US20020042544A1 - Method for the oxidation of benzene and/or toluene to phenol and/or cresols - Google Patents
Method for the oxidation of benzene and/or toluene to phenol and/or cresols Download PDFInfo
- Publication number
- US20020042544A1 US20020042544A1 US09/533,739 US53373900A US2002042544A1 US 20020042544 A1 US20020042544 A1 US 20020042544A1 US 53373900 A US53373900 A US 53373900A US 2002042544 A1 US2002042544 A1 US 2002042544A1
- Authority
- US
- United States
- Prior art keywords
- zeolite
- catalyst
- benzene
- toluene
- phenol
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
-
- 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
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
-
- 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
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/26—After treatment, characterised by the effect to be obtained to stabilize the total catalyst structure
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the proposed invention relates to the field of organic synthesis, more specifically to a method for the production of phenol and cresol by the direct selective oxidation of benzene and toluene by means of a gaseous mixture containing nitrous oxide N 2 O in the presence of a heterogeneous catalyst.
- the catalysts used are zeolite-containing catalysts modified by special treatment and additives.
- the known method most similar to the proposed method is a means of oxidizing benzene and/or toluene to phenol and/or cresols using nitrous oxide as the oxidizing agent, with a heterogeneous catalyst containing a high-silica pentasil zeolite which is modified in a preliminary step in which metal ion promoters are added by applying a compound of metals such as iron, etc. to it, then activating the catalyst at a high temperature between 300 and 500° C., and bringing the benzene and/or toluene and the nitrous oxide into contact with the modified heterogeneous catalyst at a reaction temperature between 275 and 450° C. (U.S. Pat. No. 5,110,995, IPC C07 C37/60, national code 568/800, 1992).
- the disadvantages of the known method are related to the need to introduce the iron into the zeolite and to control the state of the iron ions, the low value of the space velocity in benzene and the quite lengthy contact time necessary to achieve acceptable, but not especially high yields of the final products, as well as the low selectivity achieved at elevated temperatures.
- the result produced by the proposed method is an increase in the yield of the final products and an improvement in the selectivity and activity of the catalyst achieved by creating strong Lewis acid sites in the zeolite.
- a starting material such as benzene or toluene or a combination thereof is oxidized to form phenol, creosols or a combination thereof.
- the oxidation is performed at a temperature of 225° C. to 500° C. in the presence of a zeolite catalyst and an oxidizing agent which comprises nitrous oxide.
- the zeolite catalyst is treated according to a special procedure to form the catalyst. Specifically, the zeolite is first calcined at 500-950° C. in air or at 300-850° C. in an inert gas. Next, the zeolite is impregnated with Zn ions by ion exchange or by exposing it to an aqueous solution of zinc salt. Last, the impregnated zeolite is heated in air or an inert gas to a temperature of 300-850° C.
- the high-silica zeolite one can use a pentasil; the pentasil may be the H form of the ZSM-5 zeolite with an Si/Al ratio of 10 to 200.
- the reagents maybe taken in a ratio of N 2 O:benzene and/or toluene from 1:7 to 10:1.
- the mixture of benzene and/or toluene with nitrous oxide may be diluted with an inert gas—nitrogen and/or argon and/or helium.
- heterogeneous catalyst may be used mixed with a binder in the form of silica gel or alumina.
- the starting materials for the catalyst are commercial forms of the zeolite are:
- ZSM-5 Commercial zeolite ZSM-5, advantageously with a Si/Al ratio greater than 10 and preferably with a ratio of 40-100, is used.
- ZSM-5 zeolite is modified with compounds containing Zn ions by ion exchange from nitrates, chlorides and other salts of zinc, or by impregnating it with aqueous solutions of zinc salts.
- the zeolite is calcined at 400-950° C. in air or an inert gas (under static conditions or in a flow). The indicated temperature ensures the dehydroxylation of the zeolite.
- the zeolite is then impregnated with an aqueous solution of zinc nitrate with a normality of 0.1N to 2N in an amount sufficient to add zinc oxide at a rate of from 0.1 to 10 wt %.
- the zeolite is activated at a temperature of 300-500° C.
- This impregnation process may be accomplished in one step or in several steps with intermediate activation at 500-700° C.
- Acidic forms of the zeolite may be used to prepare the catalyst.
- the acidic H form of the high-silica zeolite may be prepared by ion-exchange of the Na form of the zeolite with an aqueous solution of an ammonium salt, a nitrate or chlorite or by treating the Na form of the zeolite with an aqueous solution of an inorganic or an organic acid.
- the degree of ion exchange of sodium by ammonia or a proton is from 30 to 100% (most preferable is 50-95%).
- the Na form of the zeolite can also be used as a starting material for preparing the zeolite containing Zn.
- the zeolite is used as a catalyst, either in the pure form or combined with a binder.
- Amorphous silica gel with a specific surface area of 100-600 m 2 /g or alumina (100-400 m 2 /g) or a mixture thereof is used as the binder.
- the content of binder in the catalyst is from 5 to 50 wt %, preferably 20-30%.
- Nitrous oxide is used either pure, or in a mixture with an inert gas—nitrogen or helium.
- Aromatic hydrocarbons benzene and toluene—are used as the substrates for the selective oxidation to phenol and cresols.
- the substrate is introduced at a rate to give a mixture with N 2 O having a molar ratio of N 2 O:substrate from 1:7 to 5:1, preferably from 1:2 to 4:1.
- the space velocity for the substrate is from 0.2 to 5 h ⁇ 1 , ordinarily 0.5-2 h ⁇ 1 .
- the reaction proceeds at a temperature of 225-500° C.
- the contact time of the reaction mixture with the catalyst is 0.5-8 sec, normally 1-4 sec.
- the gases exiting from the reactor are a mixture of the corresponding phenols and heavy products that are separated and analyzed by analytical methods.
- the catalyst may be easily and reversibly regenerated by calcining at 400-600° C. in a flow of air, oxygen, nitrous oxide, or in a mixture of these gases in inert gas for a period of 1-3 hours.
- HZSM-5 zeolite 10 grams are calcined at 900° C. in a flow of air for 3 hours and are modified by being impregnated to the zeolite's moisture-holding capacity with an aqueous solution of 1N zinc nitrate. The amount of zinc nitrate added amounts to 2 wt % zinc oxide, obtained on decomposition. The resulting zeolite is then activated at 780° C. for 2 hours to convert the nitrate to zinc oxide in the zeolite channels.
- the catalyst was prepared as in Example 1, except that the catalyst used and the calcining temperature required to dehydroxylate the starting H form of the zeolite differed.
- the rate of conversion over the given catalyst may be increased to 50-77% with no reduction in selectivity (98-100%).
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
- The present application is a U.S. non-provisional application based upon and claiming priority from Russian Application No. 99106831 which is hereby incorporated by reference.
- The proposed invention relates to the field of organic synthesis, more specifically to a method for the production of phenol and cresol by the direct selective oxidation of benzene and toluene by means of a gaseous mixture containing nitrous oxide N2O in the presence of a heterogeneous catalyst. The catalysts used are zeolite-containing catalysts modified by special treatment and additives.
- The known method most similar to the proposed method is a means of oxidizing benzene and/or toluene to phenol and/or cresols using nitrous oxide as the oxidizing agent, with a heterogeneous catalyst containing a high-silica pentasil zeolite which is modified in a preliminary step in which metal ion promoters are added by applying a compound of metals such as iron, etc. to it, then activating the catalyst at a high temperature between 300 and 500° C., and bringing the benzene and/or toluene and the nitrous oxide into contact with the modified heterogeneous catalyst at a reaction temperature between 275 and 450° C. (U.S. Pat. No. 5,110,995, IPC C07 C37/60, national code 568/800, 1992).
- In the known method, pentasil zeolites (ZSM-5, ZSM-11, ZSM-12, ZSM-23), mordenite, H-beta zeolite and EU-1 that have been modified with small amounts of iron ions at the zeolite synthesis stage have been shown to be highly active in the direct oxidation of benzene to phenol. At temperatures of 400-450° C. and a contact time of 2-4 sec (space velocity in terms of benzene 0.4 h−1) and a benzene:N2O molar ratio of 1:4, the yield of phenol reaches values of 20-30% with a selectivity of 90-97%. Other systems modified with transition metal ions (Mn, Co, Ni, V, Cu), have been shown to be less active than iron-containing zeolites.
- The disadvantages of the known method are related to the need to introduce the iron into the zeolite and to control the state of the iron ions, the low value of the space velocity in benzene and the quite lengthy contact time necessary to achieve acceptable, but not especially high yields of the final products, as well as the low selectivity achieved at elevated temperatures.
- The result produced by the proposed method is an increase in the yield of the final products and an improvement in the selectivity and activity of the catalyst achieved by creating strong Lewis acid sites in the zeolite.
- According to this method, a starting material such as benzene or toluene or a combination thereof is oxidized to form phenol, creosols or a combination thereof. The oxidation is performed at a temperature of 225° C. to 500° C. in the presence of a zeolite catalyst and an oxidizing agent which comprises nitrous oxide. The zeolite catalyst is treated according to a special procedure to form the catalyst. Specifically, the zeolite is first calcined at 500-950° C. in air or at 300-850° C. in an inert gas. Next, the zeolite is impregnated with Zn ions by ion exchange or by exposing it to an aqueous solution of zinc salt. Last, the impregnated zeolite is heated in air or an inert gas to a temperature of 300-850° C.
- As the high-silica zeolite one can use a pentasil; the pentasil may be the H form of the ZSM-5 zeolite with an Si/Al ratio of 10 to 200.
- The reagents maybe taken in a ratio of N2O:benzene and/or toluene from 1:7 to 10:1.
- Furthermore, the mixture of benzene and/or toluene with nitrous oxide may be diluted with an inert gas—nitrogen and/or argon and/or helium.
- Furthermore, the heterogeneous catalyst may be used mixed with a binder in the form of silica gel or alumina.
- The method for oxidizing benzene and/or toluene to phenol and/or cresols is accomplished as follows.
- The starting materials for the catalyst are commercial forms of the zeolite are:
- (1) the high-silica zeolite ZSM-5
- (2) H-beta zeolite
- Commercial zeolite ZSM-5, advantageously with a Si/Al ratio greater than 10 and preferably with a ratio of 40-100, is used. ZSM-5 zeolite is modified with compounds containing Zn ions by ion exchange from nitrates, chlorides and other salts of zinc, or by impregnating it with aqueous solutions of zinc salts. In a preliminary step the zeolite is calcined at 400-950° C. in air or an inert gas (under static conditions or in a flow). The indicated temperature ensures the dehydroxylation of the zeolite. The zeolite is then impregnated with an aqueous solution of zinc nitrate with a normality of 0.1N to 2N in an amount sufficient to add zinc oxide at a rate of from 0.1 to 10 wt %.
- After impregnation, the zeolite is activated at a temperature of 300-500° C.
- This impregnation process may be accomplished in one step or in several steps with intermediate activation at 500-700° C.
- Acidic forms of the zeolite may be used to prepare the catalyst. The acidic H form of the high-silica zeolite may be prepared by ion-exchange of the Na form of the zeolite with an aqueous solution of an ammonium salt, a nitrate or chlorite or by treating the Na form of the zeolite with an aqueous solution of an inorganic or an organic acid.
- The degree of ion exchange of sodium by ammonia or a proton is from 30 to 100% (most preferable is 50-95%). The Na form of the zeolite can also be used as a starting material for preparing the zeolite containing Zn.
- The zeolite is used as a catalyst, either in the pure form or combined with a binder. Amorphous silica gel with a specific surface area of 100-600 m2/g or alumina (100-400 m2/g) or a mixture thereof is used as the binder. The content of binder in the catalyst is from 5 to 50 wt %, preferably 20-30%.
- Nitrous oxide is used either pure, or in a mixture with an inert gas—nitrogen or helium. Aromatic hydrocarbons—benzene and toluene—are used as the substrates for the selective oxidation to phenol and cresols. The substrate is introduced at a rate to give a mixture with N2O having a molar ratio of N2O:substrate from 1:7 to 5:1, preferably from 1:2 to 4:1. The space velocity for the substrate is from 0.2 to 5 h−1, ordinarily 0.5-2 h−1. The reaction proceeds at a temperature of 225-500° C. The contact time of the reaction mixture with the catalyst is 0.5-8 sec, normally 1-4 sec. The gases exiting from the reactor are a mixture of the corresponding phenols and heavy products that are separated and analyzed by analytical methods. The catalyst may be easily and reversibly regenerated by calcining at 400-600° C. in a flow of air, oxygen, nitrous oxide, or in a mixture of these gases in inert gas for a period of 1-3 hours.
- 10 grams of HZSM-5 zeolite are calcined at 900° C. in a flow of air for 3 hours and are modified by being impregnated to the zeolite's moisture-holding capacity with an aqueous solution of 1N zinc nitrate. The amount of zinc nitrate added amounts to 2 wt % zinc oxide, obtained on decomposition. The resulting zeolite is then activated at 780° C. for 2 hours to convert the nitrate to zinc oxide in the zeolite channels. 1 gram of catalyst with 2% ZnO/HZSM-5 (Si/Al=21), particle size 0.2-0.5 mm, is mixed with 1 gram of quartz of the same particle size and placed in a quartz or steel reactor, i.d. 7 mm. Prior to reaction, the catalyst is activated in an air flow (60 ml/min) at a temperature of 450° C. for 1 h. The reaction is run under the following conditions: T=450° C., N2O:C6H6=1:1, space velocity of benzene V=0.3 h−1.
- The catalyst was prepared as in Example 1. The reaction was run at T=440° C., N2O:C6H6=0.5:1, V=0.5 h−1. The yield of phenol was 39% with a selectivity of 98%.
- The catalyst was prepared as in Example 1, except that the HZSM-5 catalyst was activated at 600° C. The reaction was run at T=440° C., the benzene was delivered at V=0.5 h−1 at a molar ratio N2O:C6H6=0.5:1. The yield of phenol was 35% with a selectivity of 99%.
- The catalyst was prepared as in Example 1, except that the catalyst used and the calcining temperature required to dehydroxylate the starting H form of the zeolite differed. The zeolite used was 2% ZnO/H-beta (Si/Al=25) and it was calcined at 800° C. Reaction conditions: V=1.7 h−1, N2O:C6H6=1:7. The results are shown in Table 1.
TABLE 1 Yield of phenol from benzene oxidized over 2% ZnO/H-beta zeolite (calculated for N2O) (V = 1.7 h−1, N2O:C6H6 = 1.7) Reaction temperature, ° C. Catalyst 420 440 460 ZnO/H-beta 27.3 38.5 38.0 - Catalyst prepared as in Example 1 is loaded into a 1-cm3 reactor (particle size 1-2 mm). Toluene is delivered at V=0.25 h−1 at a molar ratio of N2O:toluene=1:1. The reaction temperature is 425° C., the yield of a mixture of o-, m-, p-cresols is 21.1% with selectivity for cresol of 75%. Benzene, xylene, and phenol are the major by-products. The ratio of o-, m-, and p-cresols is 30:40:30.
- The examples cited above of the use of a Zn-containing high-silica zeolite catalyst in the oxidation of benzene and toluene to the corresponding phenols with nitrous oxide being used as the oxidizing agent demonstrate the following advantages compared to known catalysts:
- 1) The rate of conversion over the given catalyst may be increased to 50-77% with no reduction in selectivity (98-100%).
- 2) The stability of the catalyst is increased by adding zinc ions or zinc oxide, which act as strong Lewis acids, to HZSM-5 zeolite.
- 3) High activity and selectivity are achieved in the oxidation of toluene by nitrous oxide over Zn-containing zeolite catalyst.
- While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out the this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (6)
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US2000/008925 WO2000059852A1 (en) | 1999-04-05 | 2000-04-04 | Method for the oxidation of benzene and/or toluene to phenol and/or cresols |
AU40701/00A AU4070100A (en) | 1999-04-05 | 2000-04-04 | Method for the oxidation of benzene and/or toluene to phenol and/or cresols |
AT00920113T ATE280746T1 (en) | 1999-04-05 | 2000-04-04 | METHOD FOR OXIDIZING BENZENE AND/OR TOLUENE TO PHENOL AND/OR CRESOL |
DK00920113T DK1169287T3 (en) | 1999-04-05 | 2000-04-04 | Process for oxidation of benzene and / or toluene to phenol and / or cresols |
DE60015313T DE60015313T8 (en) | 1999-04-05 | 2000-04-04 | METHOD FOR OXIDIZING BENZENE AND / OR TOLUOL TO PHENOL AND / OR CRESOL |
EP20000920113 EP1169287B1 (en) | 1999-04-05 | 2000-04-04 | Method for the oxidation of benzene and/or toluene to phenol and/or cresols |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
RU99106881/04A RU2155181C1 (en) | 1999-04-05 | 1999-04-05 | Method of oxidation of toluene into phenol, and/or cresols |
RU99106881 | 1999-04-05 |
Publications (2)
Publication Number | Publication Date |
---|---|
US20020042544A1 true US20020042544A1 (en) | 2002-04-11 |
US6388145B1 US6388145B1 (en) | 2002-05-14 |
Family
ID=20218063
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/533,739 Expired - Lifetime US6388145B1 (en) | 1999-04-05 | 2000-03-23 | Method for the oxidation of benzene and/or toluene to phenol and/or cresols |
Country Status (9)
Country | Link |
---|---|
US (1) | US6388145B1 (en) |
EP (1) | EP1169287B1 (en) |
JP (1) | JP2004513062A (en) |
AT (1) | ATE280746T1 (en) |
AU (1) | AU4070100A (en) |
DE (1) | DE60015313T8 (en) |
DK (1) | DK1169287T3 (en) |
RU (1) | RU2155181C1 (en) |
WO (1) | WO2000059852A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7678343B2 (en) * | 1999-12-24 | 2010-03-16 | Ineos Vinyls Uk Ltd. | Metallic monolith catalyst support for selective gas phase reactions in tubular fixed bed reactors |
CN1297478C (en) * | 2003-11-28 | 2007-01-31 | 上海家化联合股份有限公司 | Molecular sieve based nano composite anti-ultraviolet material, its preparation method and use |
BR112017006338B1 (en) | 2014-10-02 | 2021-11-16 | Monsanto Technology Llc | PROCESSES FOR THE PRODUCTION OF 2,5-DICHLOROPHENOL AND 3,6-DICHLORO-2-METOXYBENZOIC ACID |
Family Cites Families (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5677234A (en) | 1979-11-29 | 1981-06-25 | Ube Ind Ltd | Preparation of phenol |
JPS5817174B2 (en) | 1979-12-19 | 1983-04-05 | 宇部興産株式会社 | Manufacturing method of phenol |
CA1182800A (en) | 1981-06-26 | 1985-02-19 | Warren W. Kaeding | Treatment of zeolite catalysts to enhance para- selectivity |
US4581215A (en) | 1981-06-26 | 1986-04-08 | Mobil Oil Corporation | Para-selective zeolite catalysts treated with halogen compounds |
US4367358A (en) | 1981-12-14 | 1983-01-04 | The Goodyear Tire & Rubber Company | Method for the production of ethylbenzene |
US4559314A (en) | 1982-03-22 | 1985-12-17 | Mobil Oil Corporation | Zeolite activation |
CA1202943A (en) | 1983-08-15 | 1986-04-08 | Mobil Oil Corporation | Treatment of zeolites |
US4724270A (en) | 1985-10-04 | 1988-02-09 | Mobil Oil Corporation | Catalytic conversion over dehydroxylated zeolite |
US4950829A (en) | 1987-06-06 | 1990-08-21 | Mobil Oil Corporation | Aromatization with improved selectivity |
US4837398A (en) | 1987-08-05 | 1989-06-06 | Mobil Oil Corporation | Ammonium activation of zeolites in the presence of gaseous ammonia |
FR2630733B1 (en) | 1988-05-02 | 1990-07-20 | Rhone Poulenc Chimie | PROCESS FOR THE PREPARATION OF PHENOL |
FR2630734B1 (en) | 1988-05-02 | 1990-07-27 | Rhone Poulenc Chimie | PROCESS FOR THE PREPARATION OF DIHYDROXYBENZENES |
CA1332402C (en) | 1989-02-21 | 1994-10-11 | Louise Dufresne | Catalytic aromatization of olefins and paraffins |
FR2648810B1 (en) | 1989-06-22 | 1992-02-28 | Rhone Poulenc Chimie | PROCESS FOR THE PREPARATION OF PHENOLS |
US5110995A (en) | 1991-03-12 | 1992-05-05 | Institute Of Catalysis | Preparation of phenol or phenol derivatives |
EP0568913A3 (en) | 1992-05-03 | 1995-03-22 | Dalian Chemical Physics Inst | Process for the conversion of methanol to light olefins and catalyst used for such process. |
RU2058286C1 (en) | 1994-04-12 | 1996-04-20 | Институт катализа им.Г.К.Борескова СО РАН | Method for production of phenol or its derivatives |
RU2074164C1 (en) | 1994-04-12 | 1997-02-27 | Институт катализа им.Г.К.Борескова СО РАН | Method of producing phenol and derivatives thereof |
JPH08217712A (en) * | 1995-02-10 | 1996-08-27 | Ube Ind Ltd | Production of phenol |
JPH09194412A (en) | 1996-01-12 | 1997-07-29 | Ube Ind Ltd | Production of phenol |
US5849257A (en) | 1996-04-03 | 1998-12-15 | Mitsui Chemicals, Inc. | Process for preparation of nitrous oxide |
US5892132A (en) | 1996-08-08 | 1999-04-06 | Solutia Inc. | Transport hydroxylation reactor |
US5808167A (en) | 1996-08-20 | 1998-09-15 | Solutia Inc. | Selective introduction of active sites for hydroxylation of benzene |
DE19634406C2 (en) | 1996-08-26 | 1998-11-26 | Hoechst Ag | Process for the preparation of hydroxyaromatics by reacting aromatics with N¶2¶O |
DK0929507T3 (en) | 1996-10-07 | 2003-03-24 | Solutia Inc | Process for hydroxylation of benzene |
RU2102135C1 (en) | 1996-12-10 | 1998-01-20 | Институт катализа им.Г.К.Борескова СО РАН | Catalyst for nitrous oxide synthesis |
CA2240612A1 (en) | 1997-07-29 | 1999-01-29 | Vladimir Borisovich Kazansky | Preparation of phenol and its derivatives |
-
1999
- 1999-04-05 RU RU99106881/04A patent/RU2155181C1/en active
-
2000
- 2000-03-23 US US09/533,739 patent/US6388145B1/en not_active Expired - Lifetime
- 2000-04-04 DK DK00920113T patent/DK1169287T3/en active
- 2000-04-04 DE DE60015313T patent/DE60015313T8/en active Active
- 2000-04-04 AU AU40701/00A patent/AU4070100A/en not_active Abandoned
- 2000-04-04 WO PCT/US2000/008925 patent/WO2000059852A1/en active IP Right Grant
- 2000-04-04 JP JP2000609368A patent/JP2004513062A/en active Pending
- 2000-04-04 AT AT00920113T patent/ATE280746T1/en not_active IP Right Cessation
- 2000-04-04 EP EP20000920113 patent/EP1169287B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
AU4070100A (en) | 2000-10-23 |
DE60015313D1 (en) | 2004-12-02 |
DE60015313T8 (en) | 2006-04-27 |
WO2000059852A1 (en) | 2000-10-12 |
JP2004513062A (en) | 2004-04-30 |
EP1169287A1 (en) | 2002-01-09 |
DE60015313T2 (en) | 2006-02-02 |
RU2155181C1 (en) | 2000-08-27 |
EP1169287B1 (en) | 2004-10-27 |
US6388145B1 (en) | 2002-05-14 |
DK1169287T3 (en) | 2005-02-14 |
ATE280746T1 (en) | 2004-11-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4175057A (en) | Zeolite composition | |
US4642403A (en) | Production of aromatics from ethane and/or ethylene | |
US4180689A (en) | Process for converting C3 -C12 hydrocarbons to aromatics over gallia-activated zeolite | |
Hamada et al. | Highly selective reduction of nitrogen oxides with hydrocarbons over H-form zeolite catalysts in oxygen-rich atmospheres | |
EP0050021B1 (en) | Production of aromatics from ethane and/or ethylene | |
EP1531931B1 (en) | Catalyst for aromatization of alkanes, process of making and using thereof | |
US4487843A (en) | Catalytic activity of aluminosilicate zeolites | |
US4654316A (en) | Selective dealumination of zeolites | |
US4497970A (en) | Aromatics production | |
EP0244162B1 (en) | Production of aromatics from ethane and/or ethylene | |
US6388145B1 (en) | Method for the oxidation of benzene and/or toluene to phenol and/or cresols | |
EP0604689B1 (en) | Process for the regeneration of coke-deposited, crystalline aluminogallosilicate catalyst | |
DK150190A (en) | SYNTHETIC CRYSTALLIC ALUMINUM SILICATE AND PROCEDURES FOR ITS MANUFACTURING AND USING | |
JPH04228418A (en) | Zeolite containing metal and its manufacture as well as use of said zeolite in contact reaction process | |
US5874647A (en) | Benzene hydroxylation catalyst stability by acid treatment | |
KR100584817B1 (en) | Preparation of phenol and its derivatives | |
US5929296A (en) | Catalyst based on dealuminated mordenite and its use for dismutation and/or transalkylation of aromatic hydrocarbons | |
EP0889018B1 (en) | Preparation of phenol and its derivatives | |
Ogura et al. | Formation of active sites for reduction of NO2 with methane by solid state exchange of In2O3 into H-zeolites | |
CA1236816A (en) | Modification of zeolites with ammonium fluoride | |
JPH0618798B2 (en) | Method for producing ethylbenzene | |
RU2202532C2 (en) | Method of production of phenol and its derivatives and method of oxidation of benzene and its derivatives | |
Bakhvalov | Mononitration of benzene on solid catalysts without using sulphuric acid | |
Davies et al. | Process for converting C3-C12 hydrocarbons to aromatics over gallia-activated zeolite | |
JPH0610149B2 (en) | Method for producing cyclohexanol by hydration of cyclohexene |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: GENERAL ELECTRIC COMPANY, NEW YORK Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KUSTOV, LEONID MODESTOVICH;TARASOV, ANDREI LEONIDOVICH;TYRLOV, ALEKSANDR ARUNOVICH;AND OTHERS;REEL/FRAME:010874/0687 Effective date: 20000426 |
|
FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
AS | Assignment |
Owner name: SABIC INNOVATIVE PLASTICS IP B.V., NETHERLANDS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:GENERAL ELECTRIC COMPANY;REEL/FRAME:021311/0259 Effective date: 20070831 |
|
AS | Assignment |
Owner name: CITIBANK, N.A., AS COLLATERAL AGENT, NEW YORK Free format text: SECURITY AGREEMENT;ASSIGNOR:SABIC INNOVATIVE PLASTICS IP B.V.;REEL/FRAME:021423/0001 Effective date: 20080307 Owner name: CITIBANK, N.A., AS COLLATERAL AGENT,NEW YORK Free format text: SECURITY AGREEMENT;ASSIGNOR:SABIC INNOVATIVE PLASTICS IP B.V.;REEL/FRAME:021423/0001 Effective date: 20080307 |
|
FPAY | Fee payment |
Year of fee payment: 8 |
|
FPAY | Fee payment |
Year of fee payment: 12 |
|
AS | Assignment |
Owner name: SABIC INNOVATIVE PLASTICS IP B.V., NETHERLANDS Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:032459/0798 Effective date: 20140312 |
|
AS | Assignment |
Owner name: SABIC GLOBAL TECHNOLOGIES B.V., NETHERLANDS Free format text: CHANGE OF NAME;ASSIGNOR:SABIC INNOVATIVE PLASTICS IP B.V.;REEL/FRAME:038883/0906 Effective date: 20140402 |