CA1106346A - Pillared interlayered clay materials useful as catalysts and sorbents - Google Patents
Pillared interlayered clay materials useful as catalysts and sorbentsInfo
- Publication number
- CA1106346A CA1106346A CA305,166A CA305166A CA1106346A CA 1106346 A CA1106346 A CA 1106346A CA 305166 A CA305166 A CA 305166A CA 1106346 A CA1106346 A CA 1106346A
- Authority
- CA
- Canada
- Prior art keywords
- smectite
- interlayered
- clay
- group
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/049—Pillared clays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/40—Clays
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/42—Micas ; Interstratified clay-mica products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/46—Amorphous silicates, e.g. so-called "amorphous zeolites"
Abstract
Stable pillared interlayered clay compositions are prepared by reacting smectite type clays with polymeric cationic hydroxy metal complexes of metals such as aluminum, zirconium, and/or titanium. These novel interlayered clay compositions which possess substantial surface area in pores of less than 30.ANG.
in diameter are used as catalysts, catalytic supports, and sorbents.
in diameter are used as catalysts, catalytic supports, and sorbents.
Description
1~P6346 . ~
:.
. .~ .
~¦ The present invention relates to novel clay ;I derived co~positions, and more specifically to interlayered derivatives of smectite type minerals Ilayered clays) which possess considerable internal micropore volume and have useful catalytic and adsorbent ~ properties.
¦ Layered naturally occurring and synthetic smectites ~1 such as bentonite, montmorillonites and chlorites may `~ be visualized as a "sandwich" comprising two outer layer of silicon tetrahedra and an inner layer of alumina octahedra. These "sandwiches" or platelets ;1 are stacked one upon the other to yield a clay particle.
~ Normally this yields a repeating structure every nine `1 20 angstroms or thereabouts. Much work has been done to demonstrate that these platelets can be separated ¦ further, i.e. interlayered by insertion of various polar molecules such as water, ethylene glycol, various amines, etc. and that the platelets can be separated by as much as 30 to 40A. Furthermore, p-ior workers:', :
similarly prepared phosphated or alumino-phosphated interlayered clays as low temperature traps for slow release fertilizer. The interlayered clays thus far prepared from naturally occurring smectites are~not suitable for general adsorbent and catalytic applications ', ~ A
` _"
~
..`,' , ' ` .
due to the fact -they tend to collapse when subjccted ~; to high temperatures.
Description of the Prior Art U.S. patents 3,803,026; 3,844,979; 3,887,454; and 3,892,655 descri~e layered clay-like materials and the process for using these materials. The layered clay materials are prepared from synthe-tic solutions of silica, alumina and magnesia salts. The final product has a composition similar to the composition of the clays covered in the instant application. The product of the instant application differs from the disclosed products, in that it contains non-exchangeable alumina between the sandwiches and an interlayer spaciny greater than aDout 6A is characteristic of an anhydrous product.
U.S. Patent 3,275,757 also discloses synthetic layered type silicate materials as does U.S. Patent 3,252,889. U.S. Patent 3,586,478 discloses the method of producing synthetic swelling clays of the hectorite type by forming an aqueous slurry from a water soluble magnesium salt, sodium siIicake, sodium carbonate or sodium hydroxide ana materials containing lithium and flouride ions. The slurry is then hydrothermally treated to crystallize a synthetic clay-like material.
U.S. Patents 3,666,407 and 3,671,1gO describe other methods of preparing clay~like materials. All of these i synthetic clays are acceptable raw materials ~or use in the instant invention in place of the naturally occurring clays. ~owever, by virtue of ready availability of large ., 4~
.:
quantities at low prices, the natural clays will ~enerally be prepared for use in the present invention.
; U.S. Patents 3,798,177 and 4,060,480 disclose the preparation of hydroxy-aluminum modified smectite clays ' wherein a gibbsite-like layer is formed between the crystalline layers of the clay. The gibbsite-like layer is continuous and does not substantially increase the internal pore volume (micropore characteristics) of the modified clay material.
The present invention distinguishes over the prior ~: art in that it is concerned with a novel method for modifying known smectite type minerals in such a way as to produce a subs-tantial micropore structure in the minerals and thereby yield novel catalytic and sorbent products having utility in the petroleum, cKemical and related industries. The resultant properties may be ; viewed as being more characteristic of crystalline zeolites than clays.
srief Description of the Invention The present invention relates to the preparation of novel "pïllared" interlayered clays which are obtained - ~ .
by reacting smectite type clays with polymeric cationic hydroxy metal complexes. The pillared interlayered clays-of our invention possess a unique internal micropore structure which is established by introducing discrete/
non-continuous inorganic oxide particles, i.e. pillars, .,.,, O
having a length of about 6 to 16A between the clay layers.
; These pillars serve to prop open the clay layers upon ~ removal of water and form an internal interconnected , , micropore structure throughout the interlayer in which the majority of the pores are less than a~out 30A in diameter.
,'' : - 4 -: : .
, . : ., :
6~46 . . .
More specifically, we have found that thermally stable interlayered clays which have an interlayer spacing of up to about 16A and greater than 50% of i~s surface area in pores of less than 30A in diameter may be prepared by reacting a naturally occurring or synthetic smectite type clay with a polymeric cationic hydroxy metal complex, such as aluminum chLorohydroxide complexes ("chlorhydrol"), and heating to convert the hydrolyzed polymer complex into an inorganic oxide.
Thus, in acco~clance ~ith the present teachings, an interlayered smectite clay product is provided which includes an inorganic oxide selected from the group consisting of alumina, zirconia and mixtures thereof ~etween the layers thereof, and which possesses an inter-layer distance of from about 6 to 16 A, the interlayered clay has greater than about 50 percent of its surface area in pores of less than 30 A in diameter.
.
.~ In accordance ~ith a further emhodiment of the ; present teachings, a process is provided for preparing : 20 an interlayered smect~te which comprises reacting a smectite .; with a mixture o~ a polymeric cationic hydroxy inorganic-: metal complex.selected from the group consisting of aluminum ancl zirconium complexes and mixtures thereof and water to obtain a smectite having greater than 50 percent of its surface area in pores of less than 30 A
in diameter after dehydration, and separating the inter-layered smectite from the mtxture.
.
. . .~ -, . ~ .
! - - 5 -; .
~: .
. ~ .
;34~
., A more clear understanding of our invention may be obtained from the following detailed description, specific examples, and drawing wherein:
igure 1 represents a cross-sectional view of the structure of a typical smectite type clay which may be used to prepare the novel interlayered clay products , of our invention.
' Figure 2 is a cross-sectional view of the clay of Figure 1 which has been treated with a polymeric cationic hydroxy metal complex to form a pillared interlayer between the clay layers; and Figure 3 represents the compositian of Figure 2 , which has been calcined to convert the interlayered polymeric complex into "pillars" of stable inorganic -; oxide.
`,~, To obtaïn the novel pillared interlayer clay products ~; of our invention the following general procedure may be ' used: ' , ;
1) A smectite clay lS mixed with an aqueous solution of~a polymeric' cationic hydroxy ~'¦ ' metal complex such as aluminum chlorhydrol, "~ ' .
,- , . ., .;
,: , `~`1 ,,,,., : :
,~., ~; I .
~.......................................................................... .
' ~.
,, - 5a -. ) . :
, , in amounts wherein the weight ratio of clay to metal complex solution is from 1:2 to 1000. The metal complex solution will preferably contain from about 1 to 40~ by weight solids in a suitable liquid medium such as water.
The mixture of clay and metal complex is maintained at a temperature of about 5 to 200C for a period of'0.1 to 4.0 hours.
: , . .
3) The reacted clay solids are recovered and '~ heated at a temperature of from about 200 -' to 700C to decompose the hydrolyzed metal com~lex to a pillar of inorganic oxide.
The clays used as starting materials'in the present ' invention are the group of minerals commonly called .. . . .
smectites an~ represented by the general formula:
(Si8) V(Al4) O20(OH)4 where the IV designation indicates an ion coordinated to four other ions, 'and VI designates an ion coordinated to six other ions. The IV coordinated ion is commonly -Si4+, A13+ and/or Fe3+, but could also include several other four coordinate ions (e.g., P5 , B3 ,'Ge4+, Be etc~. The VI coordinated ion is commonly Al or Mg2+, but could also include many possible hexa-coordinate ions '(e.g.' Fe3+, Pe2+,~'N12+, Co2 , Li+, etc.).' The charge cleficiencies created by the various ' substi~utions i~to these four and six coordinate cation positions, are ~al'ànced'by~one or several'cations ~
3~6 ;; located between the structural units. h7ater may also be occluded between these structural units, bonded either to the structure itself, or to the cations as -~ a hydration shell. When dehydrated, the above structural, .
units have a repeat distance of about 9.1 A, measured by X-ray diffraction. Typical commercially available clays include montmorillonite, bentonite, beidellite ; and hectorite.
The inorganic metal polymers used in the practice of the present invention are generally known as basic aluminum; zirconium, and/or titanium complexes which are formed by the hydrolysis of aluminum, zirconium, - and/or titanium salts. While there is some disagreement on the nature of the species present in hydrolyzed metal complex solutions (or suspensions), it is generally - believed that *hese mixtures contain highly charged `~ cationic complexes with several metal ions being x complexed.
,~ - The inor~anic aluminum polymers used to prepare ~0 our novel pillared interlayered clay compositions .: , . - .
-~ comprise solutions of discrete polymer particles having ,~ O
i~ a generally spherical shape and a diameter of about 8A
.. . .
~i` and in which the aluminum atoms are present in the- - ; , tetrahedral coordinated form to an extent of up to : about lO~i as determined b~ NMR measurement as shown by , ;~ Rausch and Bale, in J. Chem. Phys. 40 (11), 3391 (1964), .: . . . : ........................... . -the remaincler bei~g octahedral coordinated. The typical .,j, .
- hydroxy-aluminum polymers previously used to produce unLform gibbsite; layers ~etween cla~ }ayers,~ is~
characterized~by the presence of substantially 100 : :
1~ 346 octahedrally coordinated aluminum ln the f orm of gihb ; gibbsite-like sheet polymers.
' When AlC13 6 H20 dissolves in water, it ionizes -''- as follows: ' ' Al(H20)6 + 3Cl with most o,f theiCl being ionic. Since such solutions are acidic, then hydrolysis must take place to a substantial degree, particularly in,view of the , relatively high value of the ratio of ionic charge to "~ 10 ionic radius which characterizes the aluminum ion. The ~,~ initial hydrolysis step is ,~ Al(H20~6 ~ [Al(H~0)501I] ~ H
and the complex ion formed by this hydrolysis is basic.
~ In the usual terminology of such complexes, this ,~ hydrolysis product is "1/3 basic". Such a species is , present in acidic aluminum chloride solutions, since '~ hydrolysis is responsihle for the acidity of these solutions. , , , . . .
: As a means of better understanding these basic ~` 20 polymers, it is important to differentiate between ' the basicity of a solution and the basicity of a complex . - . . : . , ; ' ion in solution. The nature of the polymer species -- present is dependent on pH, concentration and temperature.
~;~ ' Lowering-the pH by addition of H~ shifts the hydrolysis , reaction to the le~t, causing a decrease in the average , molecular weight of the polymer. It is important to ' ~ note that thé total basicity o~ the complexes will ,~ always~be greater than the basic,ity of the solution per ~' se, because o the factor of hydrolysis. Increasing concentration and higher,temperatures fàvor incrèased,~
.~
63~f~
: .
degrees of hydrolysis, leading to larger polymers.
The hydrolysis of cations brings about polymers through a process called olatIon, which is described by C. L. Rollinson in Chemistry of the Coordination .:
Compounds, Edited by J. C. Bailar, Reinhold Publishing '- Corporation, New York, 1956, as follows:
- _ ++ _ _ ++ H 1 +4 (H20)4Al Al(H2)4 > (H20)4Al\ / l(H20)4 + 2 H20 OH2 HO _ H _ , In this process single or double OH bridges can be formed between ~1 ions. In less acidic solution, larger ,' polymers are formed by the process and the bridying OH
,- can be converted to bridging o 2, a process called ~ oxolation. Note that a doubly OH bridged complex is '~ a pair of edge-sharing octahedra, and this is the s-ame .
type of structure found in boehmite, AlOOH, where the OH
groups at the surface of the layers are each shared between two A106 octahedra. In hydrargillite, Al(,OH)3, all ` oxygens are also shared between two A106 octahedra.
,, Some of the prior art methods that have been used ' to prepare Al polymers include:
, al Tsutida and Kobayashi: J. Chem. Soc. Japan (,Pure Chem. Sec.l, 64, 1268 (,1943) discloses the reaction of solutions of AlC13-6 H20 or HCl with an excess - of metallic aluminum;
nAl+2AlX3 ~ A12+n~OH)3nX6 _ 9 _ '. ~
:
;3~6 b) Inove, Osugi and Kanaya; J. Chem. Soc. Japan (Ind. Chem. Sec.~, 61, 4Q7 (:19581 discloses that more than an equivalent amount of aluminium hydroYide :is reacted with an acid;
:.
. .~ .
~¦ The present invention relates to novel clay ;I derived co~positions, and more specifically to interlayered derivatives of smectite type minerals Ilayered clays) which possess considerable internal micropore volume and have useful catalytic and adsorbent ~ properties.
¦ Layered naturally occurring and synthetic smectites ~1 such as bentonite, montmorillonites and chlorites may `~ be visualized as a "sandwich" comprising two outer layer of silicon tetrahedra and an inner layer of alumina octahedra. These "sandwiches" or platelets ;1 are stacked one upon the other to yield a clay particle.
~ Normally this yields a repeating structure every nine `1 20 angstroms or thereabouts. Much work has been done to demonstrate that these platelets can be separated ¦ further, i.e. interlayered by insertion of various polar molecules such as water, ethylene glycol, various amines, etc. and that the platelets can be separated by as much as 30 to 40A. Furthermore, p-ior workers:', :
similarly prepared phosphated or alumino-phosphated interlayered clays as low temperature traps for slow release fertilizer. The interlayered clays thus far prepared from naturally occurring smectites are~not suitable for general adsorbent and catalytic applications ', ~ A
` _"
~
..`,' , ' ` .
due to the fact -they tend to collapse when subjccted ~; to high temperatures.
Description of the Prior Art U.S. patents 3,803,026; 3,844,979; 3,887,454; and 3,892,655 descri~e layered clay-like materials and the process for using these materials. The layered clay materials are prepared from synthe-tic solutions of silica, alumina and magnesia salts. The final product has a composition similar to the composition of the clays covered in the instant application. The product of the instant application differs from the disclosed products, in that it contains non-exchangeable alumina between the sandwiches and an interlayer spaciny greater than aDout 6A is characteristic of an anhydrous product.
U.S. Patent 3,275,757 also discloses synthetic layered type silicate materials as does U.S. Patent 3,252,889. U.S. Patent 3,586,478 discloses the method of producing synthetic swelling clays of the hectorite type by forming an aqueous slurry from a water soluble magnesium salt, sodium siIicake, sodium carbonate or sodium hydroxide ana materials containing lithium and flouride ions. The slurry is then hydrothermally treated to crystallize a synthetic clay-like material.
U.S. Patents 3,666,407 and 3,671,1gO describe other methods of preparing clay~like materials. All of these i synthetic clays are acceptable raw materials ~or use in the instant invention in place of the naturally occurring clays. ~owever, by virtue of ready availability of large ., 4~
.:
quantities at low prices, the natural clays will ~enerally be prepared for use in the present invention.
; U.S. Patents 3,798,177 and 4,060,480 disclose the preparation of hydroxy-aluminum modified smectite clays ' wherein a gibbsite-like layer is formed between the crystalline layers of the clay. The gibbsite-like layer is continuous and does not substantially increase the internal pore volume (micropore characteristics) of the modified clay material.
The present invention distinguishes over the prior ~: art in that it is concerned with a novel method for modifying known smectite type minerals in such a way as to produce a subs-tantial micropore structure in the minerals and thereby yield novel catalytic and sorbent products having utility in the petroleum, cKemical and related industries. The resultant properties may be ; viewed as being more characteristic of crystalline zeolites than clays.
srief Description of the Invention The present invention relates to the preparation of novel "pïllared" interlayered clays which are obtained - ~ .
by reacting smectite type clays with polymeric cationic hydroxy metal complexes. The pillared interlayered clays-of our invention possess a unique internal micropore structure which is established by introducing discrete/
non-continuous inorganic oxide particles, i.e. pillars, .,.,, O
having a length of about 6 to 16A between the clay layers.
; These pillars serve to prop open the clay layers upon ~ removal of water and form an internal interconnected , , micropore structure throughout the interlayer in which the majority of the pores are less than a~out 30A in diameter.
,'' : - 4 -: : .
, . : ., :
6~46 . . .
More specifically, we have found that thermally stable interlayered clays which have an interlayer spacing of up to about 16A and greater than 50% of i~s surface area in pores of less than 30A in diameter may be prepared by reacting a naturally occurring or synthetic smectite type clay with a polymeric cationic hydroxy metal complex, such as aluminum chLorohydroxide complexes ("chlorhydrol"), and heating to convert the hydrolyzed polymer complex into an inorganic oxide.
Thus, in acco~clance ~ith the present teachings, an interlayered smectite clay product is provided which includes an inorganic oxide selected from the group consisting of alumina, zirconia and mixtures thereof ~etween the layers thereof, and which possesses an inter-layer distance of from about 6 to 16 A, the interlayered clay has greater than about 50 percent of its surface area in pores of less than 30 A in diameter.
.
.~ In accordance ~ith a further emhodiment of the ; present teachings, a process is provided for preparing : 20 an interlayered smect~te which comprises reacting a smectite .; with a mixture o~ a polymeric cationic hydroxy inorganic-: metal complex.selected from the group consisting of aluminum ancl zirconium complexes and mixtures thereof and water to obtain a smectite having greater than 50 percent of its surface area in pores of less than 30 A
in diameter after dehydration, and separating the inter-layered smectite from the mtxture.
.
. . .~ -, . ~ .
! - - 5 -; .
~: .
. ~ .
;34~
., A more clear understanding of our invention may be obtained from the following detailed description, specific examples, and drawing wherein:
igure 1 represents a cross-sectional view of the structure of a typical smectite type clay which may be used to prepare the novel interlayered clay products , of our invention.
' Figure 2 is a cross-sectional view of the clay of Figure 1 which has been treated with a polymeric cationic hydroxy metal complex to form a pillared interlayer between the clay layers; and Figure 3 represents the compositian of Figure 2 , which has been calcined to convert the interlayered polymeric complex into "pillars" of stable inorganic -; oxide.
`,~, To obtaïn the novel pillared interlayer clay products ~; of our invention the following general procedure may be ' used: ' , ;
1) A smectite clay lS mixed with an aqueous solution of~a polymeric' cationic hydroxy ~'¦ ' metal complex such as aluminum chlorhydrol, "~ ' .
,- , . ., .;
,: , `~`1 ,,,,., : :
,~., ~; I .
~.......................................................................... .
' ~.
,, - 5a -. ) . :
, , in amounts wherein the weight ratio of clay to metal complex solution is from 1:2 to 1000. The metal complex solution will preferably contain from about 1 to 40~ by weight solids in a suitable liquid medium such as water.
The mixture of clay and metal complex is maintained at a temperature of about 5 to 200C for a period of'0.1 to 4.0 hours.
: , . .
3) The reacted clay solids are recovered and '~ heated at a temperature of from about 200 -' to 700C to decompose the hydrolyzed metal com~lex to a pillar of inorganic oxide.
The clays used as starting materials'in the present ' invention are the group of minerals commonly called .. . . .
smectites an~ represented by the general formula:
(Si8) V(Al4) O20(OH)4 where the IV designation indicates an ion coordinated to four other ions, 'and VI designates an ion coordinated to six other ions. The IV coordinated ion is commonly -Si4+, A13+ and/or Fe3+, but could also include several other four coordinate ions (e.g., P5 , B3 ,'Ge4+, Be etc~. The VI coordinated ion is commonly Al or Mg2+, but could also include many possible hexa-coordinate ions '(e.g.' Fe3+, Pe2+,~'N12+, Co2 , Li+, etc.).' The charge cleficiencies created by the various ' substi~utions i~to these four and six coordinate cation positions, are ~al'ànced'by~one or several'cations ~
3~6 ;; located between the structural units. h7ater may also be occluded between these structural units, bonded either to the structure itself, or to the cations as -~ a hydration shell. When dehydrated, the above structural, .
units have a repeat distance of about 9.1 A, measured by X-ray diffraction. Typical commercially available clays include montmorillonite, bentonite, beidellite ; and hectorite.
The inorganic metal polymers used in the practice of the present invention are generally known as basic aluminum; zirconium, and/or titanium complexes which are formed by the hydrolysis of aluminum, zirconium, - and/or titanium salts. While there is some disagreement on the nature of the species present in hydrolyzed metal complex solutions (or suspensions), it is generally - believed that *hese mixtures contain highly charged `~ cationic complexes with several metal ions being x complexed.
,~ - The inor~anic aluminum polymers used to prepare ~0 our novel pillared interlayered clay compositions .: , . - .
-~ comprise solutions of discrete polymer particles having ,~ O
i~ a generally spherical shape and a diameter of about 8A
.. . .
~i` and in which the aluminum atoms are present in the- - ; , tetrahedral coordinated form to an extent of up to : about lO~i as determined b~ NMR measurement as shown by , ;~ Rausch and Bale, in J. Chem. Phys. 40 (11), 3391 (1964), .: . . . : ........................... . -the remaincler bei~g octahedral coordinated. The typical .,j, .
- hydroxy-aluminum polymers previously used to produce unLform gibbsite; layers ~etween cla~ }ayers,~ is~
characterized~by the presence of substantially 100 : :
1~ 346 octahedrally coordinated aluminum ln the f orm of gihb ; gibbsite-like sheet polymers.
' When AlC13 6 H20 dissolves in water, it ionizes -''- as follows: ' ' Al(H20)6 + 3Cl with most o,f theiCl being ionic. Since such solutions are acidic, then hydrolysis must take place to a substantial degree, particularly in,view of the , relatively high value of the ratio of ionic charge to "~ 10 ionic radius which characterizes the aluminum ion. The ~,~ initial hydrolysis step is ,~ Al(H20~6 ~ [Al(H~0)501I] ~ H
and the complex ion formed by this hydrolysis is basic.
~ In the usual terminology of such complexes, this ,~ hydrolysis product is "1/3 basic". Such a species is , present in acidic aluminum chloride solutions, since '~ hydrolysis is responsihle for the acidity of these solutions. , , , . . .
: As a means of better understanding these basic ~` 20 polymers, it is important to differentiate between ' the basicity of a solution and the basicity of a complex . - . . : . , ; ' ion in solution. The nature of the polymer species -- present is dependent on pH, concentration and temperature.
~;~ ' Lowering-the pH by addition of H~ shifts the hydrolysis , reaction to the le~t, causing a decrease in the average , molecular weight of the polymer. It is important to ' ~ note that thé total basicity o~ the complexes will ,~ always~be greater than the basic,ity of the solution per ~' se, because o the factor of hydrolysis. Increasing concentration and higher,temperatures fàvor incrèased,~
.~
63~f~
: .
degrees of hydrolysis, leading to larger polymers.
The hydrolysis of cations brings about polymers through a process called olatIon, which is described by C. L. Rollinson in Chemistry of the Coordination .:
Compounds, Edited by J. C. Bailar, Reinhold Publishing '- Corporation, New York, 1956, as follows:
- _ ++ _ _ ++ H 1 +4 (H20)4Al Al(H2)4 > (H20)4Al\ / l(H20)4 + 2 H20 OH2 HO _ H _ , In this process single or double OH bridges can be formed between ~1 ions. In less acidic solution, larger ,' polymers are formed by the process and the bridying OH
,- can be converted to bridging o 2, a process called ~ oxolation. Note that a doubly OH bridged complex is '~ a pair of edge-sharing octahedra, and this is the s-ame .
type of structure found in boehmite, AlOOH, where the OH
groups at the surface of the layers are each shared between two A106 octahedra. In hydrargillite, Al(,OH)3, all ` oxygens are also shared between two A106 octahedra.
,, Some of the prior art methods that have been used ' to prepare Al polymers include:
, al Tsutida and Kobayashi: J. Chem. Soc. Japan (,Pure Chem. Sec.l, 64, 1268 (,1943) discloses the reaction of solutions of AlC13-6 H20 or HCl with an excess - of metallic aluminum;
nAl+2AlX3 ~ A12+n~OH)3nX6 _ 9 _ '. ~
:
;3~6 b) Inove, Osugi and Kanaya; J. Chem. Soc. Japan (Ind. Chem. Sec.~, 61, 4Q7 (:19581 discloses that more than an equivalent amount of aluminium hydroYide :is reacted with an acid;
2~nAl(OH~3~6HX ~ A12~n(OH)3nX6 c) H. ~. Kohlschuter et al.: Z. Anorg. Allgem. Chem~, 248, 31Y ~1941~ desc:ribes a method wherein alkali is added to an aluminum salt solution;
2~nAlX3+3nMOH ~ A12~n(OH~3n~6 d~ T. G. Owe Berg: Z. Anory. Allgem. Chem., 269 213 (1952) discloses a procedure wherein an aqueous solution of AlX3 is passed through an ion exchange column in OH form, and el R. Brun: German Patent ~ 1,102,713 describes extended heating at~ 150C. of salts such as AlC13 6H2 The inorganic aluminum polymers used in the practice of the present invention are visualized ~; as having the general formula:
A12~n (OH~3n ~ 6 wherein n has a value of about 4 to 12; and X is usually Cl, Br, and/or NO3. These inorganic metal polymers are believed to have an average molecular weight of from about 300 to 3,000.
In addition to the above described aluminum complex polymers, polymeric cationic hydroxy complexes of metals such as zirconium, titanium, and mixtures thereof may be used. Preparation and description of zirconium complexes are described in:
.~ -- 10. --.
: . .
2~nAlX3+3nMOH ~ A12~n(OH~3n~6 d~ T. G. Owe Berg: Z. Anory. Allgem. Chem., 269 213 (1952) discloses a procedure wherein an aqueous solution of AlX3 is passed through an ion exchange column in OH form, and el R. Brun: German Patent ~ 1,102,713 describes extended heating at~ 150C. of salts such as AlC13 6H2 The inorganic aluminum polymers used in the practice of the present invention are visualized ~; as having the general formula:
A12~n (OH~3n ~ 6 wherein n has a value of about 4 to 12; and X is usually Cl, Br, and/or NO3. These inorganic metal polymers are believed to have an average molecular weight of from about 300 to 3,000.
In addition to the above described aluminum complex polymers, polymeric cationic hydroxy complexes of metals such as zirconium, titanium, and mixtures thereof may be used. Preparation and description of zirconium complexes are described in:
.~ -- 10. --.
: . .
3~
1) A. Clear~ield and P. ~. Vaughan, Acta Cryst. 9, 555 (-1956);
21 A. N. Ermakov, I. N. Marov, and V. K. ~elyaeva, Zh. Neorgan. Khim. 8 (7), 1623 (1963~.
3~ G. M. Muha and P. A. Vaughan, J. Chem. Phys.
33, 194-9, (1960~.
It is also contemplated that copolymers of the above noted metal complexes with silica and magnesium may be used. Furthermore, it is contemplated -that the hydrated or dehydrated metal complex treated smectite ~^ clays may be post treated with solutions of silicate, ~`~ ~agnesium, and phosphate ionis to obtain moxe stable and attrition resistant compositions.
The catalytic and adsorbent characteristics of the interlayered smectite clays of the present invention may be modified by ion exchange with a wide variation of cations including hydrogen, ammonium, and metals of Groups IB through VIII of the periodic table. In `; particular catalytic cracking and hydrocracking catalysts which contaIn rare earth, cobalt, molybdenum, nickel, tungsten, and/or noble metal ions are active for the catalytic conversion of hydrocarbons.
Referring to the drawing, Figure 1 represents a typical smectite wherein the layers or platelets O
have a repeat distance dl of about 9 to 12A depending on the degree of hydration. As shown in Figure 2, ;~ smectites which have ~een treated with metal complex polymers in accordance with the teachings of the present invention, have an increased repeat distance of d2 of from about 16 to about 24A. In Figure 3, a platelet ~'~
, -- 11 --. , .
;3~6 ;
.
repeat distance d3 which is less than d2 is shown in exaggerated form. The repeat distance d3, which is esta~lished when the pïllared metal complex polymer i`nserted between the platelets is decomposed by calcination to temperatures of about 200 to 700C., is found in practice to be substantially the same as d2, with only minor shrinkage of the pillared layer . . O
occurring to the extent o less than 0.5 A in cases. All the distances dl, d2 and d3 (layer repeat distances) are readily obtained directly from the X-ray diffraction patterns of the various products, and represent the first-order basal reflection parameter (i.e. 001~. The "interlayer distances" are obtained by subtracting the thickness (about 9A~ of the clay layer from the basal spacing obtained by X-ray diffraction, i.e. d4 = dl-9; d5 = d2-9; and d6 = d3-9-Recent research on the clay minerals has shown that within a given clay structure the layers are not uniform, but form a heterogenous chemical mixture in which the exact composition of one layer may be somewhat different from that of an adjacent layer. This would be expected to result in slight variations in charge between layers, and therefore, slight differences in i the amount of polymer exchanged in different layers. As . . the size of the polymer is the controlling factor in setting the interlayer dis-tance, charge heterogeneity on the layers would only effect the number of polymer species between the layers (i.e. the number of resultant 3Q pillars, not their size).
~; 12 -;, 3gl6 ,,,.~
In general, the ealeined produets of our invention will have an interlayer spaci`ng of about 6 to 16A, a nitrogen sET surface area o~ about 150 to 600 m /g, and a nitrogen pore volume of ahout 0.1 to about 0.6 ee/g. Furthermore, our novel pillared interlavered . elay eompositions possess a substantial internal mieropore structure which is characterized by a pore-size distribution in whieh more than 50%, and in many eases more than 75% oE the surfaee area is located in pores less than 30A in diameter as determined by .
eonventional nitrogen pore size distribution (PSD) adsorbtion measurements. The conventional prior art gibbsite-like interlayered elay produets (synthetie ehlorites~ possess no substantial surfaee area in pores . O
less than 3QA in diameter.
Our interlayer produets are useful as adsorbents and eatalytic supports. Furthermore, it is eontemplated that our interlayered elay products may be combined ~ith other inorganic oxide adsorbents and catalysts ;; 20 sueh as siliea, alumina, siliea-magnesia, siliea-alumina hydrogel, and natural or synthetie zeolites, and elays. Our produets are partieularly useful in the preparation of eatalysts whieh eontain aetive/stabilizing metals sueh as platinum, palladium, eobalt, molybdenum, niekel, tungsten, rare-earths and so forth, as well as matrix eomponents such as silica, aluminum and silica-alumina hydrogel. These catalysts are used in conventional petroleum conversion processes such as catalytic craeking, hydrocracking, hydrotreating, 30 is-omerization and reformi`ng catalysts; and as molecular sieve adsorbents.
- 13 _ :
a~ing descri~ed the ~asic aspects of our lnvention, the followïng speci~ic examples are ~iven to illustrate preferred specific embodiments.
Example_l A clay slurry was prepaxed from the natural clay product designated Volclay~ 200 by American Colloid Co.
A total of 32,000 ml. of a clay slurry containing 2.7 percent solids and an aluminum chlorohydroxide solution, prepared to contain 50 weight percent of the salt, and 1,110 grams of this solution was added. The resulting mixture was aged for one half-hour with agitation and the temperature was increased to 160. The slurry was aged for 1/2 hour at this temperature, the product was filtered, washed once with 16 gallons of hot ; deionized water, reslurried in deionized water and spray drïed. The properties of the product are set out in Table 1.
Example 2 ;A total of 31.7 gallons of the less than or equal to 2 mïcron sized particles of the natural clay product designated Volclay~ 200 by American Colloid Corporation was prepared by centrifugatïon. A 50 weïght percent solutïon of aluminum chlorohydroxide was prepared and 6,920 grams of the resulting solution was added to the clay slurry. The slurry was aged for 1/2 hour at 160F. and filtered on a belt filter. The filter cake was reslurried ïn deionîzed water; refiltered and again reslurried ïn deionized water and spray dried. The . . .
properties of the interlayered clay product are set out in Table 1 below.
; - 14 -.' . , ~63~6 ;
The catalytic activi.ties of th.ese products were determIned using the microacti`vity -test described i`n the article by F. T. Cîapetta e-t al. in the Oil and Gas Journal of October 16, 1967. The feed stock was a West Texas gas oil boiling in th.e range of 500 to 8QQF. The reactor was operated at a temperature of 92QF., a weight hourly space velocity of 16 and had a catalyst/oil ratio of 3. The product of Ex~mple 1 gave a 98.6% conversion, and the product of Example 2 gave a conversion of 82.5%.
'~' ',',:
,.
.~
'~
''~,',;
,:~
. - 15 - , "
, ~ - ,, .
3~6 , Example 3 One of the problems in encountered in the preparation , of thes-e slurries where the particle size is equal to or .. less than 2 microns is the tendency to loose part of the ;, product through the fïlter. To combat this problem a `,' flocculating agent was added to the clay slurry.
A batch of interlayered clay was prepared in Example 1.
Varying amounts of a high molecular weight GUAR designated polymer 7050-B by Stein, Hall & Co. were added to portions of the clay slurry. Each. sample was filtered on both a coarse (2-3 cubic eet/minute~ and a fine (1 cfm) filter , cloth. Results from the 0.5 to 10 grams polymer/100 grams clay indicated thickening at all levels, but 1 to 3 grams/100 ~': grams appeared to yield the clearest filtrates. When slurries ,~ were prepared without a flocculating agent, a considerable .'., amount of product was lost through the coarse filter cloth.
, . .
. The flocculations can also be affected by an addition .,. ~
"~, of low levels of sodium silicate (0.5 grams SiO2/100 grams .,: clay~. There was little 105S in product surface area with ' 20 th.ï.s treatment. Other flocculating agents of the anionic ,.,,~ of neutral type would be equally effectïve~
Example 4 '~j This example illustrates the use of calcium ,~. bentonite as the raw material in our novel process.
,', A slurry of particles having a particle size of equal to or less than 2 microns of calcium bentonite furnished by American Colloid Corporation was prepared hy centrïfugation. A total of 26.7 grams (:dry basis), of clay- from th.is s:lurry was diluted to 5.4 1. and 38.0 grams of a 50 weïgh,t percent aluminum chlorhydroxide solution was- added. The slurry was aged for 1/2 hour at 25C., and `~ ' ``
the pH was then adjusted to 2.0 with a 3.75% hydrochlor;c acid solution~ The slurry was- then aged for 1/2 hour at a temperature of 160F., filtered, washed with 2.7 1. of hot deionized water and oven dri`ed. The product recovered had a surface area of 35Q m2~gm. and a (001) basal spacing of 17.5A.
Example 5 This example illustrates the use of beidellite clay as a raw material.
A slurry was prepared from 15 grams (dry basis) of beidellite clay from Taiwan having a particle size of equal to or less -than 2 microns. The particles having a particle size of equal to or less than 2 microns were recovered by centrifugation. A total of 15 grams (dry basis) of the clay was diluted to 3 liters and 15.1 grams of a 50 wèight percent aluminum chlorhydroxide solution was added. The resulting slurry was aged for a , . . ~ .
` period of 1/2 hour. The pH ~as adjusted to 2.0 with 3.75 percent hydrochloric acid solution. The temperature was increased to 160F. and the slurry was aged at this temperature for a period of 1/2 hour. The slurry was filtered, washed with 1 liter of hot deionized water and i oven dried. The surface area of the product was 307 m /gm.
and the ~001) basal spacing was 18.OA.
Example 6 This example illustrates a method of utilizing a beneficiatecl montmorillonite without the necessity of separating the particles that have a particle size equal to or less than 2 mïcrons. The us-e of 3~ such readily availahle commerci`al product greatly reduces the pre-processing needed to prepare the -~
.. ~ .
materials of -this invention. ~ 25 gram. (dry basis) sample of a higfi purity air-floated Wyomi`ng bentonite furni`shed by American Colloid Company ~#325 Bentonite~
was slurried in a blender wï.th 1 liter of deionized water for 1/2 minute. A total of 21.5 grams of a 5Q percent aluminum chlorohydr.oxide solution was added and the slurry was aged for 1/2 hour at 150F.
.:
. The ~roduct was filtered, washed with 1 liter of : hot deionized water, and oven dried at 110C. The , :
.. 10 surface area of this product was 308 m2/gm.
xample 7 This example i.llustrates the product distribution `~ o~ a typical product prepared from the product described ~ in Examples 1 and 2. The catalystic activity of the ;.' product was determined using the micro-activity test ~ described in the article by F. G. Ciapetta et al. in : the Oîl and Gas Journal of October 16, 1967. The `~ feed stock was a Wes.t Texas gas oil boiling in the range of 500 to 800F. The reactor was operated at a temperature of 920F., a weight hourly space velocity ~ of 16 and a catalyst/oil ratio of 3. The test was carried out after the catalysts had been exposed to a . temperature of 1000F. for a period of 3 hours. The data collected in this run is set out in Table II below.
' ,., ~
.
Table II
Pillared Interlayered Clay prepared from Conversi`on Volclay 200 Conv.,* V% 77 3 H2 ,** W% .27 Cl ~ W% . 90 C2=, W% .71 C2 ~ W% .94 Total C3, W% 5~7 Total Dry Gas, W% 8.5 C3=,V% 5.4 C3, V% 4.2 Total C3, V% 9.6 .:
C4=, V% 2.6 iso~C4, V% 8.0 ,~ normal-C4,V% 1.7 Total C4, V% 12.3 C4~gasoline., V% 66.9 C5~gasoline, V% 54.6 Coke on cat,, W% 4~5 Coke-Total feed, W% 12.8 .~
.
`: :
*V% = Volume percent **W% = Weight percent ' - 2a -34~
;.'' Example 8 It has been found that i`~ the clay was added to ~` the alumi`num chlorohydroxide solution a larger solids concentration could he affected. Such additions to the aluminum chlorAydroxide soluti`on may be as high as abou-t 40 weight percent clay without encountering problems ;n mixing, pumping, or handling the clay in the fluid state. This greatly enhances the economy of the process in that much larger volumes of the ~roduct can be obtaïned and processed in a given time for a given sized system. The addition of clay to water followed by aluminum chlorhydroxide addition does not allow high solids levels to ~e achïeved. The former process is presumably achieved hecause-the polymer is instantaneously ïntercallated by the ~,~
clay-as the clay is added, and so inhibits dispersion of the clay platelets and subsequent formation of a clay-water gel.
A further advantage is that high solids cut down the use of energy in the drying step.
In an illustration of this, a total of 2,470 grams of a 50 weight percent of aluminum chlorhydroxide solution was diluted to 22.7 liters. ~ total of 5,320 ; yrams (5,072 gram dry basis) of bentonite was added to the slurry-. The slurry was aged at ~50~F. for a period of 1 hour and spray dried. The solids concen-tration of the product ~ed to the spray drier was approximately 2a percent, the product re~overed had a surface area of 273 m ~gm and a lattice d spacing (001~ of 17.9.
:.
.
Example 9 In thi`s example a slurry containi`ng 15.9 percent solids was prepared by diluting 2,720 grams of aluminum .
chlorhydroxide to 6 gallons- and 5000 grams (~dry basis) - of the clay was added -to this slurry. The slurry was ag;tated and aged 1/2 hour at 150E'., filtered, and washed on the filter with 6 gallons of hot deionized ~ater. The product was reslurried and spray dried.
The surface area of the product recovered a 316 m2/gm and the d spaciny (Q01~ was 18A.
Example 10 ' In this example a slurry containing a 35 percent total solids was prepared by addition of 125 grams (dry basis~ #325 sentonite clay (American Colloid Co.) to ~ a solution containing 65.2 grams of the aluminum polymer ; in a total volume of 25a ml. This slurry was aged 1 hour at 150F., filtered, washed wîth 1/2 1. hot ~; deionïzed water and dried. The product surface area was 263 m2/gm. and the (~alJ d spac;ng was 17.6A.
Example 11 In this example a less basic Al polymer is used ;~ to interlayer the smectite. Ordinary aluminum chlor-., hy-droxide (chlorhydrol) contains 5 OH /2 Al 3, and is 5/6 basic. 10 gms. dry basis of 2.0 Volclay~ 200 (American Colloid Co.) as a slurry was diluted to 1.0 1., and ~.3Q gms~ of a 2/3 ~asic Al polymer (i.e.,
1) A. Clear~ield and P. ~. Vaughan, Acta Cryst. 9, 555 (-1956);
21 A. N. Ermakov, I. N. Marov, and V. K. ~elyaeva, Zh. Neorgan. Khim. 8 (7), 1623 (1963~.
3~ G. M. Muha and P. A. Vaughan, J. Chem. Phys.
33, 194-9, (1960~.
It is also contemplated that copolymers of the above noted metal complexes with silica and magnesium may be used. Furthermore, it is contemplated -that the hydrated or dehydrated metal complex treated smectite ~^ clays may be post treated with solutions of silicate, ~`~ ~agnesium, and phosphate ionis to obtain moxe stable and attrition resistant compositions.
The catalytic and adsorbent characteristics of the interlayered smectite clays of the present invention may be modified by ion exchange with a wide variation of cations including hydrogen, ammonium, and metals of Groups IB through VIII of the periodic table. In `; particular catalytic cracking and hydrocracking catalysts which contaIn rare earth, cobalt, molybdenum, nickel, tungsten, and/or noble metal ions are active for the catalytic conversion of hydrocarbons.
Referring to the drawing, Figure 1 represents a typical smectite wherein the layers or platelets O
have a repeat distance dl of about 9 to 12A depending on the degree of hydration. As shown in Figure 2, ;~ smectites which have ~een treated with metal complex polymers in accordance with the teachings of the present invention, have an increased repeat distance of d2 of from about 16 to about 24A. In Figure 3, a platelet ~'~
, -- 11 --. , .
;3~6 ;
.
repeat distance d3 which is less than d2 is shown in exaggerated form. The repeat distance d3, which is esta~lished when the pïllared metal complex polymer i`nserted between the platelets is decomposed by calcination to temperatures of about 200 to 700C., is found in practice to be substantially the same as d2, with only minor shrinkage of the pillared layer . . O
occurring to the extent o less than 0.5 A in cases. All the distances dl, d2 and d3 (layer repeat distances) are readily obtained directly from the X-ray diffraction patterns of the various products, and represent the first-order basal reflection parameter (i.e. 001~. The "interlayer distances" are obtained by subtracting the thickness (about 9A~ of the clay layer from the basal spacing obtained by X-ray diffraction, i.e. d4 = dl-9; d5 = d2-9; and d6 = d3-9-Recent research on the clay minerals has shown that within a given clay structure the layers are not uniform, but form a heterogenous chemical mixture in which the exact composition of one layer may be somewhat different from that of an adjacent layer. This would be expected to result in slight variations in charge between layers, and therefore, slight differences in i the amount of polymer exchanged in different layers. As . . the size of the polymer is the controlling factor in setting the interlayer dis-tance, charge heterogeneity on the layers would only effect the number of polymer species between the layers (i.e. the number of resultant 3Q pillars, not their size).
~; 12 -;, 3gl6 ,,,.~
In general, the ealeined produets of our invention will have an interlayer spaci`ng of about 6 to 16A, a nitrogen sET surface area o~ about 150 to 600 m /g, and a nitrogen pore volume of ahout 0.1 to about 0.6 ee/g. Furthermore, our novel pillared interlavered . elay eompositions possess a substantial internal mieropore structure which is characterized by a pore-size distribution in whieh more than 50%, and in many eases more than 75% oE the surfaee area is located in pores less than 30A in diameter as determined by .
eonventional nitrogen pore size distribution (PSD) adsorbtion measurements. The conventional prior art gibbsite-like interlayered elay produets (synthetie ehlorites~ possess no substantial surfaee area in pores . O
less than 3QA in diameter.
Our interlayer produets are useful as adsorbents and eatalytic supports. Furthermore, it is eontemplated that our interlayered elay products may be combined ~ith other inorganic oxide adsorbents and catalysts ;; 20 sueh as siliea, alumina, siliea-magnesia, siliea-alumina hydrogel, and natural or synthetie zeolites, and elays. Our produets are partieularly useful in the preparation of eatalysts whieh eontain aetive/stabilizing metals sueh as platinum, palladium, eobalt, molybdenum, niekel, tungsten, rare-earths and so forth, as well as matrix eomponents such as silica, aluminum and silica-alumina hydrogel. These catalysts are used in conventional petroleum conversion processes such as catalytic craeking, hydrocracking, hydrotreating, 30 is-omerization and reformi`ng catalysts; and as molecular sieve adsorbents.
- 13 _ :
a~ing descri~ed the ~asic aspects of our lnvention, the followïng speci~ic examples are ~iven to illustrate preferred specific embodiments.
Example_l A clay slurry was prepaxed from the natural clay product designated Volclay~ 200 by American Colloid Co.
A total of 32,000 ml. of a clay slurry containing 2.7 percent solids and an aluminum chlorohydroxide solution, prepared to contain 50 weight percent of the salt, and 1,110 grams of this solution was added. The resulting mixture was aged for one half-hour with agitation and the temperature was increased to 160. The slurry was aged for 1/2 hour at this temperature, the product was filtered, washed once with 16 gallons of hot ; deionized water, reslurried in deionized water and spray drïed. The properties of the product are set out in Table 1.
Example 2 ;A total of 31.7 gallons of the less than or equal to 2 mïcron sized particles of the natural clay product designated Volclay~ 200 by American Colloid Corporation was prepared by centrifugatïon. A 50 weïght percent solutïon of aluminum chlorohydroxide was prepared and 6,920 grams of the resulting solution was added to the clay slurry. The slurry was aged for 1/2 hour at 160F. and filtered on a belt filter. The filter cake was reslurried ïn deionîzed water; refiltered and again reslurried ïn deionized water and spray dried. The . . .
properties of the interlayered clay product are set out in Table 1 below.
; - 14 -.' . , ~63~6 ;
The catalytic activi.ties of th.ese products were determIned using the microacti`vity -test described i`n the article by F. T. Cîapetta e-t al. in the Oil and Gas Journal of October 16, 1967. The feed stock was a West Texas gas oil boiling in th.e range of 500 to 8QQF. The reactor was operated at a temperature of 92QF., a weight hourly space velocity of 16 and had a catalyst/oil ratio of 3. The product of Ex~mple 1 gave a 98.6% conversion, and the product of Example 2 gave a conversion of 82.5%.
'~' ',',:
,.
.~
'~
''~,',;
,:~
. - 15 - , "
, ~ - ,, .
3~6 , Example 3 One of the problems in encountered in the preparation , of thes-e slurries where the particle size is equal to or .. less than 2 microns is the tendency to loose part of the ;, product through the fïlter. To combat this problem a `,' flocculating agent was added to the clay slurry.
A batch of interlayered clay was prepared in Example 1.
Varying amounts of a high molecular weight GUAR designated polymer 7050-B by Stein, Hall & Co. were added to portions of the clay slurry. Each. sample was filtered on both a coarse (2-3 cubic eet/minute~ and a fine (1 cfm) filter , cloth. Results from the 0.5 to 10 grams polymer/100 grams clay indicated thickening at all levels, but 1 to 3 grams/100 ~': grams appeared to yield the clearest filtrates. When slurries ,~ were prepared without a flocculating agent, a considerable .'., amount of product was lost through the coarse filter cloth.
, . .
. The flocculations can also be affected by an addition .,. ~
"~, of low levels of sodium silicate (0.5 grams SiO2/100 grams .,: clay~. There was little 105S in product surface area with ' 20 th.ï.s treatment. Other flocculating agents of the anionic ,.,,~ of neutral type would be equally effectïve~
Example 4 '~j This example illustrates the use of calcium ,~. bentonite as the raw material in our novel process.
,', A slurry of particles having a particle size of equal to or less than 2 microns of calcium bentonite furnished by American Colloid Corporation was prepared hy centrïfugation. A total of 26.7 grams (:dry basis), of clay- from th.is s:lurry was diluted to 5.4 1. and 38.0 grams of a 50 weïgh,t percent aluminum chlorhydroxide solution was- added. The slurry was aged for 1/2 hour at 25C., and `~ ' ``
the pH was then adjusted to 2.0 with a 3.75% hydrochlor;c acid solution~ The slurry was- then aged for 1/2 hour at a temperature of 160F., filtered, washed with 2.7 1. of hot deionized water and oven dri`ed. The product recovered had a surface area of 35Q m2~gm. and a (001) basal spacing of 17.5A.
Example 5 This example illustrates the use of beidellite clay as a raw material.
A slurry was prepared from 15 grams (dry basis) of beidellite clay from Taiwan having a particle size of equal to or less -than 2 microns. The particles having a particle size of equal to or less than 2 microns were recovered by centrifugation. A total of 15 grams (dry basis) of the clay was diluted to 3 liters and 15.1 grams of a 50 wèight percent aluminum chlorhydroxide solution was added. The resulting slurry was aged for a , . . ~ .
` period of 1/2 hour. The pH ~as adjusted to 2.0 with 3.75 percent hydrochloric acid solution. The temperature was increased to 160F. and the slurry was aged at this temperature for a period of 1/2 hour. The slurry was filtered, washed with 1 liter of hot deionized water and i oven dried. The surface area of the product was 307 m /gm.
and the ~001) basal spacing was 18.OA.
Example 6 This example illustrates a method of utilizing a beneficiatecl montmorillonite without the necessity of separating the particles that have a particle size equal to or less than 2 mïcrons. The us-e of 3~ such readily availahle commerci`al product greatly reduces the pre-processing needed to prepare the -~
.. ~ .
materials of -this invention. ~ 25 gram. (dry basis) sample of a higfi purity air-floated Wyomi`ng bentonite furni`shed by American Colloid Company ~#325 Bentonite~
was slurried in a blender wï.th 1 liter of deionized water for 1/2 minute. A total of 21.5 grams of a 5Q percent aluminum chlorohydr.oxide solution was added and the slurry was aged for 1/2 hour at 150F.
.:
. The ~roduct was filtered, washed with 1 liter of : hot deionized water, and oven dried at 110C. The , :
.. 10 surface area of this product was 308 m2/gm.
xample 7 This example i.llustrates the product distribution `~ o~ a typical product prepared from the product described ~ in Examples 1 and 2. The catalystic activity of the ;.' product was determined using the micro-activity test ~ described in the article by F. G. Ciapetta et al. in : the Oîl and Gas Journal of October 16, 1967. The `~ feed stock was a Wes.t Texas gas oil boiling in the range of 500 to 800F. The reactor was operated at a temperature of 920F., a weight hourly space velocity ~ of 16 and a catalyst/oil ratio of 3. The test was carried out after the catalysts had been exposed to a . temperature of 1000F. for a period of 3 hours. The data collected in this run is set out in Table II below.
' ,., ~
.
Table II
Pillared Interlayered Clay prepared from Conversi`on Volclay 200 Conv.,* V% 77 3 H2 ,** W% .27 Cl ~ W% . 90 C2=, W% .71 C2 ~ W% .94 Total C3, W% 5~7 Total Dry Gas, W% 8.5 C3=,V% 5.4 C3, V% 4.2 Total C3, V% 9.6 .:
C4=, V% 2.6 iso~C4, V% 8.0 ,~ normal-C4,V% 1.7 Total C4, V% 12.3 C4~gasoline., V% 66.9 C5~gasoline, V% 54.6 Coke on cat,, W% 4~5 Coke-Total feed, W% 12.8 .~
.
`: :
*V% = Volume percent **W% = Weight percent ' - 2a -34~
;.'' Example 8 It has been found that i`~ the clay was added to ~` the alumi`num chlorohydroxide solution a larger solids concentration could he affected. Such additions to the aluminum chlorAydroxide soluti`on may be as high as abou-t 40 weight percent clay without encountering problems ;n mixing, pumping, or handling the clay in the fluid state. This greatly enhances the economy of the process in that much larger volumes of the ~roduct can be obtaïned and processed in a given time for a given sized system. The addition of clay to water followed by aluminum chlorhydroxide addition does not allow high solids levels to ~e achïeved. The former process is presumably achieved hecause-the polymer is instantaneously ïntercallated by the ~,~
clay-as the clay is added, and so inhibits dispersion of the clay platelets and subsequent formation of a clay-water gel.
A further advantage is that high solids cut down the use of energy in the drying step.
In an illustration of this, a total of 2,470 grams of a 50 weight percent of aluminum chlorhydroxide solution was diluted to 22.7 liters. ~ total of 5,320 ; yrams (5,072 gram dry basis) of bentonite was added to the slurry-. The slurry was aged at ~50~F. for a period of 1 hour and spray dried. The solids concen-tration of the product ~ed to the spray drier was approximately 2a percent, the product re~overed had a surface area of 273 m ~gm and a lattice d spacing (001~ of 17.9.
:.
.
Example 9 In thi`s example a slurry containi`ng 15.9 percent solids was prepared by diluting 2,720 grams of aluminum .
chlorhydroxide to 6 gallons- and 5000 grams (~dry basis) - of the clay was added -to this slurry. The slurry was ag;tated and aged 1/2 hour at 150E'., filtered, and washed on the filter with 6 gallons of hot deionized ~ater. The product was reslurried and spray dried.
The surface area of the product recovered a 316 m2/gm and the d spaciny (Q01~ was 18A.
Example 10 ' In this example a slurry containing a 35 percent total solids was prepared by addition of 125 grams (dry basis~ #325 sentonite clay (American Colloid Co.) to ~ a solution containing 65.2 grams of the aluminum polymer ; in a total volume of 25a ml. This slurry was aged 1 hour at 150F., filtered, washed wîth 1/2 1. hot ~; deionïzed water and dried. The product surface area was 263 m2/gm. and the (~alJ d spac;ng was 17.6A.
Example 11 In this example a less basic Al polymer is used ;~ to interlayer the smectite. Ordinary aluminum chlor-., hy-droxide (chlorhydrol) contains 5 OH /2 Al 3, and is 5/6 basic. 10 gms. dry basis of 2.0 Volclay~ 200 (American Colloid Co.) as a slurry was diluted to 1.0 1., and ~.3Q gms~ of a 2/3 ~asic Al polymer (i.e.,
- 4 OH ~2 Al 3~ solution contaïning lq.2% A12O3 was added. This polymer solution was prepared by refluxing an AlC13.6 H2O solution ïn the presence of excess aluminum metal until pH 2.8 was- reached. The above slurry was hot aged 1/2 hour at 150F, filtered, ' . ~-i . .. ~
:
63~i ,................................. .
...
; washed 2X with 1/2 1. hot deionized water and oven dried. The interlayered product had a surface area of 286 m2/gm. and a basal spacing of 17.lA.
Example 12 This example indicates that smectites can be interlayered with Al polymer prepared Erom dehydrated AlC13 6 ~12O. 9.1 gms. of AlC13 6 H2O was weighe~ in an evaporating dish, the dish placed in a muffle furnace set at 325F for one hour and the temperature then increased to 500F. The sample was withdrawn from the furnace after a 45~ weight loss. The salt was then added to 200 ml. of deionized water, 12.5 gms. dry basis of #325 Bentonite ~American Colloid Co.) was added, the slurry hot aged 1 hour at 150F, filtered, washed 2X with 250 ml.
hot dionized water and dried at 250F. This sample had a surface area of 281 m2/gm. and a basal spacing of 17.7 A.
Example 13 In this example a mixture of AlC13 6 H2O and ~gC12 6 H2O are dried at 250F for 18 hours to a 48~
~ ~eight loss to produce a mixed Al-Mg polymer for inter-;; layering smectite. 7.6 gms. AlC13 6 ~2 and 2.54 gams.
.
MgC12-H2O were dissolved in 25 ml. deionized water and then dried at 25QF for 18 hours. The dried salt mixture was dissolved in 25Q ml. deionized water, 12.5 gms. dry ` ~asis ~325 Bentonite added, the slurry hot aged 1 hourat 15~F, filtered, washed 2X with 250 ml. hot deionized ~ater and dried at 250F. The interlayered clay product had a surface area of 254 m2~gm. and a basal spacing of 17.7 A.
.
, Example 14 This example shows how a well interlayered smectite can ~e produced from ZrOC124 H2O dried at 500F. 11 ~r' gms. of ZrOC12 4 H2O was dried at 500F to a 11~ weight loss, dissolved in 200 ml. deïonized water, 12.5 gms.
dry basis #325 Bentonite added, the slurry hot aged 1 ~; hour at 150F, filtered, washed 2X with 200 ml. hot deionized water and dried at 250r'F. The interlayered clay had a surface area of 262 m2/ym. and a basal spacing of 18.8 A.
Example 15 This example shows that interlayering of smectite can ~e accomplished at elevated temperature and ;~ pressure. 13.6 gms. chlorhydrol (Reheis Chemical Co.) -~ was diluted to 200 ml. with deionized water, 25 gms.
dry basis #325 Bentonite added and the slurry boiled 1 hour. 20~ of the above slurry was added to a Hoke high pressure cylinder and aged 1 1/2 houxs at 150C.
The interlayered clay product was then filtered, washed 2X with 250 ml. hot deionized water and oven dried. The product had a surface area of 279 m /gm. and a basal ; spacing of 17.7A.
`~ Example 16 This example indicates that interlayered smectites prepared by chlorhydrol ~ Mg~2 coexchange are more hydrothermally stable than those prepared with chlorhydrol exchange alone. 54.~ gms. chlorhydrol was diluted to 1.6 1.
; and then 400 ml. of a solution containing 40.8 gms.
. ~
MgC12 6 H2O was added and the mixture aged 3 day at room temperature. 100 gms. dry basis of ~325 Bentonite ~ was added, the slurry hot aged 1 hour at 160F, ~iltered, !., 24 ~.`' - .
. ~ .
6~6 :, . .
washed 2X with 1.0 l. hot deionized water and oven dried.
As indicated E~elow, this preparation maintained a greater deyree of surface area after a 6 hour, 1400F, atmosphere steam tratmen t than smectite interlayered with chlorhyarol alone.
Surface Area Interlayering Species 1-1000F. 6-i4000F, ~ Atm.
Chlorhydrol 270 20 Chlorhydrol + Mg~2 31Q 104 Example 17 This example indicates that reflexed ZrOC12 4 H2O solutions are effective in interlayering smectite.
0.33 M ZrOC12 4 H2O was reflexed for 24 hours and then 120 ml. of this solution was diluted to 500 ml., 10 gms. dry basis HPM-20 ~American Colloid Co.~
added, aged 1/2 hour at room temperature~ filtered, washed 2X with 1/2 1. hot deionized water and oven dried. The interlayered product had a surface area of 288 m2/gm and a basal spacing of 22.QA.
Example 18 This example shows that ZrOC12 4 ~I2O solutions treated with Na2CO3 can effectively interlayer smectites.
125 gms. ZrOC12 4 H2O was dissolved in 1/2 1. solution.
To this solution was added dropwise 1/2 1. of solution containing 26.5 gms. Na2CO3. After aging for 24 hours,
:
63~i ,................................. .
...
; washed 2X with 1/2 1. hot deionized water and oven dried. The interlayered product had a surface area of 286 m2/gm. and a basal spacing of 17.lA.
Example 12 This example indicates that smectites can be interlayered with Al polymer prepared Erom dehydrated AlC13 6 ~12O. 9.1 gms. of AlC13 6 H2O was weighe~ in an evaporating dish, the dish placed in a muffle furnace set at 325F for one hour and the temperature then increased to 500F. The sample was withdrawn from the furnace after a 45~ weight loss. The salt was then added to 200 ml. of deionized water, 12.5 gms. dry basis of #325 Bentonite ~American Colloid Co.) was added, the slurry hot aged 1 hour at 150F, filtered, washed 2X with 250 ml.
hot dionized water and dried at 250F. This sample had a surface area of 281 m2/gm. and a basal spacing of 17.7 A.
Example 13 In this example a mixture of AlC13 6 H2O and ~gC12 6 H2O are dried at 250F for 18 hours to a 48~
~ ~eight loss to produce a mixed Al-Mg polymer for inter-;; layering smectite. 7.6 gms. AlC13 6 ~2 and 2.54 gams.
.
MgC12-H2O were dissolved in 25 ml. deionized water and then dried at 25QF for 18 hours. The dried salt mixture was dissolved in 25Q ml. deionized water, 12.5 gms. dry ` ~asis ~325 Bentonite added, the slurry hot aged 1 hourat 15~F, filtered, washed 2X with 250 ml. hot deionized ~ater and dried at 250F. The interlayered clay product had a surface area of 254 m2~gm. and a basal spacing of 17.7 A.
.
, Example 14 This example shows how a well interlayered smectite can ~e produced from ZrOC124 H2O dried at 500F. 11 ~r' gms. of ZrOC12 4 H2O was dried at 500F to a 11~ weight loss, dissolved in 200 ml. deïonized water, 12.5 gms.
dry basis #325 Bentonite added, the slurry hot aged 1 ~; hour at 150F, filtered, washed 2X with 200 ml. hot deionized water and dried at 250r'F. The interlayered clay had a surface area of 262 m2/ym. and a basal spacing of 18.8 A.
Example 15 This example shows that interlayering of smectite can ~e accomplished at elevated temperature and ;~ pressure. 13.6 gms. chlorhydrol (Reheis Chemical Co.) -~ was diluted to 200 ml. with deionized water, 25 gms.
dry basis #325 Bentonite added and the slurry boiled 1 hour. 20~ of the above slurry was added to a Hoke high pressure cylinder and aged 1 1/2 houxs at 150C.
The interlayered clay product was then filtered, washed 2X with 250 ml. hot deionized water and oven dried. The product had a surface area of 279 m /gm. and a basal ; spacing of 17.7A.
`~ Example 16 This example indicates that interlayered smectites prepared by chlorhydrol ~ Mg~2 coexchange are more hydrothermally stable than those prepared with chlorhydrol exchange alone. 54.~ gms. chlorhydrol was diluted to 1.6 1.
; and then 400 ml. of a solution containing 40.8 gms.
. ~
MgC12 6 H2O was added and the mixture aged 3 day at room temperature. 100 gms. dry basis of ~325 Bentonite ~ was added, the slurry hot aged 1 hour at 160F, ~iltered, !., 24 ~.`' - .
. ~ .
6~6 :, . .
washed 2X with 1.0 l. hot deionized water and oven dried.
As indicated E~elow, this preparation maintained a greater deyree of surface area after a 6 hour, 1400F, atmosphere steam tratmen t than smectite interlayered with chlorhyarol alone.
Surface Area Interlayering Species 1-1000F. 6-i4000F, ~ Atm.
Chlorhydrol 270 20 Chlorhydrol + Mg~2 31Q 104 Example 17 This example indicates that reflexed ZrOC12 4 H2O solutions are effective in interlayering smectite.
0.33 M ZrOC12 4 H2O was reflexed for 24 hours and then 120 ml. of this solution was diluted to 500 ml., 10 gms. dry basis HPM-20 ~American Colloid Co.~
added, aged 1/2 hour at room temperature~ filtered, washed 2X with 1/2 1. hot deionized water and oven dried. The interlayered product had a surface area of 288 m2/gm and a basal spacing of 22.QA.
Example 18 This example shows that ZrOC12 4 ~I2O solutions treated with Na2CO3 can effectively interlayer smectites.
125 gms. ZrOC12 4 H2O was dissolved in 1/2 1. solution.
To this solution was added dropwise 1/2 1. of solution containing 26.5 gms. Na2CO3. After aging for 24 hours,
5~ ml. of the above solution was diluted to l/2 1., lQ gms. dry basis HPM-2Q added, the slurry hot aged 1/2 hour at 150F, filtered, washed 2X with 1/2 1. hot -; deionized water and oven dried. The product had a 30 surface area of 3a9 m2/gm. and a basal spacing of 17.4A.
:- . , "
.
:.
1~ 4~
., Example 19 This example shc~s how CO2 treated ZrOC12 4 H2O
- solutions can effectIvely-interlayer smectite. 125 gms.
of ZrOC12 4 H2O was dissolved in 1,000 ml. deionized water.
C2 (gas) was bubbled through the solution for 2 hours, and the solution ages 24 hours at room temperature.
5Q ml. of this solution was then diluted to 1/2 1., 10 gms. dry basis HPM-20 (American Colloid Co.) was added, the slurry hot aged 1/2 hours at 150F, filtered, washed 10 2X with 1/2 1. hot deionized water and oven dried. The interlayered clay had a surface area of 279 m2/gm. and a basal spacing of 16.8A.
Example 20 - This example shows that diluted chlorhydrol when refluxed, gives interlayered smectites with improved hydrothermal stability relative to non-refluxed chlorhydrol. 217 gms. chlorhydrol was diluted to 1.0 1., yielding a solution which is 0.5 M as A12O3. This solution was refluxed for 96 hours. 87.6 ml. of this 20 solution was diluted to 400 ml., 25 gms. dry basis #325 Bentonite added, the slurry boiled 1 hour, filtered, --~ washed 2X with 1/2 1. hot deionized water and oven dried.
As indicated below, this preparation had a greater ;~ retention of surface area than an interlayered clay prepared with ordinary chlorhydrol.
Surface Area Inter_ayering Species 1-1000F. 6-1400F., 1 Atm.
'~ Chlorhydrol 270 20 Refluxed diluted chlorhy`drol 271 82 , . .
,.
:
." . . . . :
: . .
:
Example 21 This example shows that treatment with SiO3 2 of either diluted refluxed chlorhydrol or ordinary chlorhydrol results in a substantial improvement of the interlayered product. ~3.8 ml. of diluted (0.5 M in A12O3~ refluxed (48 hours~ chlorhydrol was diluted further to 500 ml. 1.26 gms. of Na2SiO3 solution (containing 28.5% SiO2 and 8.0% Na2O~ diluted to 100 ml.
was added to the refluxed chlorhydrol solution. 12.5 10 gms dry basis #325 Bentonite was added, the slurry boiled 1 hour, filtered, washed 2X with 1/2 1. hot deionized water and oven dried.
Silicating ordinary chlorhydrol also substantially improves the hydrothermal stability of the interlayered clay. 8.5 gms. chlorhydrol was diluted to 900 ml. and then 1.26 gms. of Na2SiO3 solution (28.5% SiO2, 8.0%
Na2O~ diluted to 100 ml. was added to the dilute chlorhydrol solution. After aging overnight at room ; temperature, 12.5 gms. dry basis #325 Bentonite was i::
added, hot aged 1 hour at 150F, filtered, washed 2X
with 1/2 1. hot deionized water and oven dried.
Summarized below is a comparison of the hydrothermal sta~ility of both of the a~ove interlayered clays with ~ ordinary chlorhydrol interlayered clay.
- Surface Area Interlayering Species 1-100F6-1400~F, 1 Atm.
Chlorhydrol 270 20 Chlorhydrol + SiO3 2 294 129 Refluxed diluted 2 chlorhydrol + SiO3 353 165 ,.
., '` ~
Example 22 ~' This example ïllustrates the use of the pillared ; interlayered clays -as sorbents :Eor organic molecules.
202 gms. of a ~ 2.0~ slurry of Volclay~ 200 (American - Colloid Co.~ which corresponds to 4.25 gms. (Dry Basis) clay was added to 400 ml. of solution containing 7.6 gms.
of aluminum chlorhydroxide solution (Reheis Chemical Co.).
The slurry was aged 1 hour with agitation, centrifuged, reslurried in deionized water and recentrifuged. The product was then reslurried in a second solution of 7.6 gms. aluminum chlorhydroxide diluted to l.O 1. After aging for l hour the slurry was centrifuged, reslurried in deionized water, recentrifuged and oven dried overnight at 250F. The sample was then ground and tested for n-butane and iso-butane capacity after several batches .. ~
- were prepared. This sample had an n-butane capacity ; of 7.74~ and an iso-butane capacity of 7.13~. The surface area of this sample was 393 m /gm. and the basal spacing O
was 17.7A.
~- 20 Example 23 i This example shows the usefulness of pillared inter-layered clays as hydrocracking catalyst base. 2,720 gms. of chlorhydrol was diluted to 6 gallons and 5,000 gms. dry basis #325 Bentonite was added with vigorous agitation.
~; The slurry was hot aged 1/2 hour at 150F, filtered and ,.,.~
~` washed lX on the filter with 6 gallons of hot water.
.j The filter cake was reslurried to 15.9~ solids and spray drïed. The product surface area was 316 m2/gm. and the ;~ O
basal spacing was 18.OA. A portion of this material :
~ !
~ - 28 -,.~
:.
i ' ' ' ,'`: . . , : '' , was exchanged with 0.5~ Pd, hlended at a ratio of 9 parts interlayered clay/1 part A12O3, reduced ~2 hours at 500F, 12 hours at 700F in 71 :Liters/hour flowiny H2~
and then calcined 3 hours at 1000F. The hydrocracking test was run at 1 LHSV, 15aQ psig and 8000 SCF/B H2.
The interlayered clay hydrocracking catalyst gave 16%
conversion at 675F, compared to 6% conversion for a 0.5 W% Pd impregnated 28% A12O3, 72% SiO2 catalyst.
Example 24 This example shows the general use~ulness of interlayered clays ~or water sorption. The same interlayered clay sample ~without Pd) as described in - example 24 was used ~or the water sorption measurements.
The sample was calcined 1 hour at 1000F prior to the test. The results, yiven as % water sorption with varying relative humidity (RH), indicate substantial ` -ability to sorb ~ater.
TV @1750F 4.85 - Ads. 10% RH 2.56 Ads. 20% RH 4.78 Ads. 35% RH 9.30 Ads. 60% RH 12.48 ; Ads. 100% RH 19.76 The capacity as a dehydrating agent is comparable to silica gels and zeol:Ltes.
- 2~ -'
:- . , "
.
:.
1~ 4~
., Example 19 This example shc~s how CO2 treated ZrOC12 4 H2O
- solutions can effectIvely-interlayer smectite. 125 gms.
of ZrOC12 4 H2O was dissolved in 1,000 ml. deionized water.
C2 (gas) was bubbled through the solution for 2 hours, and the solution ages 24 hours at room temperature.
5Q ml. of this solution was then diluted to 1/2 1., 10 gms. dry basis HPM-20 (American Colloid Co.) was added, the slurry hot aged 1/2 hours at 150F, filtered, washed 10 2X with 1/2 1. hot deionized water and oven dried. The interlayered clay had a surface area of 279 m2/gm. and a basal spacing of 16.8A.
Example 20 - This example shows that diluted chlorhydrol when refluxed, gives interlayered smectites with improved hydrothermal stability relative to non-refluxed chlorhydrol. 217 gms. chlorhydrol was diluted to 1.0 1., yielding a solution which is 0.5 M as A12O3. This solution was refluxed for 96 hours. 87.6 ml. of this 20 solution was diluted to 400 ml., 25 gms. dry basis #325 Bentonite added, the slurry boiled 1 hour, filtered, --~ washed 2X with 1/2 1. hot deionized water and oven dried.
As indicated below, this preparation had a greater ;~ retention of surface area than an interlayered clay prepared with ordinary chlorhydrol.
Surface Area Inter_ayering Species 1-1000F. 6-1400F., 1 Atm.
'~ Chlorhydrol 270 20 Refluxed diluted chlorhy`drol 271 82 , . .
,.
:
." . . . . :
: . .
:
Example 21 This example shows that treatment with SiO3 2 of either diluted refluxed chlorhydrol or ordinary chlorhydrol results in a substantial improvement of the interlayered product. ~3.8 ml. of diluted (0.5 M in A12O3~ refluxed (48 hours~ chlorhydrol was diluted further to 500 ml. 1.26 gms. of Na2SiO3 solution (containing 28.5% SiO2 and 8.0% Na2O~ diluted to 100 ml.
was added to the refluxed chlorhydrol solution. 12.5 10 gms dry basis #325 Bentonite was added, the slurry boiled 1 hour, filtered, washed 2X with 1/2 1. hot deionized water and oven dried.
Silicating ordinary chlorhydrol also substantially improves the hydrothermal stability of the interlayered clay. 8.5 gms. chlorhydrol was diluted to 900 ml. and then 1.26 gms. of Na2SiO3 solution (28.5% SiO2, 8.0%
Na2O~ diluted to 100 ml. was added to the dilute chlorhydrol solution. After aging overnight at room ; temperature, 12.5 gms. dry basis #325 Bentonite was i::
added, hot aged 1 hour at 150F, filtered, washed 2X
with 1/2 1. hot deionized water and oven dried.
Summarized below is a comparison of the hydrothermal sta~ility of both of the a~ove interlayered clays with ~ ordinary chlorhydrol interlayered clay.
- Surface Area Interlayering Species 1-100F6-1400~F, 1 Atm.
Chlorhydrol 270 20 Chlorhydrol + SiO3 2 294 129 Refluxed diluted 2 chlorhydrol + SiO3 353 165 ,.
., '` ~
Example 22 ~' This example ïllustrates the use of the pillared ; interlayered clays -as sorbents :Eor organic molecules.
202 gms. of a ~ 2.0~ slurry of Volclay~ 200 (American - Colloid Co.~ which corresponds to 4.25 gms. (Dry Basis) clay was added to 400 ml. of solution containing 7.6 gms.
of aluminum chlorhydroxide solution (Reheis Chemical Co.).
The slurry was aged 1 hour with agitation, centrifuged, reslurried in deionized water and recentrifuged. The product was then reslurried in a second solution of 7.6 gms. aluminum chlorhydroxide diluted to l.O 1. After aging for l hour the slurry was centrifuged, reslurried in deionized water, recentrifuged and oven dried overnight at 250F. The sample was then ground and tested for n-butane and iso-butane capacity after several batches .. ~
- were prepared. This sample had an n-butane capacity ; of 7.74~ and an iso-butane capacity of 7.13~. The surface area of this sample was 393 m /gm. and the basal spacing O
was 17.7A.
~- 20 Example 23 i This example shows the usefulness of pillared inter-layered clays as hydrocracking catalyst base. 2,720 gms. of chlorhydrol was diluted to 6 gallons and 5,000 gms. dry basis #325 Bentonite was added with vigorous agitation.
~; The slurry was hot aged 1/2 hour at 150F, filtered and ,.,.~
~` washed lX on the filter with 6 gallons of hot water.
.j The filter cake was reslurried to 15.9~ solids and spray drïed. The product surface area was 316 m2/gm. and the ;~ O
basal spacing was 18.OA. A portion of this material :
~ !
~ - 28 -,.~
:.
i ' ' ' ,'`: . . , : '' , was exchanged with 0.5~ Pd, hlended at a ratio of 9 parts interlayered clay/1 part A12O3, reduced ~2 hours at 500F, 12 hours at 700F in 71 :Liters/hour flowiny H2~
and then calcined 3 hours at 1000F. The hydrocracking test was run at 1 LHSV, 15aQ psig and 8000 SCF/B H2.
The interlayered clay hydrocracking catalyst gave 16%
conversion at 675F, compared to 6% conversion for a 0.5 W% Pd impregnated 28% A12O3, 72% SiO2 catalyst.
Example 24 This example shows the general use~ulness of interlayered clays ~or water sorption. The same interlayered clay sample ~without Pd) as described in - example 24 was used ~or the water sorption measurements.
The sample was calcined 1 hour at 1000F prior to the test. The results, yiven as % water sorption with varying relative humidity (RH), indicate substantial ` -ability to sorb ~ater.
TV @1750F 4.85 - Ads. 10% RH 2.56 Ads. 20% RH 4.78 Ads. 35% RH 9.30 Ads. 60% RH 12.48 ; Ads. 100% RH 19.76 The capacity as a dehydrating agent is comparable to silica gels and zeol:Ltes.
- 2~ -'
Claims (21)
1. An interlayered smectite clay product which in-cludes an inorganic oxide selected from the group con-sisting of alumina, zirconia and mixtures thereof be-tween the layers thereof, and which possesses an inter-layer distance of from about 6 to 16.ANG., said interlayered clay having greater than about 50 percent of its surface area in pores of less than 30 .ANG. in diameter.
2. The product of claim 1 wherein said inorganic oxide is alumina.
3. The product of claim 1 wherein said inorganic oxide is zirconia.
4. The product of claim 1 wherein said inorganic oxide is silica and alumina.
5. The product of claim 1 wherein said inorganic oxide is alumina and magnesia.
6. The product of claim 1 wherein the smectite is selected from the group consisting of hectorite, chlorite, bentonite, montmorillonite, beidellite, and mixtures thereof.
7. The smectite of claim 1 exchanged with cations selected from the group consisting of hydrogen, ammonium, Group IB to VIII of the periodic table, and mixtures thereof.
8. A process for preparing an interlayered smectite which comprises:
(a) reacting a smectite with a mixture of a polymeric cationic hydroxy inorganic metal complex selected from the group comprising aluminum and zirconium complexes and mixtures thereof and water to obtain a smectite having greater than 50 percent of its surface area in pores of less than 30 .ANG. in diameter after dehydration; and (b) separating the interlayered smectite from the mixture.
(a) reacting a smectite with a mixture of a polymeric cationic hydroxy inorganic metal complex selected from the group comprising aluminum and zirconium complexes and mixtures thereof and water to obtain a smectite having greater than 50 percent of its surface area in pores of less than 30 .ANG. in diameter after dehydration; and (b) separating the interlayered smectite from the mixture.
9. The process of claim 8 wherein said mixture is reacted at a temperature of 5° to 200°C. from a period of 0.1 to 4 hours.
10. The process of claim 8 wherein said smectite is selected from the group consisting of hectorite, chlorite, bentonite, montmorillonite, beidellite and mixtures thereof.
11. The process of claim 8 wherein said metal complex has the formula Al2+n(OH)3nX6 wherein n has the value of 4 to 12 and wherein up to about 10% of the aluminum is tetrahedrally coordinated; and X is selected from the group consisting of Cl, Br, NO3 and CO3.
12. The process of claim 8 wherein said metal com-plex is aluminum chlorhydrol.
13. The process of claim 8 wherein said metal complex contains titanium.
14. The process of claim 8 wherein said interlayered smectite is heated at a temperature of 200° to 700°C.
15. The process of claim 8 wherein from about 0.05 to 2.0 parts by weight of said metal complex is mixed with each part by weight of said smectite.
16. A hydrocarbon conversion catalyst comprising the interlayered smectite of claim 7.
17. A hydrocracking catalyst comprising the inter-layered smectite of claim 1, and a metal selected from the group consisting of Group VIII noble metals, Ni, Co, W
and Mo.
and Mo.
18. An adsorbent composition comprising the inter-layered smectite of claim 1 formed into particles having Tyler mesh sizes of from about 4 to 400.
19. A hydrocarbon conversion catalyst comprising the interlayered clay of claim 1, admixed with a crystal-line aluminosilicate zeolite which comprises a member selected from the group consisting of inorganic oxides and a matrix clay, and mixtures thereof.
20. The method of claim 8 wherein the metal complex is an aluminum complex.
21. The method of claim 8 wherein the metal complex is a zirconium complex.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US80567277A | 1977-06-13 | 1977-06-13 | |
| US805,672 | 1977-06-13 | ||
| US05/885,408 US4176090A (en) | 1975-11-18 | 1978-03-10 | Pillared interlayered clay materials useful as catalysts and sorbents |
| US885,408 | 1978-03-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1106346A true CA1106346A (en) | 1981-08-04 |
Family
ID=27122810
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA305,166A Expired CA1106346A (en) | 1977-06-13 | 1978-06-09 | Pillared interlayered clay materials useful as catalysts and sorbents |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5416386A (en) |
| AU (1) | AU518419B2 (en) |
| CA (1) | CA1106346A (en) |
| DE (1) | DE2825769A1 (en) |
| FR (1) | FR2394324A1 (en) |
| GB (1) | GB1604190A (en) |
| MX (1) | MX147711A (en) |
| NL (1) | NL7806339A (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4271043A (en) * | 1979-09-04 | 1981-06-02 | W. R. Grace & Co. | Pillared interlayered clay products |
| FR2512043A1 (en) * | 1981-08-27 | 1983-03-04 | Jacobs Pierre | PROCESS FOR THE PREPARATION OF CLAYED ARGILES, CLAYS PREPARED BY THIS METHOD AND APPLICATIONS OF SAID CLAYS |
| US4629713A (en) * | 1984-01-20 | 1986-12-16 | Agency Of Industrial Science And Technology | Finely porous clay formed preponderantly of spectite type mineral and method for manufacture of said clay |
| FR2563446A1 (en) * | 1984-04-25 | 1985-10-31 | Raffinage Cie Francaise | NEW ZEOLITE WITH TWO-DIMENSIONAL STRUCTURE AND APPLICATION OF SAID ZEOLITE |
| JPS61151020A (en) * | 1984-12-26 | 1986-07-09 | Topy Ind Ltd | Porous material consisting of synthetic fluorine mica |
| US4859648A (en) * | 1984-12-28 | 1989-08-22 | Mobil Oil Corporation | Layered metal chalcogenides containing interspathic polymeric chalcogenides |
| US4757040A (en) * | 1985-04-01 | 1988-07-12 | Research Institute Of Petroleum Processing Sinopec | Class of pillared interlayered clay molecular sieve products with regularly interstratified mineral structure |
| JPS62138318A (en) * | 1985-12-10 | 1987-06-22 | Agency Of Ind Science & Technol | Production of fine porous separation material |
| JPS62138316A (en) * | 1985-12-10 | 1987-06-22 | Agency Of Ind Science & Technol | Production of fine porous separation material |
| JPS62138317A (en) * | 1985-12-10 | 1987-06-22 | Agency Of Ind Science & Technol | Production of fine porous separation material |
| JP2656778B2 (en) * | 1986-06-26 | 1997-09-24 | モービル・オイル・コーポレイション | Layered metal oxides containing interlayer oxides and their synthesis |
| JPS6385067A (en) * | 1986-09-25 | 1988-04-15 | 松下電工株式会社 | Manufacture of inorganic layered porous body |
| FR2619024A1 (en) * | 1987-08-07 | 1989-02-10 | Total France | HYDROCRACKING CATALYSTS OF HYDROCARBON LOADS AND APPLICATION OF SAID CATALYSTS |
| FR2652079B1 (en) * | 1989-09-18 | 1991-12-13 | Rhone Poulenc Chimie | PROCESS FOR THE PREPARATION OF BRIDGE CLAYS AND BRIDGE CLAYS OBTAINED ACCORDING TO THIS PROCESS. |
| JPH0441446A (en) * | 1990-06-06 | 1992-02-12 | Mitsubishi Materials Corp | Production of dialkylnaphthalene and catalyst therefor |
| EP2310122B1 (en) * | 2008-07-30 | 2017-05-24 | Saudi Arabian Oil Company | Metallic clay based fcc gasoline sulfur reduction additive compositions |
| WO2012001663A1 (en) * | 2010-07-02 | 2012-01-05 | Basf Se | Metal-bridged pillared silicate compounds and process for their production |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL68607C (en) * | 1942-09-07 | |||
| GB1228759A (en) * | 1967-08-11 | 1971-04-21 | ||
| US3798177A (en) * | 1971-09-03 | 1974-03-19 | Chevron Res | Novel catalyst support |
| US3840477A (en) * | 1972-08-03 | 1974-10-08 | Nalco Chemical Co | Hydrotreating catalyst |
| US3887454A (en) * | 1972-12-01 | 1975-06-03 | Chevron Res | Layered clay minerals and processes for using |
-
1978
- 1978-05-31 GB GB2477578A patent/GB1604190A/en not_active Expired
- 1978-06-09 CA CA305,166A patent/CA1106346A/en not_active Expired
- 1978-06-12 FR FR7817534A patent/FR2394324A1/en active Granted
- 1978-06-12 AU AU37042/78A patent/AU518419B2/en not_active Expired
- 1978-06-12 MX MX17377578A patent/MX147711A/en unknown
- 1978-06-12 NL NL7806339A patent/NL7806339A/en not_active Application Discontinuation
- 1978-06-12 DE DE19782825769 patent/DE2825769A1/en active Granted
- 1978-06-13 JP JP7047978A patent/JPS5416386A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| GB1604190A (en) | 1981-12-02 |
| AU518419B2 (en) | 1981-10-01 |
| NL7806339A (en) | 1978-12-15 |
| DE2825769A1 (en) | 1978-12-14 |
| JPS6220130B2 (en) | 1987-05-06 |
| JPS5416386A (en) | 1979-02-06 |
| DE2825769C2 (en) | 1992-01-23 |
| FR2394324A1 (en) | 1979-01-12 |
| AU3704278A (en) | 1979-12-20 |
| FR2394324B1 (en) | 1984-12-14 |
| MX147711A (en) | 1983-01-06 |
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