CN1102074C - Catalysts for production of phenol and its derivatives - Google Patents
Catalysts for production of phenol and its derivatives Download PDFInfo
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- CN1102074C CN1102074C CN95193212A CN95193212A CN1102074C CN 1102074 C CN1102074 C CN 1102074C CN 95193212 A CN95193212 A CN 95193212A CN 95193212 A CN95193212 A CN 95193212A CN 1102074 C CN1102074 C CN 1102074C
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- benzene
- phenol
- catalyzer
- gas
- nitrous oxide
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/36—Steaming
-
- 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
- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
-
- 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
-
- 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
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/072—Iron group metals or copper
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Zeolite catalysts useful for the production of phenol and its derivatives by oxidative hydroxylation of benzene and its derivatives by nitrous oxide, e.g. at temperatures of 225 DEG -450 DEG C., having substantially enhanced process characteristics resulting from hydrothermal treatment using a gas containing from about 3 to 100 mole percent water vapor, e.g. in nitrogen, at a temperature ranging from about 500 DEG to 1000 DEG C. Two hours of hydrothermal treatment has been shown to be effective.
Description
Disclosed herein is the improved catalyzer of producing the phenol derivmives blend biology with what, and the method for making this class catalyzer; The method of described production phenol derivmives blend biology is to make benzene or other aromatic compound generation oxidation hydroxylating with one step of nitrous oxide.
Background
On multiple catalyzer, from the Vanadium Pentoxide in FLAKES on the silica to zeolite, for example ZSM-5 and ZSM-11 type zeolite catalyst, at high temperature, for example 300 to 450 ℃, the method for producing phenol with nitrous oxide partial oxidation benzene is disclosed.When benzene is replaced by a kind of derivative of benzene such as chlorobenzene, fluorobenzene, toluene or ethylbenzene, can produce the phenol of corresponding replacement.When phenol itself during as the benzene that replaces, reaction product comprises dihydroxy-benzene such as quinhydrones, Resorcinol and pyrocatechol.The phenol derivmives blend biology, dihydric phenols for example, the aromatic compound that chlorinated benzene phenols, nitrophenyl phenolic, methylbenzene phenols and other contain hydroxyl is the valuable product that has found widespread use industrial.Prevailing commodity chemical is a phenol in the middle of this class, and it mainly produces resol with what, caprolactam, nitropheneol and chlorinated benzene phenols etc.In recent decades, the investigator has searched out the method for simple and efficient synthesizing phenol and derivative thereof.People such as Iwamoto can make oxygenant with nitrous oxide at an one-step hydroxylation of " physical chemistry " (J.Physical Chemistry (ACS)) the 87th volume No.6 (1983) 903-905 pages or leaves report aromatic compound and implement under the catalyzer condition that for example support oxide of vanadium, molybdenum and tungsten exists that traditional partial oxidation is used.Iwamoto reacts at 550 ℃, and benzene is converted into 10%, and Pyrogentisinic Acid's selectivity is 72%.Though all achievements in the past of these results excellent what far away, the actual use that they still are proved to be this method of what is inadequate, and this just must need to seek more effective system.
Use novel catalyzer, for example have hydroxylating that zeolite structured high silica silico-aluminate carries out benzene by people such as Suzuki at the Chemistry of the chemical association of Japan Letters, people such as (1988) 953-956 pages or leaves, Gubelmann are at United States Patent (USP) 5,055,623 and people such as Kharitonov at United States Patent (USP) 5, reported in 110,995.The hydroxylating of benzene and other aromatic compound is 300-400 ℃ of generation under the condition that this class zeolite catalyst exists, and Pyrogentisinic Acid's selectivity is 90-100%.Yet catalyst activity still is not suitable for the commercial practical of this technology fully.
The novel method that the researchist continues to find to improve this processing parameter and/or promotes the efficient of zeolite has for example been introduced various catalyst pretreatment.In this respect, Zholobenko is at Mendeleev Commun., and (1993) No.1 28-29 page or leaf was reported a kind of method of producing phenol with zeolite catalyst, and this catalyzer once activated by high-temperature calcination in air.It can not make catalyst activity that any increase is arranged when a shortcoming of the method for zholobenko was 700 ℃ of low whats of calcining temperature.More particularly, to be only at comparatively high temps (more than 750 ℃) by the what activation significant, the actual enforcement of the difficult what of the method for zholobenko.
Brief summary of the invention
The invention solves unsatisfactory performance and some relevant problems of efficient of benzene in the production with the phenol derivmives blend biology and derivative used zeolite catalyst in nitrous oxide hydroxylation process thereof.These problems are by using the simple and effective activation treatment of a kind of warp, for example expose the zeolite catalyst in the what water vapour at elevated temperatures and are resolved astoundingly.
DESCRIPTION OF THE PREFERRED
The invention provides a kind ofly, carry out oxidation hydroxylation by the corresponding aroma compound with nitrous oxide with what and produce the phenol derivmives blend biology through improved zeolite catalyst.The catalytic performance of this class zeolite catalyst can be promoted with method of the present invention, promptly handles zeolite catalyst with steam-laden gas phase in 350～950 ℃ temperature range.The amount of water vapour is not critical in gas phase, can be from containing low-level water vapour up to pure basically water vapour a kind of diluent gas.For example, gas phase can be contain be low to moderate 3 molecular fractions (mol%) water vapour in air or preferably a kind of be the inert diluent gas substantially, comprise the gas phase of being formed in nitrogen, argon, helium, carbonic acid gas etc. or their mixture.Certainly should avoid existence can make the component of poisoning of catalyst in the gas phase basically.The water vapour that preferably can contain high level in the gas phase, 10mol% or more for example is up to 100mol%.Time in the catalyzer high temperature exposure what water vapour can change according to the active degree of required enhancement, and can easily be measured by common experiment.
Can stand the inventive method and promote the active zeolite of handling and comprise ZSM-5 and ZSM-11 type zeolite, they are acid type and contain iron preferably.This class zeolite is well-known in this area, and they are buied such as UOP, Mobil and its place with also can easily selling the merchant by catalyzer in all business methods of what.The commodity zeolite catalyst porous matrix of aluminium or silica typically can tolerate the durable ball type that weares and teares in filling type or the fluidized-bed reactor so that provide.Have been found that method of the present invention can advantageously be applicable to the zeolite of powdered or ball type.
With the zeolite catalyst through having promoted performance of method of the present invention preparation derivative, for example particularly useful in the oxidizing reaction of chlorobenzene, fluorobenzene, toluene, ethylbenzene etc. and phenol at aromatic compound such as benzene and benzene.This oxidation be by phenol, nitrous oxide and, randomly, the feed gas mixtures that diluent gas such as nitrogen, argon, carbonic acid gas etc. are formed is 225～450 ℃ or higher temperature, for example more than 500 ℃, by the zeolite catalyst bed.Processing condition comprise that feed composition, temperature of reaction, flow velocity etc. can be according to required processing parameters, and for example the conversion of the selectivity of phenol production, nitrous oxide, the phenol concentration in the product gas, catalyst efficiency etc. are changed by those skilled in the art.For example, nitrous oxide can change to 1: 100 from 100: 1 to the molar ratio of benzene in feed gas mixtures.In embodiment preferred, it is useful making aromatic compound place what molar excess operate this technology at some.
In one aspect of the invention, the feature of the zeolite catalyst of crossing through hydrothermal treatment consists is to have stable performance in required catalyzed conversion, promptly 350 ℃ with the nitrous oxide Oxybenzene with the process of producing phenol in benzene transform and have only very low decline.The preferred catalyzer of warp of the present invention, for example ZSM-5 or ZSM-11 type zeolite catalyst, the benzene that is presented after operate continuously in 3 hours transform the ratio that initial benzene is transformed and are at least 40%.This ratio of preferred catalyzer is at least 50%.Following example explanation is about 70% to this ratio of some catalyzer.
Can identify by tolerance through the catalyzer of the present invention of hydrothermal treatment consists hydrothermal treatment consists.For example, of the present invention a kind of ferruginous, can have following feature through the acidifying zeolite catalyst: this catalyzer uses the gas be made up of 50mol% air and 50mol% water in hydrothermal treatment consists under 600 ℃ the temperature after two hours, when at 350 ℃, by 75mol% helium, in the air-flow that 5mol% benzene and 20mol% nitrous oxide are formed with the catalytic hydroxylation reaction of what benzene when forming phenol, the increase of the benzene conversion performance of catalyzer can not surpass 10%.
Advantage of the present invention can illustrate by following example, the enhancing of its mesolite performance can be by confirming with the nitrous oxide Oxybenzene.
Example 1
A kind of every mole of SiO
2In contain 4.3 * 10
-4Mole Fe
2O
3With 2.3 * 10
-2Mole Al
2o
3Basic what SiO
2Zeolite catalyst can be according at United States Patent (USP) 5,110, the Kharitonov disclosed method prepares in 995.After the organic formwork material was by burn off, zeolite made it change into the H type with acid treatment and calcined two hours in 550 ℃ of exsiccant airflows.For carrying out catalyst property test, can be to prepare a tubular reactor in 0.7 centimetre the silica tube by the zeolite of about 2 milliliters of 0.5-1.0 millimeters part being filled into internal diameter.The tubular reactor of having filled zeolite is heated to 350 ℃ and charging contains 5mol% benzene and the reaction gas mixtures of 20mol% nitrous oxide in helium.Regularly analyze with gas-chromatography from the product gas flow that reactor comes out.The gasometry data are used to calculate that benzene transforms (X) and to the selectivity (S) of phenol, the result is reported in the what table 1.As can be seen in reaction process catalyzer by the what coke laydown obvious inactivation.Beginning feed stream in the reactor was measured to determine initial benzene conversion X after 20 minutes
oBe 8.5% and initial selectivity S
oBe 92.5%.After the operate continuously 3 hours, it is 3.0% after measured that benzene transforms, and shows the decline of catalyst activity.Benzene transforms the ratio (X/X that initial benzene is transformed
o) be 3 5% to have characterized the catalyst stability in the operation.In any single job, all do not observe optionally and reduce.
Example 2
Basically prepare catalyzer by the method in the example 1, but carried out hydrothermal treatment consists in addition two hours, promptly exposing in the air that whats contain 50mol% water two hours at 500 ℃ under the condition that the air that contains 50mol% water exists.In the catalytic property report what table 1 of the catalyzer that hydrothermal treatment consists is crossed, it shows that initial benzene conversion greatly increases, and reaches 18.5%.
Implement 3-8
These examples have illustrated aspects more of the present invention, and wherein the temperature to hydrothermal treatment consists changes.Catalyst samples is to prepare by the method in the example 2 basically in these examples, and just the temperature of hydrothermal treatment consists is to carry out at 550-1000 ℃.Observed catalytic property reported in the what table 1, and it shows that optimized hydrothermal treatment consists temperature can be measured at an easy rate by common test, so that catalyzer has required initial or secular conversion characteristic.More surprisingly, when the benzene conversion increases along with hydrothermal treatment consists, for example increase to 37% by 8.5%, catalyst stability has also increased coefficient 2, i.e. X/X
oIncrease to 70% by 35%.At high-temperature very, it is worthless for example carrying out such processing near 1000 ℃, because it causes active reduction significantly.
Table 1
| Example number | Treatment temp, ℃ | Initial catalytic property | Activity in the air-flow after 3 hours | ||
| X o(％) | S o(％) | X(％) | X/X o(％) | ||
| 1 2 3 4 5 6 7 8 | Be untreated 500 550 600 650 700 750 1000 | 8.5 18.5 33.6 37.0 36.5 31.5 27.5 6.6 | 92.5 93.5 93.0 95.0 93.5 95.6 96.0 95.0 | 3.0 4.5 12.0 15.5 18.0 22.0 18.5 2.7 | 35 24 34 42 49 70 67 49 |
Example 9-12
These examples have illustrated aspects more of the present invention, wherein the water-content in the hydrothermal treatment consists gas are changed.Catalyst samples is that method by example 2 prepares basically in these examples, just hydrothermal treatment consists be with 600 ℃ processing gas carry out and wherein the content of water vapour be 2.5～100mol%.The catalysis data are reported in the what table 2 that it shows that the concentration that increases water vapour in the hydrothermal treatment consists gas can make catalyzer have the process efficiency that greatly increases.For example, when benzene transforms and to be increased to 38.5% by 8.6%, stability is increased and make selectivity that to a certain degree increase also be arranged.
Hydrothermal treatment consists promptly only contains 2.5mol% water vapour carrying out under the incinerating condition by similar what catalyzer in air in example 9.Example 9 and example 1 be comparison shows that low like this water concentration is not enough to the remarkable activation of what catalyzer.
Table 2
| Example number | CH 2O (mol％) | Initial catalytic property | Operate after 3 hours active | ||
| X o(％) | S o(％) | X(％) | X/X o(％) | ||
| 9 10 11 12 | 2.5 10 60 100 | 8.6 15.5 35.0 38.5 | 92.5 93.0 94.0 95.0 | 3.0 5.0 15.5 19.0 | 35 33 45 50 |
Example 14-16
These examples have illustrated that method of the present invention is to many beneficial effects of using the nitrous oxide hydroxylation of benzene with useful catalysts in the reaction of producing phenol.The zeolite of the component that has in table 3 to be reported is all evaluated to be transformed and the phenol selectivity to measure initial benzene.These zeolites carry out hydrothermal treatment consists by expose two hours in 500 ℃ the gas that contains 50mol% water then.Can see that such hydrothermal treatment consists promoted the operational characteristic of the altered zeolite component of this class greatly.
Table 3
| Example number | Chemical constitution | Catalytic property | |||
| Before the processing | After the processing | ||||
| X o(％) | S o(％) | X o(％) | S o(％) | ||
| 14 15 16 | 1.1×10 -2Al 2O 3SiO 2 3.4×10 -3Fe 2O 38.6×10 -3 Al 2O 3SiO 2 5.7×10 -3Fe 2O 3SiO 2 | 8.0 21.5 15.0 | 97.0 83.5 91.0 | 30.0 46.5 31.5 | 98.0 87.5 90.0 |
These example tables are understood essence of the present invention, but full content anything but, mean that hydro-thermal activatory top condition (temperature, time, water vapor concentration etc.) is to the dissimilar catalyzer of what and to want to use the reaction of this catalyzer can be inequality.Specifically, the high-level efficiency of activated catalyzer not only makes can implement this method under the condition of excessive nitrous oxide, and under the condition that excessive aromatics exists, for example also can implement this method under the condition of molar ratio up to 100: 1 of aromatics to nitrous oxide.In the advantage of implementing this method under the condition of excessive aromatic compound is to reach nitrous oxide conversion completely under this condition.This can cause significant work simplification, because there is no need to separate unreacted nitrous oxide in this case and it is turned back in the reaction.
Though described specific embodiment here, obviously also can carry out various changes and not depart from true spirit of the present invention and scope to what those skilled in the art.By this, plan to contain all these classes changes within inventive concept completely with following claim.
Claims (6)
1. one kind is used to strengthen with the ZSM-5 of the reaction of nitrous oxide Oxybenzene or the preparation method of ZSM-11 type zeolite catalyst, and described method is included in 350-950 ℃ and handles zeolite catalyst with the hydro-thermal gas that can strengthen catalytic capability (hydrothermal gas) that contains 3-100mol% water.
2. according to the process of claim 1 wherein that said catalyzer is a kind of acidifying iron content zeolite.
3. according to the method for claim 2, wherein said gas contains the water of 10mol% at least.
4. according to the method for claim 3, wherein said gas temperature is at least 500 ℃.
5. zeolite catalyst according to one of claim 1-4 preparation.
6. one kind prepares the method for phenol or derivatives thereof with catalysis process, comprises benzene or derivatives thereof and nitrous oxide are reacted in the presence of the zeolite catalyst of each preparation of claim 1-4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU9494013071A RU2074164C1 (en) | 1994-04-12 | 1994-04-12 | Method of producing phenol and derivatives thereof |
| RU94013071 | 1994-04-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1148819A CN1148819A (en) | 1997-04-30 |
| CN1102074C true CN1102074C (en) | 2003-02-26 |
Family
ID=20154684
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95193212A Expired - Fee Related CN1102074C (en) | 1994-04-12 | 1995-04-12 | Catalysts for production of phenol and its derivatives |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP3507500B2 (en) |
| KR (1) | KR100231372B1 (en) |
| CN (1) | CN1102074C (en) |
| AU (1) | AU694967B2 (en) |
| BR (1) | BR9507387A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747155B (en) * | 2008-12-08 | 2013-04-24 | 中国石油天然气股份有限公司 | Method for carrying out one step oxidation of benzene to synthetize phenol by using N2O as oxidizer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4429176A (en) * | 1982-02-08 | 1984-01-31 | Mobil Oil Corporation | Active zeolite catalysts of improved stability |
| EP0406050A2 (en) * | 1989-06-22 | 1991-01-02 | 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4117511A1 (en) * | 1991-05-29 | 1992-12-03 | Vaw Ver Aluminium Werke Ag | METHOD FOR MODIFYING A PURE-TYPE PURE-SYNTHETIZED ZEOLITE OF PURE-TYPE |
-
1995
- 1995-04-12 AU AU23767/95A patent/AU694967B2/en not_active Ceased
- 1995-04-12 KR KR1019960705722A patent/KR100231372B1/en not_active IP Right Cessation
- 1995-04-12 CN CN95193212A patent/CN1102074C/en not_active Expired - Fee Related
- 1995-04-12 BR BR9507387-6A patent/BR9507387A/en not_active IP Right Cessation
- 1995-04-12 JP JP52626695A patent/JP3507500B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4429176A (en) * | 1982-02-08 | 1984-01-31 | Mobil Oil Corporation | Active zeolite catalysts of improved stability |
| EP0406050A2 (en) * | 1989-06-22 | 1991-01-02 | 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 |
Non-Patent Citations (1)
| Title |
|---|
| MENDELEEV CONNUM.(1993)NO.1 1993-01-01 V.Zholobenko Preparation of Phenol over Dehydroxylated HZSM-5Zeolites * |
Also Published As
| Publication number | Publication date |
|---|---|
| AU694967B2 (en) | 1998-08-06 |
| CN1148819A (en) | 1997-04-30 |
| JP3507500B2 (en) | 2004-03-15 |
| KR100231372B1 (en) | 1999-11-15 |
| BR9507387A (en) | 2002-04-16 |
| JPH09511445A (en) | 1997-11-18 |
| MX9604787A (en) | 1998-05-31 |
| AU2376795A (en) | 1995-10-30 |
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