~.position of AlllCr2O4(OH)2~C17.
A 0.5 gra~. CrC13 6H2O was dissolved, at roo~, te~perature, in 20 gra~.s of a 50 weight percent aqueous chlorohydrol solution (Reheis Chemical Co.). The solu-tion was stirred for 16 hours at 22C, then heated for two hours at 100C. ~ 10 gra~, sa~.ple of Bentolite s~,ectite (Georgia Kaolin Co.) was added and the slurry stirred at 95C for 75 ~.inutes. The ~.ixture was filtered and the blue-grey filter cake dried for 16 hours in a freeze dryer. X-ray diffraction analysis showed that about 30% of the clay had expanded to give an (001) layer spacing of 18.8 R. In contrast, a si~.ilar sa~,~le of the clay exchanged only with a solu-tion of CrC13 gave a green grey product that had an (001) reflection 15.1 R. After calcination at 550C
the poly~,er treated clay was a light tan-crea~. color, whereas the Cr3+ exchanged clay was a grey-brown color.
;'' Trade Mark ' ~ ~7Si~
Exa~lple 2 A O.S gran, sanlple of CrCl3 6H20 was dissolved in 10 yra~ls H2O and mixed with a 20 gram sample of chlorohydrol (as in Exa~,ple 1~. A~ter aging for 16 hours at 22C, the polymer solution was hot-aged for 75 n,inutes at 95C. A 10 gram sa~,ple of Bentolite L smectite was added and the slurry agitated at 95C
for 90 nlinutes. The clay was filtered, yielding a blue grey filter cake and a similarly colored filtrate.
After freeze drying, the exchanged clay for 16 hours, the clay powder gave an X-ray diffraction (001) spacing of 18.2 A (60%) and a spacing at 15.2 ~ (25% indicat-ing only H2O intercalcination and 9.8 a indicating no expansion). ~fter calcination the sa~,ple turned a light tan-crean, color.
Example 3 In this example Ni~+ is substituted into the pillar.
A 0.5 gra~l sa~,ple of NiC126 6H20 was dissolved in 20 grams H2O, and added to 20 grams of a 50 weight percent solution of chlorohydrol (Reheis Che~,ical Co.). The resulting mixture was stirred for 10 n,inutes at room temperatureO ~ 10 gra~, sample of Bentolite L n,ont~lorillonite was added and the whole was stirred for 16 hours at 23C. After filtration, the filter cake was freeze dried. X-ray diffraction showed the sample to have strong reflections at 21.7 A and 11.8 ~ After calcination of the material at 450C
for one hour, the sample was equilibrated at 88~ RH
over a saturated solution of CaCl2. Thern,oyravimetric analysis of this sa~,ple showed a total weight loss of 26 weight percent, 23 weight percent being lost below a te~,perature of 450C. X-ray diffraction showed the sample to have a strong t001) reflection at 18.2 ~.
Sorption of n-hexane showed a weight gain of 3.8 weight percent. After calcining in air for 2 hours at 650C
and re-equilibrating with water at 88% for 2 hours, the sa~,ple sorbed 9 weight percent H2O. If two Ni2+ have replaced two A13+ in this experi~,ent, the intercalated poly~,er will have a for~,ula [AlllNi2O4(OH)2~]5+.
Having thus described the invention and giving several examples in its practice, it should be apparent that various equivalents will be obvious to one having ordinary skill in the art and yet be within the purview of the clai~,s appended hereon.
The present invention reLates to the pre-paration of pillared interlayered clays which may be obtained by reacting smectite type clays witn polymeric cationic multimetal co~,plexes. The pillared inter-layered clays o~ the invention possess an internal microstructure which may be established by introducing discrete and non-continuous inorganic oxide particles or pillars having a length between 6 and 16 ~ between the clay 'ayers. These pillars serve to hold the space between the clay layers open after re~loval of included water and serve to ~orm an internal interconnected icropore structure throughout the inner layer in whicn the majority of the pores are less than about 30 ~ in diameter.
The invention relates to thermally stable interlayered clays having interlayer spacings up to 16 ~ and whose pillars cGntain more than one type of metal atom. T'ne product interlayered clay may be produced by reacting a naturally occurring or synthetic smectite type clay with a polymeric cationic hydroxy multimetal co~lplex, the complex being produced by reacting certain metal-containing compounds with materials such as alu~linun, chlorohydroxide complexes ("chlorohydrol"), and heating to convert the hydrolyzed polyn,er complex into an inorganic ~,ulti~,etal oxide.
The polymeric cationic hydroxy multimetal co~,plex-may be, of cour~e, produced in a variety o~ other ways, including the introduction of the additional metals into the initial acidic aluminum solutions used in polymer synthesis.
\
BRIEF DESCRIPTION OF THE DRAWING
. . _ Figure 1 represents a schematic cross-sectional view of the structure of a typical smectite type clay which has been treated with polymeric cat;onic hydroxy multimetal complex to for~l a pillared interlayer between the clay layers.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
To obtain the novel pillared interlayered clay products of the invention the following general procedure may be used:
(1) a cationic polymer oE the type believed to be (A11304(0H)247+, having a globular structure as Eirst descrioed by Johansen, Acta. Chem. Scand., V. 14 (1960), p. 771, is rea¢ted in aqueous solution with a fourtht fifth or sixth period transition ~etal. These will pri~larily be Ero~ Groups 5B, 6B, 7B and 8 of the Periodic Table. The base ~lultiatomic complex is thought to be of the type:
AliVAllv2O4(OH)24)7~.
One of ~,ore of the noted elements may be substituted into either or both o~ the iv or vi coordinate sites.
The general formula for the substituted molecule ~,ay be represented as:
Nlv(~ll2-xMx)ivo4(OH)24+a where N ~,ay be A13+, Si4~, Ga3~, Ge4~, As5+, P5+, Cr3+, Fe3+, V5+, Ru3+, Ru4+, Ni3+; M ~lay be one or more of the elements of Groups 5B, 6B, 7B and 8 of the 4th, 5th 27~
or 6th Periods of the Periodic Table. The value for "x" may be from about 1 to about 6. The value for "a"
depends upon tne nature of the metal substitutions.
Representative multimetal cationic polymer complexes include:
(FeiV(Allocr2)vio4(oH)24 (AliV(AlgFe3)vio4(OH)247~
(Aliv(AlloNi2)vio4(o~)245 .
Ooviouslyl such substitutions may change the charge on the poly.mer molecule. Depending on the solution pH, such multimetallic molecules ~,ay be hydrolyzed to produce lower charged species as indicated by Vaughan, et al., Proc. 5th Intl. Zeolite Conf., (1980), p. 94.
Other met'nods for producing (A113)7+ are discussed below and may be used as an alternative to beginning with a com~,ercial solution of lower aluminum chlorohydrol.
t2) A smectite clay is mixed with the aqueous solution of polymeric cationlc hydroxy multi-metal complex formed in step (1), in an,ounts so that the weight ratio of clay to metal complex solution is from 1:2 to 1,000. The metal complex solution will preferably contain fro~l l to 40 percent by weight solids in a suitable liquid medium, such as water.
(3) The mixture of clay and metal complex is maintained at a temperature of 5C to 200C Eor a period of 0.1 to 4.0 hours.
9~ Z7~7 (4) The reacted clay solids are xecovered and heated at a temperature of fro~l 200C to 70~C to deco~lpose the hydrolyzed metal co~lplex to a pillar believed to be of multiple metallic oxides or hydroxides.
. The clays which are suitable for use as starting materials in the present invention are the group of minerals known as smectites and are generally described above in the Background of the Invention. An extensive discussion of these materials is given in "Crystal Structures of Clay Materials and Their X-Ray IdentiEication", edited by G. W. Brindley, et al., (Mineralogical Soc.), 19~0.
The inorganic metal polymers that are used as starting material for production of the multi!TIetal poly~lers are generally known as basic alu~linu~l com-plexes which are formed by the hydrolysis of aluminulT, salts. While there is inevitably some disagreement on the nature of the species present in hydrolyzed metal complex solutions (or suspensions), it is generally believed that these ~,ixtures contain highly charged cationic colT,plexes with several ~,etal ions being co~,plexed~
The hydrolysis of cations brings about poly-~,ers through a process called olation. For alu~,inum this process is described by C. L. Rollinson in "Che~,istry of the Coordina~ion Co~,pounds", edited by J. C. Bailar, Reinhold Publishing Corp., New York, (1956) as follows:
,..G.~
OH +~ H20~ +-~
(N2O)~Al~ Al~H20)4 [(~2)4A~ (H2)~] ~2 ~O
O
In this process, single or double OH- hridges can be formed between Al ions. In less acidic solution, larger polymers are formed by the process and the bridging OH- can be converted to a bridging o-2, a process called oxolation. Note that a doubly OH
bridged complex is a pair of edged-sharing octahedra, and this is the same type of structure found in boehmite, AlOOH, where the OH- groups at the surface of the layers are each shared by two A106 octahedra. In hydrargillite, Al(OH)a3, all oxygen are also shared between two A106 octahedra. Various methods that have been used to produce Al polymers are discussed in U. S.
Patent No. 4,176,090.
However, for the purposes of ~laking the novel substituted clays of the invention, mixtures oE
aluminum salts and transition metal salts are used.
The metal ions may eitner be added to a solution already containing (All3)7+ poly~lers or may be added to a solution in which those ~olymers are being formed. Either method appears to produce similar mixed metal polymers. The present work is concerned only with the transition ~,etal cationic substituted forms of (All3)7+ having the general formula:
Niv(All2-xMx)v104(OH)2~
where N ~,ay be Al3~, Si4~, Ga3~, Ge4+, AsS+, p5+, Cr3+, Fe3+, V5+, Ru3+, Ru4+, Ni3+ or a mixture; M may be one or more of the elements selected from Groups 5B, 6B, 7B
and 8 of the 4th, 5th or 6th Periods of tne Periodic Table. Thése ~,etals include V, Cr, Mn, Fe, Co, Ni, Nb, Mo, Tc, Ru, Rh, Pd, Ta, W, Re, Os, Ir and Pt. The value for "x" ~,ay be from about l to 6. The value of "a" depends upon the ~,etal substitutions.
The preferred ~laterial is -that when N is al or ~l and Ru and M is selected fro~, V~ Cr, Mn, Fe, Co, Ni or a mixture of these metals.
The polymers described above ~,ay be exchanged into smectite-type clays by cation exchange or other ~,ethods of imibition to for~, expanded clays.
Typically the clay will be Einely ground and slurried in an excess of water. The ~,ultimetallic polyn,er is also added in a large amount to the clay slurry. The mixture is then aged for a period of time sufEicient to allow introduction of the poly~,er to a position between platelets of the host clay.
~ eferring to the drawing, Figure 1 rep-resents a typical sT,ectite which has been treated with the IT,ulti~letal complex poly~,ers in accordance with the teachinys of this invention and have a repeat distance A of 16 to 24 ~. The distance ~ between layers ranges between 6 and 16 ~. The height of the pillar b is established when the pillared ~lulti~,etal co~T,plex polymer which is inserted between the clay platelets is decolr,posed by calcination at temperatures between 200C
and 700C. The distance as shown in the drawing may be readily obtained from X-ray diffraction pattern for the various products and represent the first-order basal reflection paralrleter~ i.e., 001.
It should be unders-tood that within a given clay structure the layers are not uniform but instead form a heterogeneous chemical mixture in which the exact composition of one layer ~,ay be so~,ewhat dif-feren-t from that adjacent layer. This would be expected to result in slight variations in charge between layers, and, therefore, slight differences in the a~,ount of polymer exchange in different layers.
Since the size of the ~,ultimetal polymer is the con-trolling factor in setting the inner layer distance, charge heterogeneity on the layers would only affect the number of polymer species between the layers, that is to say, the number of pillars but not their size.
In general, calcined products of the inven-tion will have interlayer spacing oE 6 to 16 ~, a nitrogen BET surface area of 150 to 600 lTl2/gram~ and a nitrogen pore volu~,e of from 0.1 to 0.6 cc/g. Further-,ore, the novel pillared multin,etal interlayered claycomposition possess a substantial internal micropore structure, reflected by the nitrogen pore size distri-bution analyses which show a ~,ajor fraction of pores inthe range of less than 25 A. The pillars -themselves, in tha-t they are produced by heating the multimetallic poly~,ers discussed above, must contain so~,e alurninum.
A portion of the alu~inu~, may be replaced by a nu~,ber of semi ~,etals or metals, as discussecl above, i.e., NlV
may be one or more of Al, Si, Ga, Ge, As, P, Cr, Fe, V, Ru or Ni in the cationic multimetal polymer. Further-more, a substantial portion of the metal co~,pound in the pillar ~,ust be at least one or ~,ore of V, Cr, Mn, Fe, Co, Ni, Nb, Mo, Tc, Ru, Rh, Pd, Ta, W, Re, Os, Ir or Pt. The Mx component of the poly~,er intermediate is the source of these metals. The compound in the pillars is believed to be, after calcination, ~lostly an oxide of a si~,ple or co~,plex type. Some hydroxide may remain, however.
These interlayered products are useful as adsorbents, catalytic supports and in many instances as catalysts. Furthermore, it is contemplated that the interlayered clay products ~,ay be combined with other inorganic oxide adsorbents and catalysts, such as silica, alumina, silica-~,agnesia, silica-alumina, hydrogel, natural or synthetic zeolites, and clays.
These co~,positions ~,ay be useful in the preparation of catalysts which contain other active or stabilizing ~,etals, such as platinum, palladium, cobalt, molyb-denu~,, nickel, tungsten, rare-earths and so forth, as well as n,atrix components, such as silica, alumina, and silica-alu~,ina hydrogel. The resulting catalysts may be used in conventional petroleum conversion processes, such as catalytic cracking, hydrocracking, hydrotreat-ing, iso~,erization, re~orming, in polymeriza-tion and other petrochemical processes, as well as in ~,olecular sieve separations. It is contemplated that these com-~ ~5~
positions ~,ay be especially useful in preparing bifunctional catalysts wherein a primary ~.etallic catalyst is introduced into the clay by ion exchange and a secondary functional catalytic material is incor-porated in the pillars as a portion of the multi~etal pillars ~
Having described the basic aspects of the invention, the following specific exa~.ples are given to illustrate the preferred specific embodi~.ents.
Example 1 In this exa~.ple, sufficient Cr3+ was added to an alu~inu.~, chlorohydrol A113O4(OH)24C17 ("chloro-hydrol") solution to give a resulting theoretical pillar having a co~.position of AlllCr2O4(OH)2~C17.
A 0.5 gra~. CrC13 6H2O was dissolved, at roo~, te~perature, in 20 gra~.s of a 50 weight percent aqueous chlorohydrol solution (Reheis Chemical Co.). The solu-tion was stirred for 16 hours at 22C, then heated for two hours at 100C. ~ 10 gra~, sa~.ple of Bentolite s~,ectite (Georgia Kaolin Co.) was added and the slurry stirred at 95C for 75 ~.inutes. The ~.ixture was filtered and the blue-grey filter cake dried for 16 hours in a freeze dryer. X-ray diffraction analysis showed that about 30% of the clay had expanded to give an (001) layer spacing of 18.8 R. In contrast, a si~.ilar sa~,~le of the clay exchanged only with a solu-tion of CrC13 gave a green grey product that had an (001) reflection 15.1 R. After calcination at 550C
the poly~,er treated clay was a light tan-crea~. color, whereas the Cr3+ exchanged clay was a grey-brown color.
;'' Trade Mark ' ~ ~7Si~
Exa~lple 2 A O.S gran, sanlple of CrCl3 6H20 was dissolved in 10 yra~ls H2O and mixed with a 20 gram sample of chlorohydrol (as in Exa~,ple 1~. A~ter aging for 16 hours at 22C, the polymer solution was hot-aged for 75 n,inutes at 95C. A 10 gram sa~,ple of Bentolite L smectite was added and the slurry agitated at 95C
for 90 nlinutes. The clay was filtered, yielding a blue grey filter cake and a similarly colored filtrate.
After freeze drying, the exchanged clay for 16 hours, the clay powder gave an X-ray diffraction (001) spacing of 18.2 A (60%) and a spacing at 15.2 ~ (25% indicat-ing only H2O intercalcination and 9.8 a indicating no expansion). ~fter calcination the sa~,ple turned a light tan-crean, color.
Example 3 In this example Ni~+ is substituted into the pillar.
A 0.5 gra~l sa~,ple of NiC126 6H20 was dissolved in 20 grams H2O, and added to 20 grams of a 50 weight percent solution of chlorohydrol (Reheis Che~,ical Co.). The resulting mixture was stirred for 10 n,inutes at room temperatureO ~ 10 gra~, sample of Bentolite L n,ont~lorillonite was added and the whole was stirred for 16 hours at 23C. After filtration, the filter cake was freeze dried. X-ray diffraction showed the sample to have strong reflections at 21.7 A and 11.8 ~ After calcination of the material at 450C
for one hour, the sample was equilibrated at 88~ RH
over a saturated solution of CaCl2. Thern,oyravimetric analysis of this sa~,ple showed a total weight loss of 26 weight percent, 23 weight percent being lost below a te~,perature of 450C. X-ray diffraction showed the sample to have a strong t001) reflection at 18.2 ~.
Sorption of n-hexane showed a weight gain of 3.8 weight percent. After calcining in air for 2 hours at 650C
and re-equilibrating with water at 88% for 2 hours, the sa~,ple sorbed 9 weight percent H2O. If two Ni2+ have replaced two A13+ in this experi~,ent, the intercalated poly~,er will have a for~,ula [AlllNi2O4(OH)2~]5+.
Having thus described the invention and giving several examples in its practice, it should be apparent that various equivalents will be obvious to one having ordinary skill in the art and yet be within the purview of the clai~,s appended hereon.
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS
FOLLOWS:
1. A pillared smectite clay product having generally separated layers wherein the interlayer dis-tances are substantially greater than a precursor of the same but non-separated clay and wherein the product includes pillars comprising an aluminum, compound and at least one metal compound, which metal is selected from V, Cr, Mn, Fe, Cot Ni, Nb, Mo, Tc, Ru, Rh, Pd, Ta, W, Re, Os, Ir, Pt, or mixtures thereof, which pillars separate said layers.
2. The product of claim 1 wherein the pillars are a cationic polymeric complex of the formula:
N(Al12-xMx)O4(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, Pd, Ta, W, Re, Os, Ir, Pt or a mixture thereof;
x is from l to 6; and a depends upon the selection of M and N.
N(Al12-xMx)O4(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, Pd, Ta, W, Re, Os, Ir, Pt or a mixture thereof;
x is from l to 6; and a depends upon the selection of M and N.
3. The product of claim 1 wherein M is selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Ru and mixtures thereof.
4. The product of claim 1 wherein the pillars are substantially oxides.
5. The product of claim 1 wherein the smectite is selected from the group consisting of hec-torite, chlorite, bentonite, monmontmorillonite, beidel-lite and mixtures thereof.
6. A process for preparing an interlayered multimetallic smectite clay product which comprises the steps of:
(a) reacting a smectite with an aqueous composition comprising a polymeric cationic hydroxy multimetal comlplex of the formula:
N(Al12-xMx)O4(OH)24 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, Pd, Ta, W, Re, Os, Ir, Pt, or a mixture thereof;
x is from 1 to 6; and a depends upon the selection of M and N, and to produce an interlayered smectite product;
(b) separating the interlayered smectite product from the mixture.
(a) reacting a smectite with an aqueous composition comprising a polymeric cationic hydroxy multimetal comlplex of the formula:
N(Al12-xMx)O4(OH)24 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, Pd, Ta, W, Re, Os, Ir, Pt, or a mixture thereof;
x is from 1 to 6; and a depends upon the selection of M and N, and to produce an interlayered smectite product;
(b) separating the interlayered smectite product from the mixture.
7. The process of claim 6 wherein M is selected from the group consisting of V, Cr, Mn, Fe, Co, Ni, Ru and mixtures thereof.
8. The process of claim 6 wherein said mixture is reacted at a temperature between about 5°C
and 200°C for a period of from 0.1 to 4 hours.
and 200°C for a period of from 0.1 to 4 hours.
9. The process of claim 6 wherein the inter-layered smectite product is heated at a temperature of from 200°C to 700°C.
10. The process of claim 6 wherein from about 0.05 to about 2.0 parts by weight of said metal complex is fixed with each part by weight of said smectite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000516085A CA1275087A (en) | 1986-08-15 | 1986-08-15 | Multimetallic pillared interlayered clay products and processes of making them |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000516085A CA1275087A (en) | 1986-08-15 | 1986-08-15 | Multimetallic pillared interlayered clay products and processes of making them |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1275087A true CA1275087A (en) | 1990-10-09 |
Family
ID=4133742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000516085A Expired CA1275087A (en) | 1986-08-15 | 1986-08-15 | Multimetallic pillared interlayered clay products and processes of making them |
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| Country | Link |
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| CA (1) | CA1275087A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111468185A (en) * | 2020-04-16 | 2020-07-31 | 江苏星诺新材料科技有限公司 | Supported photocatalyst and preparation method and application thereof |
-
1986
- 1986-08-15 CA CA000516085A patent/CA1275087A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111468185A (en) * | 2020-04-16 | 2020-07-31 | 江苏星诺新材料科技有限公司 | Supported photocatalyst and preparation method and application thereof |
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