GB2151603A - Modified clay - Google Patents
Modified clay Download PDFInfo
- Publication number
- GB2151603A GB2151603A GB8431326A GB8431326A GB2151603A GB 2151603 A GB2151603 A GB 2151603A GB 8431326 A GB8431326 A GB 8431326A GB 8431326 A GB8431326 A GB 8431326A GB 2151603 A GB2151603 A GB 2151603A
- Authority
- GB
- United Kingdom
- Prior art keywords
- beryllium
- layered clay
- pillared
- process according
- clay
- 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.)
- Granted
Links
- 239000004927 clay Substances 0.000 title claims abstract description 29
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 27
- 239000000413 hydrolysate Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 3
- 229910021647 smectite Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 230000007062 hydrolysis Effects 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 9
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 150000001573 beryllium compounds Chemical class 0.000 claims description 2
- PPYIVKOTTQCYIV-UHFFFAOYSA-L beryllium;selenate Chemical compound [Be+2].[O-][Se]([O-])(=O)=O PPYIVKOTTQCYIV-UHFFFAOYSA-L 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 14
- 239000003463 adsorbent Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract 1
- 150000001336 alkenes Chemical class 0.000 description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- -1 beryllium cations Chemical class 0.000 description 3
- KQHXBDOEECKORE-UHFFFAOYSA-L beryllium sulfate Chemical compound [Be+2].[O-]S([O-])(=O)=O KQHXBDOEECKORE-UHFFFAOYSA-L 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- LWBPNIJBHRISSS-UHFFFAOYSA-L beryllium dichloride Chemical compound Cl[Be]Cl LWBPNIJBHRISSS-UHFFFAOYSA-L 0.000 description 2
- RFVVBBUVWAIIBT-UHFFFAOYSA-N beryllium nitrate Chemical compound [Be+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O RFVVBBUVWAIIBT-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000006053 organic reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical group C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229910001627 beryllium chloride Inorganic materials 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- PWOSZCQLSAMRQW-UHFFFAOYSA-N beryllium(2+) Chemical compound [Be+2] PWOSZCQLSAMRQW-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002432 hydroperoxides Chemical group 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
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
- B01J20/16—Alumino-silicates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A novel pillared layered clay having beryllium-containing pillars is produced by in a first step hydrolysing a hydrolysable compound of beryllium, for example a salt, and thereafter in a second step cation-exchanging a cation-exchangeable layered clay, for example a smectite, with the hydrolysate so- obtained. Pillared clays so produced are useful as catalysts, catalyst supports and adsorbents.
Description
SPECIFICATION
Novel pillared layered clays, process for their production, and uses thereof
The present invention relates to novel pillared layered clays or, as they are sometimes referred to, crosslinked interlayered clays, a process for their production and their use as catalysts, catalyst supports or sorbents.
Layered clays, that is clays having a lamellar structure with interlamellar spaces disposed therebetween in which pillars or crosslinks are substantially absent, are well-known as catalysts in organic reactions which are catalysed by protons. See for example our
European patent publications Nos. 0031252 and 0031687. It is generally recognised that such clays when heated in air suffer irreversible collapse of their layered structures at temperatures of 180"C and above, the actual value of this temperature depending upon the nature of the exchangeable cation present in the interlamellar region of the structure. The collapse of the layered structure is associated with a loss in the catalytic activity of the clay.
Layered clays can also suffer from the disadvantage that they suffer particle/granule instability in the presence of polar liquids such as methanol or ethanol. This does not impair catalytic activity in batch or continuous reactions in which the catalyst particles are subject to agitation, thereby maintaining them in suspension. However, the catalyst particles have at some stage to be separated from the reactor product by filtration, centrifugation or other solid/liquid separation methods. For fixed bed operation, the layered clay catalyst must be mixed with suitable binders to ensure granule or pellet stability.
Also known from, for example, US Patents
No. 4216188 and 4248739 are stabilised pillared layered clays, sometimes referred to as crosslinked interlayered clays in which the layers are separated and supported by "pillars" of monomeric, oligomeric or polymeric species derived from metal hydroxides. Such clays can inherently possess a higher degree of thermal stability and improved hydrothermal stability when compared with non-pillared layered clays. In USP 4248739 the use of the pillared layered clays as sorbents, catalysts and catalytic supports is described. The clays are said to be useful as hydrocarbon conversion catalysts for use in conventional catalytic cracking, hydrocracking, hydrotreating, isomerisation and reforming processes. Similar uses are described for the pillared clays of
USP 4216188.Our published European Application No. 83970 describes their use as catalysts in a number of different reactions catalysed by protons, for example the production of esters by reaction of an olefin with a carboxylic acid and the production of alkylaromatic compounds by reaction of an aromatic compound with an olefin or an alcohol.
The present invention provides a pillared layered clay having beryllium-containing pillars.
The beryllium-containing pillars suitably may comprise oligomeric beryllium species.
In another aspect the present invention provides a process for the production of a pillared layered clay having beryllium-containing pillars which process comprises in a first step hydrolysing a hydrolysable compound of beryllium and thereafter in a second step cationexchanging a cation-exchangeable layered clay with the hydrolysate so-obtained.
The compound of beryllium which is to be hydrolysed may suitabley be a beryllium salt, for example beryllium sulphate, beryllium chloride or beryllium nitrate.
Hydrolysis of the beryllium compound may suitably be effected by reaction with either an aqueous or an aqueous alcoholic solution of an inorganic base. Suitable inorganic bases include oxides and hydroxides of metals of
Groups I and II of the Periodic Table, for example sodium hydroxide. Other inorganic bases such as sodium carbonate may also be employed.
The ratio of the concentration of base, expressed in terms of moles of hydroxide per litre, to the concentration of beryllium, expressed in terms of gm ions of beryllium per litre, may suitably be in the range from 20:1 to 1:20, preferably in the range from 5:1 to 1:5, even more preferably about 2.5:1.
The hydrolysis may suitably be effected at ambient temperature, but elevated temperatures, suitably in the range from 30 to 90"C may be employed.
It is believed that the hydrolysis produces monomeric, dimeric and polymeric beryllium cations, the distribution of which in the hydrolysis can be influenced by the nature of the base and the ratio of the hydroxyl ion concentration to the beryllium ion concentration.
The layered clay as used in the second step of the process may be a natural layered clay or a synthetic layered clay. Of the many types of layered clays available (see for example 'Encyclopedia of Chemical Technology' [Kirk
Othmer], 3rd Edition, published by John
Wiley and Sons, pages 190-206) it is preferred to use the smectite class of layered clays, which may be either dioctahedral or trioctahedral. For an explanation as to the difference between dioctahedral and trioctahedral type clays reference is made to the book entitled 'The Chemistry of Clay-Organic Reactions' by B.K.G. Theng, published by John
Wiley and Sons, New York-Toronto, at page 2. Examples of suitable smectite-type layered clays include montmorillonite, bentonite, belidellite, nontronite and hectorite.
Examples of suitable synthetic smectite-type layered clays and methods for their prepara tion are described in US Patent No. 3855147 (NL Industries). It is also possible to use a pillared layered clay in which the pillars are derived from other materials, for example those of US Patents Nos. 4216188 and 4248739.
The layered clay may be cation-exchanged with the hydrolysate using any technique known in the art, preferably at a temperature below 100"C, even more preferably at a tem- perature less than 50"C, most preferably at a temperaure about ambient. It will usually be found convenient to add the clay to the hydrolysate and leave it in contact therewith, preferably with stirring, for a period of from a few minutes to several days, preferably from 30 minutes to 6 hours.
The pillared clay so-obtained may thereafter be separated from the hydrolysate by conventional means, such as by centrifugation or filtration.
It is preferred in a final step to heat the pillared clay to a temperature suitably in the range from 250 to 450"C, preferably about 400on, for a period of, for example, from i to 1 2 hours to drive off water. The heating may suitably be carried out in air, oxygen or an inert gas, such as nitrogen.
Pillared layered clays in which the pillars contain beryllium may be used as catalysts in a wide variety of chemical reactions, for example reaction which are catalysed by protons. Example of reactions which are catalysed by protons include:
(i) a process for the production of an ether by reacting either an olefin or an olefin oxide with an alcohol, (ii) a process for the production of an ether by conversion of either a primary or secondary aliphatic alcohol, a polyol or an olefin oxide,
(iii) a process for the production of an alkyl aromatic compound by reacting an aromatic compound with either an alcohol or an olefin,
(iv) a process for the production of an alcohol by reacting an olefin with water,
(v) a process for the production of an ester by reacting either an olefin or an olefin oxide with a carboxylic acid,
(vi) a process for the decomposition of hydroperoxides,
(vii) a process for the production of alkylphenols by the alkylation of phenol, and
(viii) a process for the transalkylation or dealkylation of alkyl aromatic hydrocarbons.
Further details of processes (i) to (vii) may be found in our copending European patent application Publication No. 83970 (BP Case
No. 5306) and of process (viii) in our copending European Application No. 83307022.0 (BP Case No 5445), which are incorporated herein by reference.
Because the pillared interlayered clays according to the invention have a characteristic interlayer spacing and a substantiai micropore structure, they are also useful as adsorbents and as catalyst supports.
The invention will now be further illustrated by reference to the following Examples:
Example 1
(i) Hydrolysis of beryllium sulphate
Beryllium sulphate (8.89; 0.05 mole) was hydrolysed at 60"C in the presence of base (sodium carbonate or potassium hydroxide).
Samples were taken during the course of the hydrolysis and examined by beryllium NMR spectroscopy. Samples were taken:
A. before addition of base,
B. after addition of an amount of base corresponding to about 20% hydrolysis, and
C. after addition of 2.5 mole equivalents of base (i.e. 13.149 Na2COX or 24.89 KOH) corresponding to substantially complete hydrolysis.
The NMR signal of aqueous beryllium (11) (Sample A) was assigned as reference (0 ppm). The partially hydrolysed sample (B) contained a small peak at 0.1 5 ppm assigned to the dimeric species and a large peak at
Oppm assigned to the unreacted beryllium monomer. The substantially hydrolysed sample (C)- showed a large peak at 0.57 ppm which was assigned to the trimeric species with a small shoulder at Oppm indicating a trace of unreacted beryllium (11) monomer.
= = [mole equivalent of base]/[moles of be- ryllium= 2.5
(ii) Preparation of beryllium pillared layered clay
The substantially hydrolysed beryllium solution (C) (500 ml, 0.5 molar) prepared as described in (i) above was added to a portion of natural sodium montmorillonite (Wyoming) (1009) at 60"C for 1 hour accompanied by rapid stirring. The suspension was cooled to room temperature and the clay decanted from the aqueous media. The clay was washed with deionised water (4 x 500 ml), dried in an oven at 80 to 100"C and subsequently calcined at 350"C.
XRD analysis showed the material to have a basal doo, spacing of about 1 3 Angstroms.
Example 2
The beryllium pillared layered clay (20 ml) obtained in Example 1 was charged to a reactor in a small continuous flow unit and ethanol/ethylene oxide (10:1 wt) was passed over the catalyst at 90 C with a contact time of about 1 5 minutes. A 63% conversion of ethylene oxide was obtained under these conditions. The percentage ratio of mono-: diglycol ether was 92:8 (wt).
Claims (9)
1. A pillared layered clay having beryllium-containing pi!lars.
2. A pillared layered clay according to claim 1 wherein the beryllium-containing pil lars comprise oligomeric beryllium species.
3. A process for the production of a pillared layered clay having beryllium-containing pillars which process comprises in a first step hydrolysing a hydrolysable compound of beryllium and thereafter in a second step cationexchanging a cation-exchangeable layered clay with the hydrolysate so-obtained.
4. A process according to claim 3 wherein the hydrolysable compound of beryllium is a beryllium salt.
5. A process according to either claim 3 or claim 4 wherein hydrolysis of the hydrolysable beryllium compound is effected by reaction with either an aqueous or an aqueous alcoholic solution of an inorganic base.
6. A process according to claim 5 wherein the ratio of the concentration of base, expressed in terms of moles of hydroxide per litre, to the concentration of beryllium, expressed in terms of g ions of beryllium per litre is in the range from 5:1 to 1:5.
7. A process according to any one of claims 3 to 6 wherein the layered clay is a smectite.
8. A process according to any one of claims 3 to 6 wherein the layered clay is a pillared clay in which the pillars are derived from another material.
9. A process according to any one of claims 3 to 8 wherein the layered clay is cation-exchanged with the hydrolysate at a temperature less than 50"C.
1 0. A process according to any one of claims 3 to 9 wherein the pillared clay is separated from the hydrolysate and heated to a temperature in the range from 250 to 450"C to drive off water.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8333614A GB8333614D0 (en) | 1983-12-16 | 1983-12-16 | Pillared layered clays |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8431326D0 GB8431326D0 (en) | 1985-01-23 |
| GB2151603A true GB2151603A (en) | 1985-07-24 |
| GB2151603B GB2151603B (en) | 1987-04-08 |
Family
ID=10553423
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8333614A Pending GB8333614D0 (en) | 1983-12-16 | 1983-12-16 | Pillared layered clays |
| GB8431326A Expired GB2151603B (en) | 1983-12-16 | 1984-12-12 | Modified clay |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8333614A Pending GB8333614D0 (en) | 1983-12-16 | 1983-12-16 | Pillared layered clays |
Country Status (1)
| Country | Link |
|---|---|
| GB (2) | GB8333614D0 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4866020A (en) * | 1987-03-26 | 1989-09-12 | The British Petroleum Company P.L.C. | Lithiated clays and uses thereof |
| EP0240359A3 (en) * | 1986-04-04 | 1989-10-25 | Exxon Research And Engineering Company | A method of pillaring micas and the resulting pillared micas |
| US4952544A (en) * | 1987-03-05 | 1990-08-28 | Uop | Stable intercalated clays and preparation method |
| US4957889A (en) * | 1987-03-05 | 1990-09-18 | Uop | Stable intercalated clays and preparation method |
| US4980047A (en) * | 1987-03-05 | 1990-12-25 | Uop | Stable intercalated clays and preparation method |
| US4995964A (en) * | 1987-03-05 | 1991-02-26 | Uop | Midbarrel hydrocracking process employing rare earth pillared clays |
-
1983
- 1983-12-16 GB GB8333614A patent/GB8333614D0/en active Pending
-
1984
- 1984-12-12 GB GB8431326A patent/GB2151603B/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0240359A3 (en) * | 1986-04-04 | 1989-10-25 | Exxon Research And Engineering Company | A method of pillaring micas and the resulting pillared micas |
| US4952544A (en) * | 1987-03-05 | 1990-08-28 | Uop | Stable intercalated clays and preparation method |
| US4957889A (en) * | 1987-03-05 | 1990-09-18 | Uop | Stable intercalated clays and preparation method |
| US4980047A (en) * | 1987-03-05 | 1990-12-25 | Uop | Stable intercalated clays and preparation method |
| US4995964A (en) * | 1987-03-05 | 1991-02-26 | Uop | Midbarrel hydrocracking process employing rare earth pillared clays |
| US4866020A (en) * | 1987-03-26 | 1989-09-12 | The British Petroleum Company P.L.C. | Lithiated clays and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2151603B (en) | 1987-04-08 |
| GB8431326D0 (en) | 1985-01-23 |
| GB8333614D0 (en) | 1984-01-25 |
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