GB2518274A - Catalyst for aldehyde production - Google Patents
Catalyst for aldehyde production Download PDFInfo
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- GB2518274A GB2518274A GB1412144.6A GB201412144A GB2518274A GB 2518274 A GB2518274 A GB 2518274A GB 201412144 A GB201412144 A GB 201412144A GB 2518274 A GB2518274 A GB 2518274A
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- alkanol
- methanol
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- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 96
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 53
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 29
- 239000011574 phosphorus Substances 0.000 claims abstract description 29
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000011949 solid catalyst Substances 0.000 claims abstract description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical group CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 20
- 229910052750 molybdenum Inorganic materials 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052816 inorganic phosphate Inorganic materials 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- AOJJSUZBOXZQNB-VTZDEGQISA-N 4'-epidoxorubicin Chemical compound O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@@H](O)[C@H](C)O1 AOJJSUZBOXZQNB-VTZDEGQISA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000000975 co-precipitation Methods 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 54
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 14
- 239000011733 molybdenum Substances 0.000 description 14
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 230000032683 aging Effects 0.000 description 5
- 239000013529 heat transfer fluid Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- -1 phosphorus compound Chemical class 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920004482 WACKER® Polymers 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 3
- 229910017354 Fe2(MoO4)3 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002751 molybdenum Chemical class 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/881—Molybdenum and iron
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/28—Phosphorising
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A catalyst for aldehyde production through selective oxidation of alkanol with oxygen comprises: iron molybdate and molybdenum trioxide wherein the Mo/Fe molar ratio is 1.5-5 and the specific surface area is 1-20 m²/g, the catalyst further comprising phosphorus. The alkanol maybe methanol or ethanol. The catalyst may contain 50-50,000 ppm of phosphorus. A process for producing the catalyst comprises impregnating a solid catalyst comprising iron molybdate and molybdenum trioxide with a solution of a phosphorus containing compound. The catalyst may be calcined after the treating step, or the solid catalyst calcined before the treating step. The solid catalyst may be prepared by a co-precipitation method.
Description
Catalyst for Aldehyde Production The present invention refers to a catalyst for aldehyde production, in particular formaldehyde or acetaldehyde production, through selective oxidation of alkanol, especially methanol or ethanol, with oxygen, said catalyst comprising iron molybdate arid molybdenum thoxide and being doped with phosphorus. In a further aspect, the present invention refers to a process for producing said catalyst and to the use of said catalyst for selective oxidation of alkanol, preferably methanol or ethanol, with oxygen to aldehyde, preferably formaldehyde or acetal dehyde.
The dominant production method for acetaldehyde today is the Wacker process, which catalyzes the oxidation of ethylene to acetaldehyde. The catalyst is a two-component system consisting of palladium chloride and copper chloride. Prior to the Wacker process acetaldehyde was produced by hydration of acetylene. Converting ethanol into acetaldehyde by catalyzed oxidation is a potential alternative to the Wacker process today due to the increasing availability of ethanol.
Commercial production of formaldehyde from methanol and oxygen is today performed either in the silver-or the metal oxide catalyzed process operated at methanol-rich and methanol-lean conditions, respectively. Historically, due to lower investment costs the silver process has been preferred over the oxide process but as a result of process improvements and increasing methanol prices the more selective oxide process has won market shares and is today the most common choice for new capacities.
In the oxide process, formaldehyde is produced in multi-tube reactors. Typically, a reactor consists of 10-20 000 tubes filled up with ring-shaped catalysts and cooled by oil as heat transfer fluid (HTF). Since the reaction is highly exothermic (All = -156 kJ/mol), isothermal conditions are difficult to obtain and consequently a hotspot is formed at the reaction zone, In order to limit the hot spot temperature, at the first part of the reactor the catalyst can be diluted with inert rings.
The catalyst used in the oxide process is a mixture of iron molybdate Fe2(Mo04)3 and molybdenum trioxide MoO3 with a Mo:Fe atomic ratio between 2 and 3. Inmost aspects the catalytic performance is satisfactory; the plant yield is high (88-93%) and neither molybdenum nor iron are toxic, which is favorable considering both environmental and human health aspects.
However, in methanol oxidation the catalyst suffers from deactivation due to volatilization of molybdenum from the catalyst. Molybdenum sublimes from the upper part of the reactor where the methanol concentration is high and decompose in the lower parts of the reactor, forming needle-shaped MoO3 crystals. As a result of the molybdenum sublimation and condensationldecomposition, the catalytic activity and selectivity to formaldehyde decrease and the pressure drop over the reactor increase. Consequently, after about 1-2 years, or even less than a year, on stream the catalyst has to be replaced depending on the reaction conditions.
To increase the capacity of existing plants and to decrease the size and cost for new plants it is desirable to increase the formaldehyde production per reactor tube and time unit. One possibility doing so is to increase the inlet concentration of methanol. However, as a consequence of higher methanol concentrations, the hot spot temperature might increase since more methanol molecules have to be converted. Since higher temperatures and methanol concentration facilitate the volatilization of molybdenum from the present catalyst, any attempt to increase the plant capacity by increasing the methanol inlet concentration would risk accelerating the vol atilizati on of molybdenum.
Therefore, alternative catalysts showing lower volatility of the active elements are of interest provided that they are active and show comparable selectivity to formaldehyde.
Further, due to the concern of environmental and health aspects it is preferable to limit the amount of harmful substances in the catalyst.
An object of the present invention is to provide a stable catalyst that is suitable for aldehyde production, in particular formaldehyde or acetaldehyde production, through alkanol oxidation, especially methanol or ethanol oxidation. A further object is to provide a catalyst that overcomes some of the problems associated with prior art catalysts. A further object is to provide a catalyst that shows high selectivity to the aldehyde, preferably formaldehyde or acetaldehyde and has a limited amount of harmful substances.
It has quite surprisingly been found that these obj ects can be achieved with a catalyst comprising iron molybdate and molybdenum trioxide and further comprising phosphorus.
The catalyst may be doped with phosphorus. The catalyst according to the invention may have a Mo/Fe molar ratio of from 1.5 to 5 and a specific surface area of from 1 to 20 m2/g.
The catalyst can be in form of cylinders, rings, balls, granules, saddles etc. Besides showing high selectivity to formaldehyde (>90%) from methanol and oxygen in an inert agent, decreased volatilization of molybdenum from the catalyst of the present invention can be detected compared to a catalyst only comprising iron molybdate and molybdenum trioxide. h one embodiment, the catalyst consists of or consists essentially of iron molybdate, molybdenum trioxide and a phosphorus compound. "Consists essentially of' has the meaning that the catalyst consists of the named compounds to the exclusion of other compounds which have a material effect on the catalytic effect or activity of the catalyst.
A suitable amount of phosphorus is 50-50000 ppm. The catalyst may contain 50-1000 ppm, preferably 50-250 ppm, phosphorus if located at the catalyst surface. The catalyst may contain 100-20000 ppm, preferably 500-10000 ppm, phosphorus if located in the catalyst bulk and surface. Phosphorus is suitably added in the form of an organic or inorganic compound, for example an organic or inorganic phosphate, e.g. an alkylphosphate such as trimethylphosphate, a phosphine or a phosphorus-containing acid such as phosphoric acid. The phosphorus may be present in the final catalyst in the form of a discrete phosphorus compound, for example as an oxide, or it may be present in the lattice of the crystalline phases of Fe and/or Mo.
The catalyst according to the invention has a specific surface area in the range of 1 -20 m /g, The catalyst may have a specific surface area of from 1 -10 m7g, more preferably 4 -8 m2/g.
In a further aspect, the present invention refers to a process for producing said catalyst. A process for producing a catalyst comprises the step of treating a solid catalyst comprising iron molybdate and molybdenum trioxide with a phosphorus-containing compound.
A solid catalyst comprising iron molybdate and molybdenum trioxide may be prepared by precipitation from a homogenous water solution containing desired amounts of iron and molybdenum. The desired amounts of iron and molybdenum are selected according to the molar ratio of Mo/Fe desired in the catalyst. The homogenous solution may be prepared from one or two separate water solutions, containing dissolved iron salt and molybdenum salt, respectively at appropriate concentrations. The iron salt may be selected from the group consisting of Fe(N0$)Tr 9H20 and FeC!3 61120. The molybdenum salt may be selected from the group consisting of' (NH4)5Mo7024 4 H20, (NH4)4MogO26, (N1-14)2Mo04, (N1-[4)2Mo40i3 2 H20, (NH4)2Mo2O7, (NH4)3PMoi2O4u molybdenum chloride, molybdenum oxide (MoO2, MoO3).
If necessary, in order to obtain a homogenous mixture of the elements, the solution can be heated and/or the pH can be lowered by adding acids like HNO3, H2S04 and/or HC1. A solid precipitate is then obtained when pH is sufficiently raised by adding a base, The base may be selected from NH3 and/or NaOH or any other suitable base. If necessary, in order to simplify the separation of the solid from the liquid phase by increasing the size of the precipitates the temperature of the liquid containing the precipitate may be raised to 35- 100°C, typically 40-70°C. The particles are separated by centrifugation and then washed with water. As an alternative, the particles are separated by filtration and then washed with water. Finally, the dried particles are calcined at temperatures from 300 to 650°C, preferable from 350 to 550°C, in an oxidizing atmosphere of flowing air. The oxidation lasts generally for at least three hours. The catalyst may be impregnated with a solution containing a phosphoms compound either before or after calcination. The impregnated catalyst is dried and optionally calcined at a temperature of 300-650°C, preferably 350- 450°C, preferably in an oxidizing atmosphere, which may be of flowing air for at least three hours. The final catalyst has a specific surface area (BET) in the range of 1 -20 m2/g, more preferably 1-] 0 m2/g, most preferably 4-8 m2/g.
An alternative way of doping the catalyst is to add phosphorus to the homogenous mixed solution of the iron and molybdenum prior to the precipitation. Yet another alternative is to impregnate the washed particles obtained by centrifugation or filtration with a solution containing phosphorns, where after they are dried and optionally calcined. A combination of the different doping techniques is also possible. Optionally, a calcination step may take place after the phosphorus compound has been added to the catalyst.
The catalyst is useful for production of aldehyde by selective oxidation of alkanol with oxygen. The aldehyde may be selected from formaldehyde or acetaldehyde. The alkanol may be selected from methanol or ethanol, The selective oxidation reaction may take place in a cooled multi-tube reactor.
The present invention further refers to the use of said catalyst in a cooled multi-tube reactor for selective oxidation of methanol with oxygen to formaldehyde. In the gas mixture at the inlet of the reactor methanol may be present in concentrations of 6 to 13% and oxygen in concentrations of 8 to 15% together with an inert gas, most typically nitrogen. The catalyst of the present invention can be used either alone or together with other catalysts at any position in the reactor.
The present invention is further explained with reference to enclosed embodiment examples, which are to be construed as illustrative and not limiting in any way.
Example I illustrates the preparation of a catalyst according to the invention comprising iron molybdate and molybdenum trioxide and being doped with phosphorus.
Example 2 is a comparative example illustrating the performance and the ageing of the reference catalyst shown by the amount of Mo lost during use in methanol oxidation.
Example 3 illustrates the performance and the ageing of the catalyst according to the invention shown by the amount of Mo lost during use in methanol oxidation.
The reference catalyst is a commercially produced iron molybdate catalyst with a slight excess of molybdenum oxide, Mo01-Fe2(Mo04)3, produced by Formox AB. The Mo/Fe ratio is 2.29 and the surface area of the catalyst is 6.3 m2/g
Example
Preparation of a catalyst according to the invention A catalyst according to the invention is prepared by impregnation of the reference catalyst with phosphorus, P-Mo03-Fe2(Mo04)3, First the phosphorus doping solution is prepared by making an aqueous solution. This is done by mixing 0. 1235g of trimethylphosphate (PO(OCH3)3) in 100 ml water. 350g of the reference iron molybdate catalyst, MoO3-Fe2(Mo04)3 is impregnated with the trimethylphosphate solution, allowed to dry at 100 °C for 1 hour followed by calcination in an oxidizing atmosphere of flowing air at 450 °C.
The oxidation generally lasts for I hour. The Mo/Fe ratio is 2.29 and the surface area of the catalyst is 5.6 m2/g.
Example 2
Performance and ageing of the reference catalyst Usually a reactor tube for methanol oxidation is loaded with two or more catalytic layers.
In these experiments only the top most layer of catalyst is loaded in the reactor, since the loss of molybdenum is known to reach its maximum at the inlet part of the catalytic bed.
A reactor tube surrounded with a heat tnmsfer fluid (HTF) was loaded with three layers of inert and catalytic material from the top arranged according to the following description: 37 cm inert layer; ceramic rings 48 cm catalytic layer 30 cm inert layer; ceramic rings The reactor was operated under pressure (t.7 bar) with a methanol inlet concentration of 10% by volume. The oxygen content in the feed gas stream, before mixing with methanol, was 10% by volume and the rest inert nitrogen gas. The reactor was then heated up to the I-liT boiling temperature, i.e. 258 °C. The gas mixture was fed to the reactor at a flow rate of 42.8 Nl/min, The HTF was adjusted to give a desired outlet concentration of methanol of 3%. The reactor was run until the concentration of methanol at the outlet passed above 4% at a HTF temperature of 274 °C.
Methanol, formaldehyde (FA), dimethyl ether (DME) and CO were analysed on a gas chromatograph and the results found at the termination of the reaction are presented in Table 1. The amount of molybdenum lost during the reaction was determined and is shown
in Table 2.
Example 3
Performance and ageing of a catalyst according to the invention A reactor tube was loaded in the same way as in Example 2 but with the catalyst prepared in Example 1 instead of the reference catalyst. The reactor was then operated like in
Example 2.
Methanol, formaldehyde (FA), dimethyl ether (DME) and CO were analysed on a gas chromatograph and the results found at the termination of the reaction are presented in Table I The amount of molybdenum lost during the reaction was determined and is shown
in Table 2.
Table 1. Catalytic performance of the catalysts Conversion (%) Selectivity (%) Sample MeOH FA CO DME Mo03-Fe,(Mo04)3 57,7 93.7 1.5 4.8 P-Mo03-Fe2(MoO4)3 62.9 93.3 1.9 4.8 Table 2. Ageing of the catalysts shown by the amount of Mo lost during methao1 oxidation Sample (g Mo lost) / (ton MeOH cony.) MoOi-Fe7(Mo04)3 18,8 P-Mo03-Fe2(MoO4)3 5.5 Doping the commercial catalyst with phosphorus decreased the Mo loss and consequently improved the catalyst lifetime without affecting methanol conversion or selectivity to formaldehyde.
Claims (6)
- Claims 1. A catalyst for aldehyde production through selective oxidation of alkanol with oxygen, comprising iron molybdate and molybdenum trioxide where the Mo/Fe molar ratio is 15-5 and the specific surface area is 1-20 m2/g, characterised in that said catalyst further comprises phosphorus.
- 2. A catalyst according to claim 1, characterised in that said aldehyde is fonnaldehyde and said alkanol is methanol.
- 3, A catalyst according to claim 1, characterised in that said aldehyde is acetaldehyde and said alkanol is ethanol.
- 4, A catalyst according to claim 1, characterised in that the catalyst contains 50-50000 ppm of phosphorus.
- 5, A catalyst according to claim 4, characterised in that the catalyst contains 50-] 000 ppm phosphoms, preferably 50-250 ppm, located at the catalyst surface.
- 6. A catalyst according to claim 4, characterised in that the catalyst contains 100-20000 ppm phosphorus, preferably 500-10000 ppm.7, A catalyst according to any of claims Ito 6, characterised in that said phosphorus is added to the catalyst in the form of an organic or inorganic phosphate, a phosphine or a phosphorus-containing acid, 8, A catalyst according to any of claims Ito 7, characterised in that said catalyst has a specific surface area of 1-10 m2/g, more preferably 4 -8 m2/g.9, A catalyst according to any of claims Ito 8, wherein said catalyst consists essentially of iron molybdate, molybdenum trioxide and a compound of phosphorus.ID, A process for producing a catalyst according to any of the claims I to 9, comprising the step of treating a solid catalyst comprising iron molybdate and molybdenum trioxide with a phosphorus-containing compound.11 A process according to claim 10, wherein said treating step is carried out by impregnating said solid catalyst comprising iron molybdate and molybdenum trioxide with a solution of a phosphorus-containing compound.12. A process according to claim 10 or 11, wherein said catalyst is calcined before or after said treating step.13. A process according to any one of claims 10 to 12, characterised in that said catalyst comprising iron molybdate and molybdenum trioxide is prepared by precipitation from a homogenous water solution containing desired amounts of Fe and Mo, separation of said precipitate from said solution, washing, and drying.14. Use of a catalyst according to any of the claims 1-9 in a cooled multi-tube reactor for selective oxidation of alkanol, with oxygen to form an aldehyde.15. Use according to claim 14, characterised in that said alkanol is methanol and is present in concentrations of 6 to 13% and oxygen in concentrations of 8 to I 5% in a gas mixture together with an inert gas, at the inlet of the reactor.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201313012315A | 2013-07-09 | 2013-07-09 |
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| GB201412144D0 GB201412144D0 (en) | 2014-08-20 |
| GB2518274A true GB2518274A (en) | 2015-03-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB1412144.6A Withdrawn GB2518274A (en) | 2013-07-09 | 2014-07-08 | Catalyst for aldehyde production |
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| GB (1) | GB2518274A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016177999A1 (en) * | 2015-05-01 | 2016-11-10 | Johnson Matthey Public Limited Company | Process for aldehyde manufacture |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114618507A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Iron-molybdenum catalyst for preparing formaldehyde through methanol oxidation assisted by ink-jet printing, and preparation and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060135821A1 (en) * | 2004-12-22 | 2006-06-22 | Sud-Chemie Catalysts Italia S.R.L. | Catalysts for oxidation of methanol to formaldehyde |
| EP1674156A1 (en) * | 2004-12-23 | 2006-06-28 | Süd Chemie - Catalysts Italia S.R.L. | Method for preparing a catalyst for oxidation of methanol to formaldehyde |
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2014
- 2014-07-08 GB GB1412144.6A patent/GB2518274A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060135821A1 (en) * | 2004-12-22 | 2006-06-22 | Sud-Chemie Catalysts Italia S.R.L. | Catalysts for oxidation of methanol to formaldehyde |
| EP1674156A1 (en) * | 2004-12-23 | 2006-06-28 | Süd Chemie - Catalysts Italia S.R.L. | Method for preparing a catalyst for oxidation of methanol to formaldehyde |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016177999A1 (en) * | 2015-05-01 | 2016-11-10 | Johnson Matthey Public Limited Company | Process for aldehyde manufacture |
| US10239810B2 (en) | 2015-05-01 | 2019-03-26 | Johnson Matthey Public Limited Company | Process for aldehyde manufacture |
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| GB201412144D0 (en) | 2014-08-20 |
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