|Publication number||US2892858 A|
|Publication date||Jun 30, 1959|
|Filing date||Jul 27, 1955|
|Publication number||US 2892858 A, US 2892858A, US-A-2892858, US2892858 A, US2892858A|
|Export Citation||BiBTeX, EndNote, RefMan|
|Non-Patent Citations (1), Referenced by (82), Classifications (7)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent PRODUCTION OF ALCOHOLS Karl Ziegler, Muelheim, Ruhr, Germany No Drawing. Application July 27, 1955 Serial No. 524,798
Claims priority, application Germany August 7, 1954 17 Claims. (Cl. 260-448) This invention relates to and has as its object, the production of alcohols from organic aluminum compounds.
In accordance with the invention, it has been found that aluminum hydrocarbons containing a methylene radical bound to the aluminum, will undergo autooxidation when contacted with oxygen forming aluminum alcoholates which are readily decomposed with water and/or acids into primary alcohols. Alumina in practically, pure form may be recovered as a by-product of the reaction.
While it was known that certain organic metal compounds as, for example, alkyl and aryl compounds of the alkali metals, magnesium, zinc, boron, etc., would react vigorously with oxygen, the oxidation would not proceed smoothly and generally several reaction products were obtained as a result of the oxidation. Furthermore, the reaction products obtained from the oxidation of the various difierent compounds would vary widely from each other and it was not possible to predict or foresee how the oxidation of the organic aluminum compounds in accordance with the invention, would proceed.
The starting aluminum hydrocarbons, in accordance with the invention, may be any of the known aluminum hydrocarbons containing a methylene radical bound to the aluminum as, for example, aluminum trialkyls or aluminum alkyl hydrides. These aluminum compounds may be represented by the general formula in which R and R represent hydrogen or a hydrocarbon radical such as an alkyl radical and in which may be in the form of a hydrocarbon ring.
These aluminum hydrocarbons may be readily and economically prepared as, for example, in accordance with the method of co-pending applications, Serial No. 484,576 filed January 27, 1955 and Serial No. 524,797 filed July 27, 195 5, now Patent No. 2,835,689.
As a result of the oxidation of these aluminum hydro carbons, aluminum alcoholates are formed which correspond in structure to the starting aluminum hydrocarbons except that an oxygen atom is interposed between the organic radical and the aluminum. 7
Starting aluminum hydrocarbons may also be obtained in accordance with West German Patents Nos. 917,006 and 889,229. In accordance with these German patents,
higher molecular trialkyl aluminum compounds are built up from triethyl aluminum by reaction with ethylene. As
the alcohol ultimately produced in accordance with the invention corresponds to the organic radical portion connected to the aluminum in the starting aluminum aluminum to form aluminum hydrocarbons having an,
organic radical portion corresponding to the a-olefines. It is thus possible, in accordance with the invention, to convert olefines into the corresponding primary alcohols. Thus, for example, the a-olefines obtained from the cracking of the higher boiling fractions of the Fischer-Tropsch synthesis, may be converted into the corresponding alcohols.
Prior to the instant invention, it was not, as a rule, possible to obtain primary alcohols directly from olefines as, for example, by the addition of water. In accordance with the present invention, however, olefines may be very easily converted via the corresponding aluminum compound into primary alcohols. In this manner, in accordance with the invention, in mation of many known alcohols, it a very large number of completely have not been literature.
The formation of the aluminum hydrocarbon from the olefine in accordance with application Serial No. 524,797 filed July 27, 1955 which are subsequently converted into the alcohol by the oxidation and decomposition, in accordance with the invention, is merely effected by contacting an aluminum hydrocarbon having a methylene is possible to produce novel alcohols which previously produced nor described in the radical connected to the aluminum as, for example, tri-- isobutyl aluminum with an olefine at a temperature between about 50 and C. The olefines used for this purpose may be any olefine having a terminal double bond, cyclo olefines having 4, 5, 7 and 8 carbon atoms and at least one R C=CH group in the ring and fulvenes. When starting, in accordance with the invention, with aluminum hydrocarbons in which the aluminum has all its valence linkages bound to hydrocarbons, as may be represented by the formula omR AICH2R CHgR in which R is a hydrocarbon radical, during the course of the auto-oxidation, in accordance with the invention, the compounds pass successively into OOHZR OCH R Al-CHgR AlOCHgR CHgR 01113 and OCHzR AlOCH2R OCH2R The oxidation forming the first two types of compounds,
takes place extremely rapidly while the oxidation forming the third type of re-oxidation at ordinary or even slightly increased temperatures. It is therefore preferable to effect the auto addition to the for-' compound requires a rather lengthy oxidation initially with a gas containing only a small amount of oxygen as, for example, nitrogen to which only a small amount of air has been added and to gradually increase the oxygen concentration during the course of the reaction until finally pure oxygen is present in the final stage. The gases used for the oxidation should be extensively dried since otherwise due to side reactions, hydrocarbon radicals as such in non-oxidized form can prematurely split off the aluminum resulting in a decrease in yield. For effecting the oxidation, the oxidizing gases may be maintained in circulation and oxygen may be added at some point in the circuit.
The temperature of the oxidation may vary widely as, for example, between temperatures of minus 20 and plus 150 C. It is more practical to use temperatures between and 100 C. with temperatures between about 3.0 and 60 C. being preferred.
In many cases, the aluminum alcoholates produced by the oxidation of the aluminum hydrocarbons, are liquids of rather low viscosity. In such cases, the auto-oxidation may be elfected using undiluted starting aluminum hydrocarbons. While proceeding in such a manner, however, it is necessary to be particularly careful at the start of the reaction in determining the oxygen content of the oxidizing gas mixture. In other cases, it is advisable to effect the oxidation in the presence of solvents, as, for example, primary aliphatic or aromatic hydrocarbons.
As mentioned, the starting aluminum hydrocarbons may be in the form of monohydrides and monohydrides may be formed to a greater or lesser extent when producing the aluminum hydrocarbons have the three hydrocarbon radicals bound to the aluminum.
When oxidizing and decomposing these monohydrides, in accordance with the invention, to form alcohols, the yield is substantially less than proceeding with the aluminum hydrocarbons having three hydrocarbon radicals bound to the aluminum since in the case of the monohydrides, a maximum of two mols of alcohol can be theoretically produced per mol of monohydride. In operation, however, it is not even possible to obtain this reduced theoretical yield since the first resultant product of the oxidation is a hydroperoxide, i.e., an aluminum compound having an OOH group bound to the aluminum which contains a mobile hydrogen atom which then releases a hydrocarbon radical from the aluminum in the form of an unoxidized hydrocarbon further reducing the ultimate yield of alcohol by about one-third.
Losses of this type may be avoided by using a starting aluminum hydrocarbon which contains a minimum quantity of hydride. The formation of hydrides may be kept at a minimum when preparing the aluminum hydrocarbons, by various methods. Thus, for example, when preparing the starting aluminum hydrocarbons in accordance with US. patent application Serial No. 524,797 an excess of olefine may be used in the reaction and then this excess may be removed under as gentle conditions as possible at the lowest possible temperature, or the first oxidation in accordance with the invention may be etlected in the presence of this excess olefine and the olefine may be subsequently separated from the formed aluminum alcoholate by distillation.
It is often desirable, particularly when using more expensive olefines to completely convert these olefines into the alcohols via the alcoholate without the use of an excess. In such cases, the olefines may be converted into the corresponding aluminum hydrocarbons using an ex-- cess of the initial aluminum hydrocarbon which is re acted with the olefine as, for example, triisobutyl aluminum. Under these conditions, however, monohydrides are formed since the triisobutyl aluminum readily loses an isobutyl radical while hot forming diisobutyl' alumi num monohydride, After treatment of the olefine with the triisobutyl aluminum, it is therefore advisable to again treat the reaction product prior to the oxidation in accordance with the invention, with a less expensive olefine which may, for example, be isobutylene, at the lowest. possible temperature in order to convert. all the AlH bonds present in the reaction mixture into Al-R bonds and, in particular, when using isobutylene to isobutyl radicals. As side products there is then produced upon the oxidation-decomposition, in accordance with the invention, a certain quantity of isobutyl alcohol. On the other hand, however, the conversion of the olefine employed corresponding to the desired reaction product into the alcohol takes place substantially more easily than if this after-treatment were omitted and if quantities of aluminum monohydrides were present.
It is of particular advantage that the oxidation, in accordance with the invention, may be efiected in the presence of inert hydrocarbons. It is thus possible when converting the olefines ultimately to be converted to alcohols, in accordance with the invention, into the starting aluminum hydrocarbons, to use hydrocarbon mixtures which consist only in part of these olefines. The
aluminum hydrocarbons formed will therefore be formed in admixture with these inert hydrocarbons. Accordingly, the oxidation in accordance with the invention, is efiected using this entire mixture and after the oxidation, the formed aluminum alcoholates may easily be separated from the other hydrocarbons by distillation, possibly under vacuum. The aluminum alcoholates are generally difiiculty volatile and remain as the distillation residue. This distillation residue which is substantially free from the other hydrocarbons, may then be directly converted into the desired alcohols, free of the hydrocarbons with water and/ or acids. This obtaining of the hydrocarbonfree alcohol in a simple manner is a substantial advantage as compared with the known methods for the conversion of olefines into oxygen-containing compounds as, for example, in accordance with the so-called oxosynthesis. As is well known, hydrocarbon mixtures may not be used in the oxo process. if pure reaction products are desired since it is not possible to separate the aldehydes formed in the oxo process from the hydrocarbons with the same boiling point by distillation alone.
The following examples are given by way of illustration and not limitation:
Example 1 Nitrogen was blown through 366 grams tri-n-octyl aluminum prepared by the process of patent application, Serial No. 524,797 and triisobutyl aluminum in a recycle apparatus. Oxygen was carefully added to the circuit in such a manner that the oxygen content in the circulating gas was about 5%. The aluminum tri-n-octyl warmed up and the reaction vessel used was cooled from the outside. As the heat given off in the reaction vessel became smaller, the oxygen content in the circulating stream was increased first of all to 10 to 20% and finally pure oxygen was employed. The oxidation required 3 to 8 hours depending on the intensity of the cooling. Towards the end, the absorption of oxygen slowed down greatly. The apparatus was so arranged that the oxygen absorption was under control and the operation discontinued when no more oxygen had been absorbed for at least one-halt hour to one hour. The gases used were very carefully dried by a good drying agent, for example, potassium hydroxide heated to 400 0., dried and applied to pumice stone or magnesium perchlorate. During the oxidation,
the aluminum trioctyl which initially had a thin liquid consistency became viscous, but the reaction could be carried out without difliculty. The thick, oily aluminum octylate finally obtained was decomposed by the addition of water with heating. Thereupon the octyl alcohol formed was distilled over by steam distillation. The oil which passed over with the distillate was separated and I dried over potassium carbonate. Distillation, preferably in a vacuum, was then effected. There were obtained 320to 350-grams of the primary normal octyl alcohol.
having an entirelyconstant boiling point of 81.5/8 mm. and of excellent odor.
As residue of the steam distillation, there were obtained an aluminum hydroxide paste from which the aluminum hydroxide could easily be separated in the known manner by filtration orcentrifuging, and can thereupon be convetted by the removal of water into an alumina of very high purity.
Example 2 A solution of tri phenyl-ethyl aluminum in hexane is first of all prepared in accordance with Example 3 of patent application Serial No. 524,797 and then oxidized in the manner described in Example 1. The treatment carried out in the manner indicated in Example 1 results in the formation of phenylethyl alcohol of a boiling point of 98-10l C./ 8 mm. or 220 at ordinary pressure, which corresponds to the value given in the literature. The yield is about 70% of the theoretical quantity.
' Example 3 To 10 kgs. of a product obtained by the cracking of higher Fischer-Tropsch paratfins and having a boiling point of ISO-230 Cfwith an olefine content determined by bromine titration of 8 moles of olefine per kilogram and an tat-olefine content determined spectroscopically in infrared light of 5.8 moles per kilogram, there were added 3 kilograms aluminum triisobutyl. The mixture was thereupon converted, in accordance with Example 5 of patent application Serial No. 524,797 at 120-130 C. in vacuum into the aluminum compound. The solution of the aluminum hydrocarbons formed in the inert accompanying substances of the OL-OIefiIICS was then transferred into a high cylindrical iron vessel provided on the outside with water cooling and thereupon very thoroughly dried air was blown through, first of all cautiously, and thereupon continuously more intensively. The cooling of the reaction mixture and the gas velocity were so regulated that the temperature as far as possible did not exceed +30 C. Finally, the temperature was increased to 50 C. and oxidation was continued for about 2 hours with pure oxygen. The solution obtained in this manner of the aluminum compounds of the alcohols produced was thereupon transferred into a distilling vessel and freed as completely as possible from the hydrocarons by heating under vacuum. If importance is placed on the absolute freedom of the alcohols to be obtained from hydrocarbons, after the hydrocarbons have been driven ofi, superheated vapors of a hydrocarbon of relatively low boiling point, for instance, benzene, can be blown through the liquid aluminum alcoholate remaining in the residue, whereupon the last traces of higher hydrocarbons still adhering to the liquid aluminum alcoholate will be driven oil, or a very effective continuously operating thin-layer vacuum evaporator may be used to drive off the hydrocarbons.
In each case, there is obtained the oily alcoholate which is then advisedly further treated by decomposition with water in accordance with Example 1. The higher boiling fractions of the alcohols obtained are finally separated from the aluminum hydroxide paste by distillation with superheated steam under a vacuum. The aluminum hydroxide paste can be very readily converted back into pure alumina by calcining. The entire organic portions of the distillate are collected.
The quantity of crude alcohols to be obtained depends somewhat on the initial olefines employed. In one special case, there were obtained, for example, 6 kilograms of crude alcohol which could be further split up by fractional vacuum distillation. The individual fractions to be obtained in this connection depend, of course, on the sharpness of the hydrocarbon cut introduced. With an introduced fraction of a boiling point of 180- 6 230 0., there were regularly still presentsmall portions of C -olefines so that the first alcohol obtained upon dis tillation in an effective column in vacuum, is customarily the primary octyl alcohol. By further distillation on an efiective column, there can be obtainedone after the other all primary straight-chain fatty alcohols having 9 to 16 carbon atoms, with which however, if a hydrocarbon prepared by Fischer-Tropsch synthesis is initially used, there are also admixed certain quantities of methylbranched fatty alcohols. The pure primary fatty alcohols, praticularly the higher carbon atoms, can readily be caused to crystallize from the corresponding fractions by cooling and then removed by suction filtering or centrifuging.
Example 4 Example 5 118 grams of the aluminum compound obtained from 1-vinylcyclohexene-( 3) were diluted with 200 cc. octane and subjected to oxidation in accordance with'Examp'le 1. Upon working-up there is obtained tetrahydrophenylalcohol of the following formula: 1
This alcohol is a colorless oil of a to 107 C./15 mm.; n =1.4831.
From limonene and camphene there can be obtained in a simple manner the alcohol having the formul Example 6 patent application Serial No. 524,797, filed July 27, 1955, i
with aluminumtriisobutyl into the aluminum compound 12 Al CHg-O which is then oxidized with 600 cc. of toluene, diluted in the manner described in the other examples, and there are obtained 300 gm. of the alcohol 12 H O-QHg-C members having 12 or more 20 carbon atoms with a maximum boiling point of aseassa alcohol is a colorless oil of a boiling point of hydrocarbon having a radical bound to the aluminum in methylene linkage therewith, at a temperature between -20 and 150 C. thereafter decomposing the aluminum alcoholate formed with a member selected from the group consisting of water and acid, and recovering the primary alcohol formed.
2. Process according to claim 1, in which said contactingisjeiiected in the presence of a solvent.
1 3.-Processaccording to claim 2, in which said solvent is a? member selected from the group consisting of aliphatic and aromatic hydrocarbons.
4. Process according to claim 1, in which said contacting with oxygen is effected by contacting the aluminumhydrocarbon with a gas having a low oxygen content, and increasing the oxygen content of the gas during said contacting until the gas has a high oxygen content.
5. Process according to claim 1, in which said contacting is effected at a temperature between about 20 to l50 C.
j 6. Process according to claim 1, in which said contactingisefiected at a temperature between about and 100 ,C.
7. Process according to claim 1, in which said contacting is efiected at a temperature at 30 to 60 C.
8. Process according to claim 1, in which an aluminum hydrocarbon is substantially free from aluminum hydride.
9. Process according to claim 1, in which said aluminum hydrocarbon contains aluminum hydride and which includes contacting the aluminum hydrocarbon with an olefine prior to said contacting with oxygen.
10. Process according to claim 9, in which said olefine is isobutylene.
' ll. Process according to claim 1, in which said aluminum hydrocarbon is in admixture with hydrocarbons and which includes after said contacting with oxygen, distilling oi the hydrocarbons from the formed aluminum alcoholate prior to said decomposition.
12. Process for the production of aluminum alcoholates which comprises contacting with oxygen an aluminum hydrocarbon having a radical bound to the aluminum in methylene linkage therewith at a temperature between about --20 to C., and recovering the aluminum alcoholate formed.
13. Process according to claim 12, in which said contacting is effected with a gas mixture containing a, low. oxygen content, and in which the oXYgcn content of the gas mixture is increased during said contacting until the gas mixture has a high oxygen content.
14. Process for the production of primary alcohols from olefines which comprises contacting an aluminum hydrocarbon with an olefine having a terminal'double bond, at a temperature between about 50 and 150 C., thereafter contacting the aluminum hydrocarbon formed by displacement of the initial hydrocarbon radical with a hydrocarbon radical corresponding to the olefine with oxygen at a temperature between about -20 and +150 C., decomposing the aluminum alcoholate formed with a member selected from the group consisting of water and acid, and recovering the primary alcohol formed.
15. Process according to claim 14, in which said start ing aluminum hydrocarbon is triisobutyl aluminum and in which said olefine is an olefine other than isobutylene.
16. Process according to claim 14, in which said olefine is present in admixture with other hydrocarbons and which includes distilling oil the hydrocarbons from the formed aluminum alcoholate prior to said decomposition. Y
17. A process for the production of primary alcohols having the general formula ROH which comprises contacting with molecular oxygen under anhydrous conditions an aluminum trialkyl compound having the general formula AlR wherein R is an alkyl group containing at least two carbon atoms hitting a radical bound to the aluminum in methylene linkage therewith, at an oxidizing reaction temperature maintained at less than about, 150 C. and hydrolyzing the aluminum trialkoxides formed and recovering the primary alcohols thus produced.
References Cited in the file of this patent UNITED STATES PATENT OFFICE CERTIFICATE OF CQRRECTEQN Patent Noo 2392,8523 June 139, 1959 Karl Ziegler It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 2, line 46, for "RgC 'CH" ree C GH a Signed and sealed this 3rd day of November 1959,
KARL HG AXLINE Atteszing Officer RGBERT C. WATSGN Commissioner of Patents
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US3016397 *||Sep 25, 1958||Jan 9, 1962||Goodrich Gulf Chem Inc||Process for oxidizing aluminum hydrocarbons|
|US3030402 *||Apr 27, 1959||Apr 17, 1962||Exxon Research Engineering Co||Production of higher aluminum alkyls|
|US3035077 *||Mar 31, 1960||May 15, 1962||Sun Oil Co||Preparation of diols|
|US3038887 *||Mar 12, 1959||Jun 12, 1962||Eastman Kodak Co||Norcamphanyl esters of alpha, beta-unsaturated dicarboxylic acids and polymers thereof|
|US3042696 *||Jul 20, 1956||Jul 3, 1962||Exxon Research Engineering Co||Preparation of aluminum alcoholates|
|US3070616 *||Mar 31, 1960||Dec 25, 1962||Continental Oil Co||Oxidation of trialkylaluminum in the presence of aluminum trialkoxide|
|US3097226 *||Jul 25, 1961||Jul 9, 1963||Continental Oil Co||Two step preparation of aluminum alkoxides|
|US3100231 *||Mar 30, 1959||Aug 6, 1963||Goodrich Gulf Chem Inc||Process for producing telomer alcohols|
|US3104251 *||Jul 7, 1960||Sep 17, 1963||Continental Oil Co||Purification of organo-aluminum compounds by spray stripping|
|US3153076 *||Dec 5, 1962||Oct 13, 1964||Exxon Research Engineering Co||Two-stage process for aluminum alkyl oxidation|
|US3217058 *||Nov 2, 1961||Nov 9, 1965||Continental Oil Co||Preparation of alpha-olefins from aluminum alkoxides|
|US3238237 *||Aug 10, 1959||Mar 1, 1966||Jefferson Chem Co Inc||Method of producing trialkoxy aluminum compounds|
|US3247264 *||Jul 22, 1960||Apr 19, 1966||Goodrich Gulf Chem Inc||Method of manufacturing solid alcohols|
|US3262957 *||Apr 18, 1960||Jul 26, 1966||Max E Roha||Process for oxidizing alkyl aluminum halides in presence of potassium salt|
|US3270065 *||Jul 6, 1961||Aug 30, 1966||Recovery from metal-free oxygenated alcohol products arising during mod- ified oxidation of aluminum alkyls|
|US3278262 *||Nov 25, 1960||Oct 11, 1966||Continental Oil Co||Preparation of alpha-olefins, alkanols and alumina|
|US3281443 *||Feb 24, 1961||Oct 25, 1966||Continental Oil Co||Preparation and use of dialkoxyaluminum hydride reducing agents|
|US3282974 *||Jan 12, 1961||Nov 1, 1966||Henkel & Cie Gmbh||Preparation of aluminum trialkyl compounds|
|US3293274 *||Jun 19, 1961||Dec 20, 1966||Continental Oil Co||Process for preparation of high molecular weight aluminum alkyls|
|US3309416 *||Jan 18, 1962||Mar 14, 1967||Continental Oil Co||Preparation of alpha-olefins|
|US3313836 *||Nov 13, 1961||Apr 11, 1967||Continental Oil Co||Preparation of dialkylaluminum aralkoxide by decomposition of etherates|
|US3350360 *||Nov 25, 1966||Oct 31, 1967||Continental Oil Co||Separation of olefins from aluminum trialkoxides|
|US3391175 *||Jun 26, 1964||Jul 2, 1968||Ethyl Corp||Process for producing high alkyl trialkyl aluminum compounds and vinyl olefins|
|US3412127 *||Oct 22, 1965||Nov 19, 1968||Continental Oil Co||Alkylaluminum oxidation process|
|US3455978 *||Sep 19, 1966||Jul 15, 1969||Union Carbide Corp||Process for producing trialkoxyaluminum compounds|
|US3852190 *||Oct 27, 1972||Dec 3, 1974||Chevron Res||Reforming with platinum on alumina derived from a byproduct of a ziegler process|
|US3986844 *||Jul 23, 1975||Oct 19, 1976||Continental Oil Company||Organic silicon removal from stripper overhead|
|US4055634 *||Feb 11, 1975||Oct 25, 1977||Hoffmann-La Roche, Inc.||Antiperspirants|
|US4104154 *||Apr 18, 1977||Aug 1, 1978||Uop Inc.||Reforming of a naphtha fraction in contact with an alumina-supported catalyst|
|US4210522 *||Oct 25, 1978||Jul 1, 1980||Uop Inc.||Hydrocracking catalyst|
|US4295959 *||Oct 20, 1980||Oct 20, 1981||Uop Inc.||Hydrocarbon dehydrocyclization with an attentuated superactive multimetallic catalytic composite|
|US4295960 *||Nov 3, 1980||Oct 20, 1981||Uop Inc.||Hydrocarbon dehydrocyclization with an attenuated superactive multimetallic catalytic composite|
|US4298462 *||Nov 17, 1980||Nov 3, 1981||Uop Inc.||Hydrocarbon dehydrocyclization with an acidic multimetallic catalytic composite|
|US4299689 *||Oct 23, 1980||Nov 10, 1981||Uop Inc.||Hydrocarbon conversion with an attenuated superactive multimetallic catalytic composite|
|US4304950 *||Nov 3, 1980||Dec 8, 1981||Uop Inc.||Hydrocarbon dehydrogenation method using a nonacidic multimetallic catalytic composite|
|US4309277 *||Aug 18, 1980||Jan 5, 1982||Uop Inc.||Conversion of hydrocarbons with a catalyst comprising an alumina-zeolite, a group VI-B metallic component and a group VIII metallic component|
|US4313020 *||Nov 24, 1980||Jan 26, 1982||Uop Inc.||Hydrocarbon dehydrogenation with an attenuated superactive multimetallic catalytic composite for use therein|
|US4329259 *||Oct 20, 1980||May 11, 1982||Uop Inc.||Acidic multimetallic catalytic composite|
|US4333854 *||Oct 23, 1980||Jun 8, 1982||Uop Inc.||Sulfided superactive multimetallic catalytic composite|
|US4341664 *||Oct 20, 1980||Jul 27, 1982||Uop Inc.||Hydrocarbon dehydrogenation with an attenuated superactive multimetallic catalytic composite for use therein|
|US4343724 *||Nov 24, 1980||Aug 10, 1982||Uop Inc.||Hydrocarbon dehydrogenation with an attenuated superactive multimetallic catalytic composite for use therein|
|US4353815 *||Nov 3, 1980||Oct 12, 1982||Uop Inc.|
|US4362653 *||Apr 27, 1981||Dec 7, 1982||Uop Inc.||Hydrocarbon conversion catalyst|
|US4400571 *||Sep 10, 1982||Aug 23, 1983||Uop Inc.||Hydrocarbon isomerization process|
|US4416804 *||Jun 7, 1982||Nov 22, 1983||Uop Inc.||Acidic multimetallic catalytic composite|
|US4594334 *||Feb 19, 1985||Jun 10, 1986||Uop Inc.||Platinum-, rhenium-, indium-containing catalysts for conversion of hydrocarbons|
|US5382350 *||Oct 16, 1992||Jan 17, 1995||Uop||High hydrogen and low coke reforming process|
|US5430165 *||Nov 26, 1993||Jul 4, 1995||Albemarle Corporation||Method of oxidizing aluminum alkyls|
|US5604072 *||Sep 19, 1995||Feb 18, 1997||Canon Kabushiki Kaisha||Toner for developing electrostatic images, image forming method and process cartridge|
|US5660963 *||Nov 28, 1995||Aug 26, 1997||Canon Kabushiki Kaisha||Toner for developing electrostatic image|
|US6403526||Jan 13, 2000||Jun 11, 2002||W. R. Grace & Co.-Conn.||Alumina trihydrate derived high pore volume, high surface area aluminum oxide composites and methods of their preparation and use|
|US7012104||Oct 16, 2003||Mar 14, 2006||Conocophillips Company||Fischer-Tropsch processes and catalysts made from a material comprising boehmite|
|US7071239||Oct 16, 2003||Jul 4, 2006||Conocophillips Company||Fischer-Tropsch processes and catalysts using stabilized supports|
|US7163963||Sep 8, 2003||Jan 16, 2007||Conocophillips Company||Chemically and thermally stabilized alumina for Fischer-Tropsch catalysts|
|US7186757||Oct 14, 2004||Mar 6, 2007||Conocophillips Company||Silica-alumina catalyst support with bimodal pore distribution, catalysts, methods of making and using same|
|US7271303||Sep 22, 2004||Sep 18, 2007||Uop Llc||Multi-zone process for the production of diesel and aromatic compounds|
|US7307034||Oct 19, 2006||Dec 11, 2007||Uop Llc||Alumina guard bed for aromatics transalkylation process|
|US7341976||Apr 26, 2005||Mar 11, 2008||Conocophillips Company||Stabilized boehmite-derived catalyst supports, catalysts, methods of making and using|
|US7402612||Oct 16, 2003||Jul 22, 2008||Conocophillips Company||Stabilized transition alumina catalyst support from boehmite and catalysts made therefrom|
|US7410565||Dec 17, 2004||Aug 12, 2008||Uop Llc||Multi-catalyst selection for chlorided reforming catalyst|
|US7541310||Oct 12, 2004||Jun 2, 2009||Conocophillips Company||Silica-alumina catalyst support, catalysts made therefrom and methods of making and using same|
|US7692052||Jun 14, 2007||Apr 6, 2010||Uop Llc||Multi-zone process for the production of xylene compounds|
|US8758599||Jul 15, 2011||Jun 24, 2014||Uop Llc||Reforming catalyst and process|
|US20040127352 *||Oct 16, 2003||Jul 1, 2004||Conocophillips Company||High hydrothermal stability catalyst support|
|US20040127586 *||Oct 16, 2003||Jul 1, 2004||Conocophillips Company||Stabilized transition alumina catalyst support from boehmite and catalysts made therefrom|
|US20040132833 *||Oct 16, 2003||Jul 8, 2004||Conocophillips Company||Fischer-Tropsch processes and catalysts made from a material comprising boehmite|
|US20040132834 *||Oct 16, 2003||Jul 8, 2004||Conocophillips Company||Fischer-tropsch processes and catalysts using stabilized supports|
|US20050054738 *||Sep 8, 2003||Mar 10, 2005||Conocophillips Company||Chemically and thermally stabilized alumina for Fischer-Tropsch catalysts|
|US20050107479 *||Oct 14, 2004||May 19, 2005||Conocophillips Company||Silica-alumina catalyst support with bimodal pore distribution, catalysts, methods of making and using same|
|US20050119116 *||Oct 12, 2004||Jun 2, 2005||Conocophillips Company||Silica-alumina catalyst support, catalysts made therefrom and methods of making and using same|
|US20050234137 *||Apr 26, 2005||Oct 20, 2005||Conocophillips Company||Stabilized boehmite-derived catalyst supports, catalysts, methods of making and using|
|US20060102520 *||Nov 12, 2004||May 18, 2006||Lapinski Mark P||Reforming process using high density catalyst|
|US20070037733 *||Sep 21, 2004||Feb 15, 2007||Johannes Panten||Use of 3-cyclohexenyl-1-propanol as a fragrance|
|US20070042905 *||Oct 19, 2006||Feb 22, 2007||Antoine Negiz||Alumina Guard Bed for Aromatics Transalkylation Process|
|US20070086933 *||Oct 19, 2006||Apr 19, 2007||Antoine Negiz||Alumina Guard Bed for Aromatics Transalkylation Process|
|US20070215523 *||Dec 10, 2002||Sep 20, 2007||Moser Mark D||Dilute phosphorus incorporation into a naphtha reforming catalyst|
|US20080161622 *||Jun 14, 2007||Jul 3, 2008||Frey Stanley J||Multi-zone process for the production of xylene compounds|
|EP0064372A1 *||Apr 26, 1982||Nov 10, 1982||Uop Inc.||Silica-containing catalytic composite and hydrocarbon conversion processes using it|
|EP0707239A1||Sep 20, 1995||Apr 17, 1996||Canon Kabushiki Kaisha||Toner for developing electronstatic images, image forming method and process cartridge|
|EP0716351A2||Nov 27, 1995||Jun 12, 1996||Canon Kabushiki Kaisha||Toner for developing electrostatic image|
|EP1634643A1||Aug 5, 2005||Mar 15, 2006||Institut Français du Pétrole||Doped catalyst on silica-alumina support and improved process for treating hydrocarbon feed streams|
|EP2083002A1||Dec 16, 2008||Jul 29, 2009||Ifp||Method for oligomerising olefins using a catalyst based on silica-alumina|
|U.S. Classification||556/185, 568/715, 568/826, 568/911, 568/840, 568/820|