NL8201665A - Phenol cpds. prodn. by gas phase oxidn. of benzoic acid derivs. - using copper contg. catalyst with vanadium, silver, lithium or magnesium cpds. and cobalt co:catalyst - Google Patents
Phenol cpds. prodn. by gas phase oxidn. of benzoic acid derivs. - using copper contg. catalyst with vanadium, silver, lithium or magnesium cpds. and cobalt co:catalyst Download PDFInfo
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- NL8201665A NL8201665A NL8201665A NL8201665A NL8201665A NL 8201665 A NL8201665 A NL 8201665A NL 8201665 A NL8201665 A NL 8201665A NL 8201665 A NL8201665 A NL 8201665A NL 8201665 A NL8201665 A NL 8201665A
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- catalyst
- benzoic acid
- gas phase
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- copper
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000005711 Benzoic acid Substances 0.000 title claims abstract description 27
- 235000010233 benzoic acid Nutrition 0.000 title claims abstract description 27
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 23
- 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
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 6
- 239000010941 cobalt Substances 0.000 title claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 23
- 239000010949 copper Substances 0.000 title claims description 22
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 8
- 229910052709 silver Inorganic materials 0.000 title claims description 8
- 229910052744 lithium Inorganic materials 0.000 title claims description 7
- 229910052749 magnesium Inorganic materials 0.000 title claims description 7
- 239000011777 magnesium Substances 0.000 title claims description 7
- 239000004332 silver Substances 0.000 title claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title abstract description 9
- 238000000034 method Methods 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 26
- 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 10
- 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 description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 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
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-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
- 150000001869 cobalt compounds Chemical class 0.000 claims description 2
- 125000004436 sodium atom Chemical group 0.000 claims description 2
- 239000012876 carrier material Substances 0.000 claims 3
- 238000006555 catalytic reaction Methods 0.000 claims 1
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000002474 experimental method Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 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
- 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
- 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
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 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
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 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
- 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
- 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
-
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/89—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
- B01J23/8926—Copper and noble 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
- B01J23/89—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
-
- 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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Description
mm
Stamicarbon B.V*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 3383Antonius J.J.M. TEUNISSEN in Geleen 1 PN 3383
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 natriumverbindingea 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* 15 Een dergelijke werkwijze en katalysator zijn bekend uit deThe 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. Such a process and catalyst are nd 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* 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.European patent application 40452 * This patent application describes such a method and catalyst. The catalyst exhibits a reasonable conversion to the desired phenol, which is still subject to improvement. The object of the invention is to provide a catalyst which exhibits a greatly increased conversion to the desired phenol compared to the previously 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 natriumver-bindingen en/of magnesium en/of een of meer magnesiumverbindingen met een atoomverhouding tussen vanadium en koper van ten hoogste 1:2, 8201665 * j· Λ *<► 2 tussen zilver en koper ven 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 cobalt en/o£ een of meer cobaltverbindingen toepast als cokatalysator waarbij men een 5 atoomverhouding tussen cobalt en koper toepast van ten hoogste 1:10» en bij voorkeur een atoomverhouding tussen 1:1000 en 3:40·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, 8201665 * j · Λ * < ► 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 also cobalt and / o One or more cobalt compounds is used as a cocatalyst, wherein a 5 atomic ratio between cobalt and copper is used of at most 1:10 and preferably an atomic ratio between 1: 1000 and 3:40.
Het deze werkwijze verkrijgt men onder overigens gelijke omstandigheden een bijzonder sterke verhoging van de conversie naar het gewenste fenol ten opzichte van de conversie naar het gewenste 10 fenol welke men verkrijgt als men werkt volgens de werkwijze beschreven in bovengenoemde Europese octrooiaanvrage. Hen constateert dat deze conversie soms met meer dan 60 % van de waarde, welke bij het werken volgens de stand van de techniek wordt bereikt bij overigens dezelfde omstandigheden, wordt verhoogd door te werken volgens de 15 huidige uitvinding * . De katalysator volgens de uitvinding bestaat bij voorkeur uit een innig mengsel van CuO, V2O5 en/of Ag20 en U2O en/of Na^O en/of HjgO en cobalt oxide, in het bijzonder een innig mengsel van CuO, V2O5,Under otherwise identical conditions, this process produces 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. They find that this conversion is sometimes increased by more than 60% of the value achieved in prior art work under otherwise the same conditions, by operating in accordance with the present invention *. The catalyst according to the invention preferably consists of an intimate mixture of CuO, V2O5 and / or Ag20 and U2O and / or Na2O and / or HjgO and cobalt oxide, in particular an intimate mixture of CuO, V2O5,
Ag20, U.2O en cobaltoxide. Daarnaast bevat de katalysator bij voorkeur 20 Q-95 gew.-% dragermateriaal, meer in het bijzonder 20-80 gew.-% dra- germateriaal· Bij voorkeur wordt een siliciumbevattend dragermateriaal toegepast.Ag20, U.2O and cobalt oxide. In addition, the catalyst preferably contains 20 Q-95 wt.% Support material, more in particular 20-80 wt.% Support material. Preferably, a silicon-containing support material is used.
Een geschikte bereidingswijze voor de katalysator volgens de uitvinding is als volgt.A suitable preparation method for the catalyst according to the invention is as follows.
25 Het dragermateriaal wordt gesuspendeerd in gedestilleerd water. Vervolgens wordt bij nagenoeg kamertemperatuur, bijvoorbeeld 280-320 K, een oplossing van kopemitraat, een oplossing van ammonium-metavanadaat en/of een oplossing van zilvernitraat en een oplossing van cobaltdinitraat aan deze suspensie toegevoegd.The support material is suspended in distilled water. Subsequently, a solution of copper nitrate, a solution of ammonium metavanadate and / or a solution of silver nitrate and a solution of cobalt dinitrate are added to this suspension at substantially room temperature, for example 280-320 K.
30 Onder krachtig roeren worden de metalen als hydroxide of oxide neergeslagen door een ten minste equivalente hoeveelheid van een 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 35 gewassen. De filterkoek wordt gebroken, gedroogd en gedurende een bepaalde tijd, bijvoorbeeld 1-50 uur en bij voorkeur gedurende 10-25 8201665 3 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 afgezeefd. De gewenste katalysatordeeltjesgrootte is afhankelijk van 5 de soort en de grootte van de bepaalde reactor waarin de katalysator-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 3 hours at a temperature of, for example, 500-1000 K, and preferably of 500-750 K., for a certain time, for example, 1-50 hours and preferably for 10-25 8201665. Finally, the catalyst thus obtained, if necessary, comminuted by mechanical means and optionally sieved. 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 10 met 1-100 moldelen water, bijvoorbeeld in de vorm van stoom, en bij voorkeur 5-20 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 15 bij een druk van bij voorkeur 50-2000 kPa, waarbij hogere en lagere 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 bij-20 zonder 0,1-2 gew.-dln. gesubstitueerd of ongesubstitueerd benzoëzuur per gew.-deel katalysator per uur. Hogere en lagere katalysator-belastingen zijn ook toepasbaar, maar zijn om economische redenen minder aantrekkelijk.1 mol part of substituted or unsubstituted benzoic acid is added with 1-100 mold water, for example in the form of steam, and preferably 5-20 mold water, and 0.1-10 mold oxygen and preferably 0.3-3 mold 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 are less attractive for economic reasons.
De gasfaseoxidatie volgens de uitvinding kan in allerlei 25 reactoren geschieden. Zeer goed toepasbaar zijn vast-bed reactoren en vooral gefluidiseerd-bed reactoren. In een vast-bed reactor wordt bij voorkeur katalysatordeeltjes toegepast met een diameter tussen 1 en 10 mm. In een gefluidiseerd-bed reactor worden bij voorkeur katalysator-.deeltjes toegepast welke een drager bevatten met een hoog specifiek 30 oppervlak, bij voorkeur groter dan 100 m^/g, meer in het bijzonder groter dan 200 m^/g en welke deeltjes bij voorkeur een diameter hebben tussen 20 en 500 μια·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 support with a high specific surface area, preferably greater than 100 m / g, more in particular greater than 200 m / g, and which particles are preferably have a diameter between 20 and 500 μια ·
Een zeer geschikte wijze om de gasfase-oxidatie volgens de uitvinding in een gefluidiseerd-bed reactor uit te voeren is als 35 volgt.A very suitable way to carry out the gas phase oxidation according to the invention in a fluidized bed reactor is as follows.
8201665 48201665 4
De fluidisatie van de katalysatordeeltjes geschiedt door de toevoer van oxiderend gas en 3toom· Aldus ontstaat een gefluidiseerd bed met een hoogte h. Het te oxideren gesubstitueerd of ongesubstitueerd benzoëzuur wordt opeen plaats apart van de oxiderend 5 gastoevoer in gasvorm ingebracht in het gefluidiseerde bed op een hoogte bij voorkeur tussen k en % h.The fluidization of the catalyst particles is effected by the supply of oxidizing gas and steam. Thus a fluidized bed with a height h is formed. The substituted or unsubstituted benzoic acid to be oxidized is introduced into the fluidized bed at a height preferably between k and% h, separately from the oxidizing gas feed in gaseous form.
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 10 componenten, bij voorbeeld door destillatie* Ook kan men in plaats van gewone condensatie van de hete reactiegassen gefractioneerde condensatie 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, distillative separation may become unnecessary afterwards.
De uitvinding omvat tevens katalysatoren voor de gasfase oxi-15 datie van gesubstitueerd of ongesubstitueerd benzoëzuur. Deze katalysatoren bevatten per 1000 koperatomen 4-100 vanadiumatomen en/of 2-250 zilveratomen, 5-2000 lithiumatomen en/of 5-2000 natriumatomen en/of 5-2000 magnesiumatomen en 1-75 cobaltatomen.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 1-75 cobalt atoms.
De uitvinding wordt verder toegelicht aan de hand van de - - - -20 volgende niet beperkende voorbeelden en vergelijkende experimenten·The invention is further illustrated by the following - - - -20 following non-limiting examples and comparative experiments
Voorbeelden en vergelijkende experimenten _ _________________________Examples and comparative experiments _ _________________________
In onderstaande tabel worden voorbeelden 1 en 2 en het vergelijkende experiment A weergegeven· De voorbeelden en het vergelijkende experiment zijn uitgevoerd in een gefluidiseerd-bed reactor, 25 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 Comparative Experiment were conducted in a fluidized bed reactor, as described above, into which the benzoic acid was introduced at approximately atmospheric pressure.
De belasting tijdens de experimenten bedroeg telkens ca· 0,4 g benzoëzuur per g katalysator per uur, de molverhouding H£0 : benzoëzuur tussen ca* 10:1 en 20:1 en de molverhouding O2:benzoëzuur 30 ca. 0,5* De benzoëzuuroxidatie werd telkens uitgevoerd bij ca. 575 K.The load during the experiments was in each case about 0.4 g of benzoic acid per g of catalyst per hour, the molar ratio of H 0 0: benzoic acid between about 10: 1 and 20: 1 and the molar ratio of O2: benzoic acid about 0.5 *. The benzoic acid oxidation was always 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.
8201665 58201665 5
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 silieiumbevattend dragermateriaal met een specifiek 5 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
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 10 * IV gew.-% Ag in katalysator V gew.-% Li in katalysator VI gew.-Z Co in katalysator VII tijdsduur van de proef tot de meting in uren VIII conversie tot fenol in mol.-%The table below shows the following: __ column I number of example or comparative experiment II wt.% Cu in catalyst III wt.% V in catalyst 10 * IV wt.% Ag in catalyst V wt.% Li in catalyst VI wt-Z Co in catalyst VII time from test to measurement in hours VIII conversion to phenol in mole%
15 IX conversie tot benzeen in mol.-ZIX conversion to benzene in mol.-Z
X conversie tot difenylether in mol.-ZX conversion to diphenyl ether in mol.-Z
Het restant van het reactiegas bestond uit verbran-dingsprodukten en onomgezet benzoëzuur.The remainder of the reaction gas consisted of combustion products and unconverted benzoic acid.
1 II III IV V VI VII VIII IX X1 II III IV V VI VII VIII IX X
20 1 32,5 1,4 0,5 1,5 0,5 1 52,6 5,4 1,6 24 47,4 ____L»5________ 96 47,0 7,1 1,7 120 46,9 - 7,3 1,6 2 32,1 1,4 0,5 1,5 1,4 1 52,8 3,7 1,9 25 24 50,2 6,2 2,0 96 48,7 6,8 2,2 120 48,0 7,2 2,3 A 32,7 1,5 0,5 1,5 1 32,6 2,1 0,8 24 30,4 2,0 0,6 30 96 30,1 2,3 Q,6 120 29,8 2,5 0,7 820166520 1 32.5 1.4 0.5 1.5 0.5 1 52.6 5.4 1.6 24 47.4 ____ L »5 ________ 96 47.0 7.1 1.7 120 46.9 - 7 .3 1.6 2 32.1 1.4 0.5 1.5 1.4 1 52.8 3.7 1.9 25 24 50.2 6.2 2.0 96 48.7 6.8 2 .2 120 48.0 7.2 2.3 A 32.7 1.5 0.5 1.5 1 32.6 2.1 0.8 24 30.4 2.0 0.6 30 96 30.1 2.3 Q, 6 120 29.8 2.5 0.7 8201665
Claims (28)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL8201665A NL8201665A (en) | 1982-04-22 | 1982-04-22 | Phenol cpds. prodn. by gas phase oxidn. of benzoic acid derivs. - using copper contg. catalyst with vanadium, silver, lithium or magnesium cpds. and cobalt co:catalyst |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL8201665A NL8201665A (en) | 1982-04-22 | 1982-04-22 | Phenol cpds. prodn. by gas phase oxidn. of benzoic acid derivs. - using copper contg. catalyst with vanadium, silver, lithium or magnesium cpds. and cobalt co:catalyst |
| NL8201665 | 1982-04-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NL8201665A true NL8201665A (en) | 1983-11-16 |
Family
ID=19839631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NL8201665A NL8201665A (en) | 1982-04-22 | 1982-04-22 | Phenol cpds. prodn. by gas phase oxidn. of benzoic acid derivs. - using copper contg. catalyst with vanadium, silver, lithium or magnesium cpds. and cobalt co:catalyst |
Country Status (1)
| Country | Link |
|---|---|
| NL (1) | NL8201665A (en) |
-
1982
- 1982-04-22 NL NL8201665A patent/NL8201665A/en not_active Application Discontinuation
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