NL8201666A - Phenol(s) prodn. by gas phase oxidn. of benzoic acid derivs. - using copper contg. catalyst with vanadium, silver, lithium or magnesium cpds. and rare earth co:catalyst - Google Patents
Phenol(s) prodn. by gas phase oxidn. of benzoic acid derivs. - using copper contg. catalyst with vanadium, silver, lithium or magnesium cpds. and rare earth co:catalyst Download PDFInfo
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- NL8201666A NL8201666A NL8201666A NL8201666A NL8201666A NL 8201666 A NL8201666 A NL 8201666A NL 8201666 A NL8201666 A NL 8201666A NL 8201666 A NL8201666 A NL 8201666A NL 8201666 A NL8201666 A NL 8201666A
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- catalyst
- process according
- gas phase
- benzoic acid
- copper
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000010949 copper Substances 0.000 title claims abstract description 31
- 239000005711 Benzoic acid Substances 0.000 title claims abstract description 27
- 235000010233 benzoic acid Nutrition 0.000 title claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 25
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 18
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 18
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000011777 magnesium Substances 0.000 title claims abstract description 10
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 8
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 8
- 239000004332 silver Substances 0.000 title claims abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims description 8
- 229910052744 lithium Inorganic materials 0.000 title claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000011734 sodium Substances 0.000 claims abstract description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 7
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 27
- 230000003647 oxidation Effects 0.000 claims description 21
- 238000007254 oxidation reaction Methods 0.000 claims description 21
- 150000001559 benzoic acids Chemical class 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 150000002989 phenols Chemical class 0.000 claims description 5
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000005749 Copper compound Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001880 copper compounds Chemical class 0.000 claims description 3
- 239000011872 intimate mixture Substances 0.000 claims description 3
- 150000002681 magnesium compounds Chemical class 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229940100890 silver compound Drugs 0.000 claims description 3
- 150000003379 silver compounds Chemical class 0.000 claims description 3
- 150000003388 sodium compounds Chemical class 0.000 claims description 3
- 150000003682 vanadium compounds Chemical class 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 2
- 150000002909 rare earth metal compounds Chemical class 0.000 claims description 2
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims description 2
- 125000004436 sodium atom Chemical group 0.000 claims description 2
- 239000012876 carrier material Substances 0.000 claims 4
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 238000002474 experimental method Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 2
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000007700 distillative separation Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/898—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with vanadium, tantalum, niobium or polonium
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- 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
- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
- C07C37/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by replacing a carboxyl or aldehyde group by a hydroxy group
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- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Description
C' *· > 4 . Stamicarbon B.V.C '*> 4. Stamicarbon B.V.
Uitvinders: Paul C. van GEEM te SpaubeekInventors: Paul C. van GEEM in Spaubeek
Antonius J.J.M. TEUNISSEN te Geleen 1 PN 3382Antonius J.J.M. TEUNISSEN in Geleen 1 PN 3382
WERKWIJZE VOOR DE BEREIDING VAN GESUBSTITUEERD OF ONGESUBSTITUEERD FENOL EN KATALYSATOREN DAARVOORMETHOD FOR PREPARING SUBSTITUTED OR UNSUBSTITUTED PHENOL AND CATALYSTS THEREFOR
De uitvinding betreft een werkwijze voor de bereiding van een gesubstitueerd of ongesubstitueerd fenol door oxidatie van het overeenkomstige gesubstitueerde of ongesubstitueerde benzoëzuur in de gasfase in aanwezigheid van een katalysator bestaande uit koper en/of 5 een of meer koperverbindingen, vanadium en/of een of meer vanadiumver-bindingen en/of zilver en/of een of meer zilververbindingen en lithium en/of een of meer lithiumverbindingen en/of natrium en/of een of meer natriumverbindingen en/of magnesium en/of een of meer magnesiumverbin-dingen met een atoomverhouding tussen vanadium en koper van ten 10 hoogste 1:2, tussen zilver en koper van ten hoogste 1:2, tussen lithium en koper van ten hoogste 5:1 tussen natrium en koper van ten hoogste 5:1, en tussen magnesium en koper van ten hoogste 5:1 en katalysatoren daarvoor* Met name betreft de uitvinding de gasfase-oxidatie van ongesubstitueerd benzoëzuur tot ongesubstitueerd fenol.The invention relates to a process for the preparation of a substituted or unsubstituted phenol by oxidation of the corresponding substituted or unsubstituted benzoic acid in the gas phase in the presence of a catalyst consisting of copper and / or one or more copper compounds, vanadium and / or one or more vanadium compounds and / or silver and / or one or more silver compounds and lithium and / or one or more lithium compounds and / or sodium and / or one or more sodium compounds and / or magnesium and / or one or more magnesium compounds with an atomic ratio between vanadium and copper of at most 1: 2, between silver and copper of at most 1: 2, between lithium and copper of at most 5: 1 between sodium and copper of at most 5: 1, and between magnesium and copper of at most 5: 1 and catalysts therefor * In particular, the invention relates to the gas phase oxidation of unsubstituted benzoic acid to unsubstituted phenol.
15 Een dergelijke werkwijze en katalysator zijn bekend uit deSuch a process and catalyst are known from the
Europese octrooiaanvrage 40452* Deze octrooiaanvrage beschrijft een dergelijke werkwijze en katalysator. De katalysator vertoont een redelijke conversie naar het gewenste fenol, welke wel nog voor verbetering vatbaar is.European patent application 40452 * This patent application describes such a method and catalyst. The catalyst shows a reasonable conversion to the desired phenol, which can still be improved.
20 Doel van de uitvinding is een katalysator te verschaffen die een sterk verhoogde conversie naar het gewenste fenol vertoont ten opzichte van de reeds bekende katalysator*The object of the invention is to provide a catalyst which shows a strongly increased conversion to the desired phenol compared to the already known catalyst *
Een werkwijze volgens de uitvinding wordt gekenmerkt, doordat men naast de katalysator bestaande uit koper en/of een of meer koper-25 verbindingen, vanadium en/of een of meer vanadiumverbindingen en/of zilver en/of een of meer zilververbindingen en lithium en/of een of meer lithiumverbindingen en/of natrium en/of een of meer natriumverbindingen en/of magnesium en/of een of meer magnesiumverbindingen met een atoomverhouding tussen vanadium en koper van ten hoogste 1:2, 8201666 ^ > Λ» - 2 tussen 2ilver en koper van ten hoogste 1:2, tussen lithium en koper van ten hoogste 5:1, tussen natrium en koper van ten hoogste 5:1 en tussen magnesium en koper van ten hoogste 5:1 tevens een of meer zeldzame aardmetalen en/of een of meer zeldzame aardmetaalverbindingen 5 toepast als cokatalysator waarbij men een atoomverhouding tussen zeldzaam aardmetaal en koper toepast van ten hoogste 1:10, en hij voorkeur een atoomverhouding tussen 1:1000 en 1:20· Bij voorkeur past men als zeldzaam aardmetaal praseodymium toe.A process according to the invention is characterized in that in addition to the catalyst consisting of copper and / or one or more copper compounds, vanadium and / or one or more vanadium compounds and / or silver and / or one or more silver compounds and lithium and / or one or more lithium compounds and / or sodium and / or one or more sodium compounds and / or magnesium and / or one or more magnesium compounds with an atomic ratio between vanadium and copper of at most 1: 2, 8201666 ^> Λ »- 2 between 2ilver and copper of not more than 1: 2, between lithium and copper of not more than 5: 1, between sodium and copper of not more than 5: 1 and between magnesium and copper of not more than 5: 1, also one or more rare earth metals and / or one or more rare earth metal compounds 5 is used as a cocatalyst, with an atomic ratio between rare earth metal and copper of at most 1:10, and preferably an atomic ratio between 1: 1000 and 1:20. Preferably, a rare earth metal prase is used odymium.
Met deze werkwijze verkrijgt men onder overigens gelijke 10 omstandigheden een bijzonder sterke verhoging van de conversie naar het gewenste fenol ten opzichte van de conversie naar het gewenste fenol welke men verkrijgt als men werkt volgens de werkwijze beschreven in bovengenoemde Europese octrooiaanvrage· Men constateert dat deze conversie soms met meer dan 60 % van de waarde, welke bij het 15 werken volgens de stand van de techniek wordt bereikt bij overigens dezelfde omstandigheden, wordt verhoogd door te werken volgens de huidige uitvinding·Under otherwise equal conditions, this method provides a particularly strong increase in the conversion to the desired phenol relative to the conversion to the desired phenol, which is obtained when one works according to the method described in the above-mentioned European patent application. It has been found that this conversion sometimes increased by more than 60% of the value achieved in the prior art under otherwise the same conditions, is increased by operating in accordance with the present invention ·
Opgemerkt wordt dat in de reeds genoemde Europese octrooiaanvrage 40452 de zeldzame aardmetalen worden genoemd in een 20 opsomming van een groot aantal elementen welke eventueel als cokatalysator voor de daar beschreven katalysatoren zouden kunnen dienen* Uit deze aanvrage is echter in het geheel niet af te leiden dat juist het volgens de huidige uitvinding toepassen van zeldzame aardmetalen, en met name van praseodymium, in de specifieke hoeveelheid volgens de 25 huidige uitvinding de bijzonder sterke verbetering van de conversie naar het gewenste fenol te weeg brengt.It is noted that in the aforementioned European patent application 40452 the rare earth metals are mentioned in a list of a large number of elements which could possibly serve as a cocatalyst for the catalysts described therein. However, it is not at all inferred from this application that it is precisely the use according to the present invention of rare earth metals, and in particular praseodymium, in the specific amount according to the present invention which produces the particularly strong improvement of the conversion to the desired phenol.
De katalysator volgens de uitvinding bestaat bij voorkeur uit een innig mengsel van CuO, V2O5 en/of AgjO en Li20 en/of Na20 en/of MgO en praseodymiumoxide, in het bijzonder een innig mengsel van CuO, 30 V2O5, Ag20, Li2Ö en praseodymiumoxide. Daarnaast bevat de katalysator bij voorkeur 0-95 gew.-% dragermateriaal, meer in het bijzonder 20-80 gew.-% dragermateriaal. Bij voorkeur wordt een siliciumbevattend dragermateriaal toegepast.The catalyst according to the invention preferably consists of an intimate mixture of CuO, V2O5 and / or AgjO and Li20 and / or Na20 and / or MgO and praseodymium oxide, in particular an intimate mixture of CuO, V2O5, Ag20, Li2O and praseodymium oxide . In addition, the catalyst preferably contains 0-95 wt% support material, more in particular 20-80 wt% support material. A silicon-containing support material is preferably used.
Een geschikte bereidingswijze voor de katalysator volgens de 35 uitvinding is als volgt.A suitable preparation method for the catalyst of the invention is as follows.
8201666 !ï ' * > 38201666! Ï '*> 3
Het dragenaateriaal wordt gesuspendeerd in gedestilleerd water. Vervolgens wordt bij nagenoeg kamertemperatuur, bijvoorbeeld 280-320 K, een oplossing van kopernitraat, een oplossing van ammonium-metavanadaat en/of een oplossing van zilvemitraat en een of meer 5 oplossingen van een of meer zeldzaam aardmetaalbevattende verbindingen, bij voorkeur een oplossing van praseodymiumtrinitraat, aan deze suspensie toegevoegd.The support material is suspended in distilled water. Then, at near room temperature, for example 280-320 K, a solution of copper nitrate, a solution of ammonium metavanadate and / or a solution of silver nitrate and one or more solutions of one or more rare earth metal-containing compounds, preferably a solution of praseodymium trinitrate added to this suspension.
Onder krachtig roeren worden de metalen als hydroxide of oxide neergeslagen door een ten minste equivalente hoeveelheid van een 10 oplossing van lithiumhydroxide en/of natriumhydroxide en/of magne-siumhydroxide toe te druppelen. Vervolgens wordt de suspensie gefiltreerd en de filterkoek tweemaal met gedestilleerd water gewassen. De filterkoek wordt gebroken, gedroogd en gedurende een bepaalde tijd, bijvoorbeeld 1-50 uur en bij voorkeur gedurende 10-25 15 uur gecalcineerd bij een temperatuur van bijvoorbeeld 500-1000 K en bij voorkeur van 500-750 K. Tenslotte wordt de aldus verkregen katalysator indien nodig met mechanische middelen verkleind en eventueel af gezeefd. De gewenste katalysatordeeltjesgrootte is afhankelijk van de soort en de grootte van de bepaalde reactor waarin de katalysator-20 deeltjes worden toegepast.With vigorous stirring, the metals are precipitated as hydroxide or oxide by dripping an at least equivalent amount of a solution of lithium hydroxide and / or sodium hydroxide and / or magnesium hydroxide. The suspension is then filtered and the filter cake washed twice with distilled water. The filter cake is broken, dried and calcined for a specified period of time, for example 1-50 hours and preferably for 10-25 hours at a temperature of, for example, 500-1000 K and preferably of 500-750 K. Finally, the thus obtained If necessary, the catalyst is reduced by mechanical means and sieved if necessary. The desired catalyst particle size depends on the type and size of the particular reactor in which the catalyst particles are used.
De werkwijze volgens de uitvinding wordt als volgt uitgevoerd .The method according to the invention is carried out as follows.
1 Moldeel gesubsitueerd of ongesubstitueerd benzoëzuur wordt met 1-100 moldelen water, bijvoorbeeld in de vorm van stoom, en bij 25 voorkeur 5-30 moldelen water, en 0,1-10 moldelen zuurstof en bij voorkeur 0,3-3 moldelen zuurstof, bijvoorbeeld in de vorm van lucht in de gasfase in contact gebracht met een katalysator volgens de uitvinding bij een temperatuur van 450-700 K, bij voorkeur 500-650 K, en bij een druk van bij voorkeur 50-2000 kPa, waarbij hogere en lagere 30 drukken niet uitgesloten zijn zolang de gasfase in het reac- tiemedium gehandhaafd blijft. Bij voorkeur wordt een katalysator-belasting van 0,05-5 gew.-dln. gesubsitueerd of ongesubstitueerd benzoëzuur per gew.-deel katalysator per uur toegepast, in het bijzonder 0,1-2 gew.-dln. gesubstitueerd of ongesubstitueerd benzoëzuur 35 per gew.-deel katalysator per uur. Hogere en lagere katalysator-belastingen zijn ook toepasbaar, maar zijn om economische redenen 8201666 * «' ;» minder aantrekkelijk.1 mole portion of substituted or unsubstituted benzoic acid is mixed with 1-100 moles of water, for example in the form of steam, and preferably 5-30 moles of water, and 0.1-10 moles of oxygen, and preferably 0.3-3 moles of oxygen, for example in the form of air in the gas phase contacted with a catalyst according to the invention at a temperature of 450-700 K, preferably 500-650 K, and at a pressure of preferably 50-2000 kPa, with higher and lower Pressures are not excluded as long as the gas phase is maintained in the reaction medium. Preferably, a catalyst load of 0.05-5 parts by weight is used. substituted or unsubstituted benzoic acid per part by weight of catalyst per hour used, in particular 0.1-2 parts by weight. substituted or unsubstituted benzoic acid per part by weight of catalyst per hour. Higher and lower catalyst loads are also applicable, but for economic reasons are 8201666 * «';» less attractive.
De gasfaseoxidatie volgens de uitvinding kan in allerlei reactoren geschieden. Zeer goed toepasbaar zijn vast-bed reactoren en vooral gefluidiseerd-bed reactoren. In een vast-bed reactor wordt bij 5 voorkeur katalysatordeeltjes toegepast met een diameter tussen 1 en 10 mm. In een gefluidiseerd-bed reactor worden bij voorkeur katalysatordeeltjes toegepast welke een drager bevatten met een hoog specifiek oppervlak, bij voorkeur groter dan 100 m2/g, meer in het bijzonder groter dan 200 m2/g en welke deeltjes bij voorkeur een diameter hebben 10 tussen 20 en 500 pm.The gas phase oxidation according to the invention can take place in all kinds of reactors. Fixed bed reactors and especially fluidized bed reactors are very suitable for use. In a fixed bed reactor, catalyst particles with a diameter between 1 and 10 mm are preferably used. In a fluidized bed reactor, catalyst particles are preferably used which contain a carrier with a high specific surface area, preferably larger than 100 m2 / g, more in particular larger than 200 m2 / g, and which particles preferably have a diameter between 20 and 500 pm.
Een zeer geschikte wijze om de gasfase-oxidatie volgens de uitvinding in een gefluidiseerd-bed reactor uit te voeren is als volgt.A very suitable way to carry out the gas phase oxidation according to the invention in a fluidized bed reactor is as follows.
De fluidisatie van de katalysatordeeltjes geschiedt door de 15 toevoer van oxiderend gas en stoom. Aldus ontstaat een gefluidiseerd bed met een hoogte h. Het te oxideren gesubstitueerd of ongesubstitueerd benzoëzuur wordt op een plaats apart van de oxiderend gastoevoer in gasvorm ingebracht in het gefluidiseerde bed op een hoogte bij voorkeur tussen ^ en | h.The fluidization of the catalyst particles is effected by the supply of oxidizing gas and steam. This results in a fluidized bed with a height h. The substituted or unsubstituted benzoic acid to be oxidized is introduced into the fluidized bed at a height preferably between 1 and 2 in a location separate from the oxidizing gas supply in gaseous form. h.
20 Het tijdens de gasfaseoxidatie ontstane reactiemengsel kan worden opgevangen en gecondenseerd. Het zo ontstane vloeibare reactiemengsel kan dan op bekende wijze gescheiden worden in de diverse componenten, bij voorbeeld door destillatie. Ook kan men in plaats van gewone condensatie van de hete reactiegassen gefractioneerde conden-25 satie toepassen. Zodoende kan een destillatieve scheiding naderhand overbodig worden.The reaction mixture formed during the gas phase oxidation can be collected and condensed. The resulting liquid reaction mixture can then be separated in known manner into the various components, for example by distillation. Fractional condensation can also be used instead of ordinary condensation of the hot reaction gases. Thus, a distillative separation may subsequently become unnecessary.
De uitvinding omvat tevens katalysatoren voor de gasfase oxidatie van gesubstitueerd of ongesubstitueerd benzoëzuur. Deze katalysatoren bevatten per 1000 koperatomen 4-100 vanadiumatomen en/of 2-250 30 zilveratomen, 5-2000 lithiumatomen en/of 5-2000 natriumatomen en/of 5-2000 magnesiumatomen en 1-50 atomen van een of meer zeldzame aardmetalen, bij voorkeur van praseodymium.The invention also includes catalysts for the gas phase oxidation of substituted or unsubstituted benzoic acid. These catalysts contain per 1000 copper atoms 4-100 vanadium atoms and / or 2-250 silver atoms, 5-2000 lithium atoms and / or 5-2000 sodium atoms and / or 5-2000 magnesium atoms and 1-50 atoms of one or more rare earth metals, preference of praseodymium.
De uitvinding wordt verder toegelicht aan de hand van de volgende niet beperkende voorbeelden en vergelijkende experimenten.The invention is further illustrated by the following non-limiting examples and comparative experiments.
8201666 58201666 5
Voorbeelden en vergelijkende experimentenExamples and comparative experiments
In onderstaande tabel worden voorbeelden 1 en 2 en het vergelijkende experiment A weergegeven. De voorbeelden en het vergelij-' kende experiment zijn uitgevoerd in een gefluidiseerd-bed reactor, 5 als boven beschreven, waarin het benzoëzuur op ca. \ h ingevoerd werd bij nagenoeg atmosferische druk.The table below shows Examples 1 and 2 and Comparative Experiment A. The examples and the comparative experiment were conducted in a fluidized bed reactor, as described above, into which the benzoic acid was introduced at about 1 hr at substantially atmospheric pressure.
De belasting tijdens de experimenten bedroeg telkens ca.The load during the experiments was always approx.
0,4 g benzoëzuur per g katalysator per uur, de molverhouding H2O : benzoëzuur tussen ca. 10:1 en 20:1 en de molverhouding 02:benzoëzuur 10 ca. 0,5· De benzoëzuuroxidatie werd telkens uitgevoerd bij ca. 575 K.0.4 g of benzoic acid per g of catalyst per hour, the molar ratio of H2O: benzoic acid between about 10: 1 and 20: 1 and the molar ratio of 02: benzoic acid 10 about 0.5 · The benzoic acid oxidation was carried out at about 575 K.
Na 1 uur, 24 uur, 96 uur en 120 uur werden monsters van de vrijkomende reactorgassen gekoeld, gewassen met dimethylformamide en geanalyseerd. De resultaten van deze analyses zijn in de tabel weergegeven.After 1 hour, 24 hours, 96 hours, and 120 hours, samples of the released reactor gases were cooled, washed with dimethylformamide, and analyzed. The results of these analyzes are shown in the table.
15 De bij de gasfaseoxidatie gebruikte katalysator was bereid als bovenbeschreven. Er werd bij deze bereiding een calcineertijd van 16 uur in acht genomen. Naast de metaaloxides bestond de katalysator uit Aerosil, een siliciumbevattend dragermateriaal met een specifiek oppervlak groter dan 200 m^/g.The catalyst used in the gas phase oxidation was prepared as described above. A calcination time of 16 hours was observed in this preparation. In addition to the metal oxides, the catalyst consisted of Aerosil, a silicon-containing support material with a specific surface area greater than 200 m 2 / g.
20 De onderstaande tabel geeft het volgende weer: kolom I nummer van voorbeeld of vergelijkend experiment II gew.-% Cu in katalysator III gew.-£ V in katalysator IV gew.-% Ag in katalysator 25 V gew.-% Li in katalysator VI gew.-% Pr in katalysator VII gew.-Z Nd in katalysator VIII tijdsduur van de proef tot de meting in urenThe table below shows the following: column I number of example or comparative experiment II wt.% Cu in catalyst III wt.% V in catalyst IV wt.% Ag in catalyst 25 V wt.% Li in catalyst VI wt.% Pr in catalyst VII wt. Z Nd in catalyst VIII from test run to measurement in hours
IX conversie tot fenol in mol.-ZIX conversion to phenol in mol.-Z
30 X conversie tot benzeen in mol.-% XI conversie tot difenylether in mol.-%30 X conversion to benzene in mol.% XI conversion to diphenyl ether in mol.%
Het restant van het reactiegas bestond uit verbran-dingsprodukten en onomgezet benzoëzuur* 8201666 6 i II in iv v Vi vu viri ix x xi 1 32,1 1,4 0,5 1,5 1,4 1 44,2 3,3 1,3 24 51,4 4,8 1,7 96 46,3 4,3 1,4 5- 120 48,2 4,4 1,5 2 32,2 1,4 0,5 1,5 1,3 1 43,0 3,1 1,5 24 38,8 2,5 1,0 96 39,1 2,5 1,2 120 37,5 2,6 1,4 .The remainder of the reaction gas consisted of combustion products and unconverted benzoic acid * 8201666 6 i II in iv v Vi vu viri ix x xi 1 32.1 1.4 0.5 1.5 1.4 1 44.2 3.3 1.3 24 51.4 4.8 1.7 96 46.3 4.3 1.4 5- 120 48.2 4.4 1.5 2 32.2 1.4 0.5 1.5 1, 3 1 43.0 3.1 1.5 24 38.8 2.5 1.0 96 39.1 2.5 1.2 120 37.5 2.6 1.4.
10 A 32,7 1,5 0,5 1,5 1 32,6 2,1 0,8 24 30,4 2,0 0,6 96 30,1 2,3 0,6 120 29,8 2,5 0,7 820166610 A 32.7 1.5 0.5 1.5 1 32.6 2.1 0.8 24 30.4 2.0 0.6 96 30.1 2.3 0.6 120 29.8 2, 5 0.7 8201666
Claims (30)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL8201666A NL8201666A (en) | 1982-04-22 | 1982-04-22 | Phenol(s) prodn. by gas phase oxidn. of benzoic acid derivs. - using copper contg. catalyst with vanadium, silver, lithium or magnesium cpds. and rare earth co:catalyst |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL8201666A NL8201666A (en) | 1982-04-22 | 1982-04-22 | Phenol(s) prodn. by gas phase oxidn. of benzoic acid derivs. - using copper contg. catalyst with vanadium, silver, lithium or magnesium cpds. and rare earth co:catalyst |
| NL8201666 | 1982-04-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NL8201666A true NL8201666A (en) | 1983-11-16 |
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ID=19839632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NL8201666A NL8201666A (en) | 1982-04-22 | 1982-04-22 | Phenol(s) prodn. by gas phase oxidn. of benzoic acid derivs. - using copper contg. catalyst with vanadium, silver, lithium or magnesium cpds. and rare earth co:catalyst |
Country Status (1)
| Country | Link |
|---|---|
| NL (1) | NL8201666A (en) |
-
1982
- 1982-04-22 NL NL8201666A patent/NL8201666A/en not_active Application Discontinuation
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