WO2011067363A2 - Herstellung von acetaldehyd und/oder essigsäure aus bioethanol - Google Patents
Herstellung von acetaldehyd und/oder essigsäure aus bioethanol Download PDFInfo
- Publication number
- WO2011067363A2 WO2011067363A2 PCT/EP2010/068793 EP2010068793W WO2011067363A2 WO 2011067363 A2 WO2011067363 A2 WO 2011067363A2 EP 2010068793 W EP2010068793 W EP 2010068793W WO 2011067363 A2 WO2011067363 A2 WO 2011067363A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oxidation
- sulfur
- oxidation catalyst
- ethanol
- acetic acid
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
Definitions
- the present invention relates to a process for the preparation of production of acetaldehyde and / or acetic acid from ethanol which contains at least one impurity selected from sulfur compounds, in particular from bioethanol.
- GB 1 301 145 describes a process for preparing an aliphatic monocarboxylic acid from an alkanol having two to four carbon atoms, in which the alkanol is introduced in vapor form into a reaction zone with a solid catalyst containing palladium metal and reacted with an oxygen-containing gas.
- EP-A 0294846 describes a process for producing an organic acid 20 by catalytic oxidation of an alcohol in contact with a calcined mixed oxide catalyst of the composition: Mo x V y Z z where Z is absent or represents a particular metal.
- US 5,840,971 discloses a process for the production of acetic acid by controlled oxidation of ethanol. The reaction takes place in the presence of a catalyst whose active mass consists of vanadium, titanium and oxygen.
- DE 1097969 describes a process for the preparation of aldehydes by dehydrogenation of primary aliphatic alcohols using a chromate-activated copper contact.
- Bioethanol is defined as ethanol made exclusively from biomass, ie. H. renewable carbon carriers.
- the polysaccharides in the form of starch or cellulose contained in the biomass are enzymatically broken down into glucose and subsequently fermented to ethanol.
- Bioethanol contains production-related impurities, especially sulfur compounds. Sulfur compounds are effective catalyst poisons that can lead to the formation of alkali-reacting metal sulfides on many catalyst surfaces, especially of precious metals. Purification of the bioethanol to remove the sulfur compounds is not useful for economic reasons.
- the invention is therefore based on the object to provide a process for the preparation of acetaldehyde and / or acetic acid from bioethanol, in which a previous purification of the bioethanol is not required.
- the object is achieved by a process for the production of acetaldehyde and / or acetic acid, wherein a gaseous stream containing molecular oxygen, ethanol and at least one impurity selected from sulfur compounds is contacted at elevated temperature with a sulfur-resistant oxidation catalyst.
- the ethanol is bioethanol, d. H. Ethanol derived from biomass.
- the gaseous stream generally contains 2 to 100 ppm, usually 5 to 50 ppm, sulfur compounds, based on the ethanol content.
- the determination of the content of sulfur compounds can be carried out by gas chromatography.
- the sulfur compounds include organic sulfur compounds, especially dimethyl sulfate and / or dimethyl sulfoxide.
- An oxidation catalyst is referred to as "sulfur resistant" if the concentration of organic sulfur compounds, e.g. For example, dimethylsulfoxide in the ethanol used to lower the activity of the catalyst to 90% (the initial activity) within 200 hours of operation is greater than 500 ppm (based on the ethanol content).
- the activity may suitably be determined as ethanol conversion at a catalyst loading of 50-200 g of ethano l.h, e.g. B. at 80 g of ethanol / 1 cat and hour.
- Preferred sulfur-resistant oxidation catalysts include vanadium oxide as the catalytically active ingredient; More preferred catalysts include, in addition to vanadium oxide, at least one oxide of zirconium, titanium and / or aluminum.
- Vanadium oxide-containing catalysts are known per se. They are z. Obtainable by the following methods: i) impregnating a porous support with a solution of a vanadium compound, removing the solvent and calcining the impregnated support, see e.g. For example, US 4,048,112; ii) treating finely divided titanium dioxide with a vanadium compound, optionally applying the composition to an inert support and calcining, see, for example, US Pat. For example, US 3,464,930; iii) treating titania with water and vanadium oxychloride until the desired vanadium content is achieved, see, e.g.
- preparation method (i) is generally preferred.
- a porous carrier are z. Zirconia, titania or alumina.
- the carrier may take any suitable form, e.g. As spheres, rings, pellets, extruded extruded or honeycomb shape.
- Suitable vanadium compounds are z.
- vanadium pentoxide or a vanadium salt such as vanadyl sulfate, vanadyl chloride or ammonium metavandate, which are preferably dissolved in water in the presence of a complexing agent such as oxalic acid.
- the impregnation may be followed by an optional drying step in which the solvent is added to e.g. B. at a temperature of 100 to 200 ° C is removed.
- the impregnated support is then heated at a temperature of at least 450 ° C, e.g. B. 500 to 800 ° C calcined.
- the calcination may be carried out in the presence of oxygen, e.g. B. in the air, or in an inert atmosphere.
- the dried and / or calcined support may optionally be re-impregnated to achieve a desired loading of vanadium oxide.
- finely divided titanium dioxide preferably in the anatase modification
- a vanadium compound e.g.
- the solution may optionally contain complexing agents such as oxalic acid.
- one may treat the finely divided titania under hydrothermal conditions with a sparingly soluble vanadium compound such as vanadium pentoxide.
- composition obtained can be used in powder form as well as molded to specific catalyst geometries, wherein the shaping can be carried out before or after the final calcination.
- the active composition or its uncalcined precursor composition can be compressed (for example, by tableting, extruding or
- Vollkatalysatoren be prepared, where appropriate aids such.
- graphite or stearic acid as a lubricant and / or molding aids and Ver- Toners such as microfibers of glass, asbestos, silicon carbide or potassium titanate can be added.
- Ver- Toners such as microfibers of glass, asbestos, silicon carbide or potassium titanate can be added.
- Suitable Vollkatalysatorgeometrien are z.
- an inert carrier is coated with the resulting powdery active composition or its pulverulent, not yet calcined precursor composition, whereby a so-called coated catalyst is obtained.
- the coating of the carrier body for the preparation of the coated catalysts is usually carried out in a suitable rotatable container, for. B. by spraying in a coating drum, coating in a fluidized bed or powder coating plant.
- a suspension of the mass to be applied is used to coat the carrier bodies.
- the layer thickness of the applied to the support body mass is suitably in the range z. B. in a layer thickness of 10 ⁇ to 2 mm.
- non-porous inert carriers are materials which are substantially free of pores or have a low specific surface area, preferably less than 3 m 2 / g. Quartz, silica glass, sintered silica, sintered or smelted clay, porcelain, sintered or melt silicates, such as aluminum silicate, magnesium silicate, zinc silicate, zirconium silicate and, in particular, steatite, may be considered.
- the carrier body may be regularly or irregularly shaped, with regularly shaped carrier body, for. As balls or hollow cylinders, are preferred. Suitable is the use of substantially non-porous carriers of steatite.
- the carrier may suitably have an average particle size of 1 to 10 mm.
- the catalytically active compositions obtained by Preparations (iii) to (iv) can also be applied to an inert support as described above.
- the sulfur-resistant oxidation catalyst comprises 0.1 to 30% by weight, preferably 5 to 20% by weight, of V2O5, based on the total weight of the catalyst.
- the reaction can be carried out in any reactor for carrying out heterogeneously catalyzed reactions in the gas phase, wherein the catalyst can be arranged as a fixed bed or fluidized bed.
- a tube bundle reactor consists of a plurality of Reaktorroh ren, in which a fixed bed of the catalyst is arranged, which are surrounded for heating and / or cooling of a heat transfer medium.
- the tube bundle reactors used industrially contain more than three to several ten thousand reactor tubes connected in parallel.
- a reactor is understood to mean the smallest extent which is perpendicular to the direction of flow.
- the characteristic dimension of the reaction zone of a microreactor is significantly smaller than that of a conventional reactor (eg at least a factor of 10 or at least a factor of 100 or at least a factor of 1000) and is usually in the range of a hundred nanometers to a few tens of millimeters. Often it is in the range of 1 ⁇ to 30 mm.
- the gaseous stream contains 0.5 to 20% by volume, in particular 1 to 5% by volume, of ethanol.
- the gaseous stream contains 0.5 to 20% by volume, in particular 5 to 10% by volume, of oxygen.
- the gaseous stream also contains water vapor, preferably in an amount up to 40% by volume, e.g. B. 1 to 15 vol .-%.
- water vapor facilitates the desorption of the oxidation products from the catalyst surface and can also improve the dissipation of the heat of reaction.
- the difference to 100 vol .-% is usually made of at least one inert gas, preferably nitrogen, for. B. nitrogen.
- the reaction of the gaseous stream on the oxidation catalyst is generally carried out at a temperature of 150 to 300 ° C, wherein at higher temperatures acetic acid is the predominant oxidation product.
- acetic acid is the desired oxidation product
- the reaction can be carried out in one or more stages, in particular two stages.
- the intermediate oxidation mixture obtained after one stage is preferably not worked up but instead fed to the subsequent stage.
- a possible embodiment of a two-stage process relates to a process in which reacting the gaseous stream on the sulfur-resistant oxidation catalyst to a first oxidation mixture, wherein acetaldehyde is the predominant oxidation product, and converts the first oxidation mixture of another oxidation catalyst to a second oxidation mixture, wherein acetic acid is the predominant Oxidation product is.
- the further oxidation catalyst can be arranged in the same reactor as a bed located downstream of the bed of the sulfur-resistant oxidation catalyst.
- the term downstream refers to the flow direction of the gaseous stream.
- the reactor can have two temperature zones, wherein the zone of the further oxidation catalytic converter can be temperature-controlled independently of the zone of the sulfur-resistant oxidation catalytic converter.
- any gas phase oxidation catalyst capable of selectively oxidizing aldehydes to carboxylic acids is suitable.
- the oxidation catalyst comprises a multimetal oxide containing at least molybdenum and vanadium.
- Such catalysts are used, for example, for the partial oxidation of acrolein to acrylic acid.
- the two-stage oxidation of ethanol to acetic acid allows better control of heat generation.
- the loading of the gas stream with ethanol can be increased.
- the oxidation of acetaldehyde to acetic acid on Mo and V containing multimetal oxide active materials is carried out with high selectivity. It is achieved a high acetic acid yield over both stages.
- Such Mo and V-containing Multimetalloxiditmassen for example, US-A 3775474, US-A 3954855, US-A 3893951 and US-A 4339355 or EP-A 614872 or EP-A 1041062 or WO 03/055835 , WO 03/057653.
- the multimetal are also the DE-A 10 32 5487, DE-A 10 325 488, EP-A 427508, DE-A 29 09 671, DE-C 31 51 805, DE-AS 26 26 887, DE-A 43 02 991, EP-A 700 893, EP-A 714 700 and DE-A 19 73 6105.
- Particularly preferred in this connection are the exemplary embodiments of EP-A 714 700 and DE-A 19 73 6105.
- Suitable multimetal oxide active compounds correspond to the general formula I,
- X 2 Cu, Ni, Co, Fe, Mn and / or Zn,
- X 3 Sb and / or Bi
- X 4 one or more alkali metals
- X 5 one or more alkaline earth metals
- X 6 Si, Al, Ti and / or Zr
- n a number determined by the valence and frequency of the elements other than oxygen in IV.
- the variables have the following meaning:
- X 1 W, Nb, and / or Cr
- X 2 Cu, Ni, Co, and / or Fe
- X 5 Ca, Sr and / or Ba
- X 6 Si, Al, and / or Ti
- n a number determined by the valency and frequency of the elements other than oxygen in I.
- the multimetal oxide active masses containing Mo and V in particular those of the general formula I, can be used as solid catalysts both in powder form and in particular catalyst geometries. They can also be applied to preformed inert catalyst supports.
- Example 1 Preparation of a Vanadium Oxide-Containing Oxidation Catalyst 380.0 g of water were placed in a 21-beaker and heated to 55 ° C. While heating, 220.0 g of oxalic acid dihydrate were added. After complete dissolution of the oxalic acid dihydrate, 16 g of V2O5 were added in small portions, forming a deep blue vanadium complex. After complete addition of V20s, the solution was warmed to 80 ° C, stirred for a further 10 min and then cooled to room temperature.
- Example 2 Ten ml of the catalyst from Example 1 were installed as a fixed bed in an electrically heated vertical tubular reactor (diameter 15 mm, length 1000 mm). In the gas inlet facing upper half of the bed, the catalyst was diluted with 75 wt .-% steatite, in the lower half with 66 wt .-% steatite. The length of the catalyst bed was about 250 mm. On both sides of the bed was in each case a layer of 300 mm steatite balls (2 to 3 mm in diameter) arranged. Under the steatite was a catalyst chair with a height of about 100 mm. The apparatus was heated externally to 240 ° C. Evaporated ethanol, evaporated water, air and nitrogen were added to the reactor.
- the composition of the gas stream was 1.4% by volume of ethanol, 14% by volume of H 2 O, 5% by volume of O 2 , balance N 2 .
- the ethanol used had a sulfur content of 3 ppm.
- the HotSpot temperature reached 260 ° C.
- Example 4 Preparation of a Second Stage Oxidation Catalyst
- the oxygen content was adjusted so that there was an O 2 content of 1.5% by volume at the outlet of the recirculating air oven.
- the kneaded mass was first heated at a rate of 10 K / min to 300 ° C and then maintained at this temperature for 6 h. Thereafter, it was heated at a rate of 10 K / min to 400 ° C and this temperature was maintained for 1 h.
- the furnace loading O (g catalyst precursor per I internal volume of the recirculating oven), the input volume flow ES (Nl / h) of the oxygen / nitrogen mixture and the residence time VZ (sec) of the oxygen / nitrogen feed (ratio Internal volume of the circulating air oven and volume flow of the supplied oxygen / nitrogen mixture) selected as listed below.
- the circulating air oven used had an internal volume of 3 l. O: 250 g / l, VZ: 135 sec and ES: 80 Nl / h.
- the resulting catalytically active material was based on the following stoichiometry:
- catalytically active material After grinding the calcined, catalytically active material to particle diameter in the range of 0.1 to 50 ⁇ were coated with the resulting active powder in a rotary drum, nonporous, rough surface steatite spheres of a diameter of 2 to 3 mm with the addition of water, so that an active material content of 20% by weight resulted. It was then dried with 1 10 ° C hot air.
- EXAMPLE 5 Two-Stage Ethanol Oxidation on the Catalyst Fixed Bed Ten ml of the catalyst from Example 1 were diluted with 10 ml of steatite chippings (1 to 1.5 mm) and, as a fixed bed facing the gas inlet, into an electrically heated tubular reactor (diameter 15 mm , Length 1000 mm) installed. Adjacent to this first bed, 5 ml of the second stage oxidation catalyst of Example 4 was introduced.
- the apparatus was heated from the outside in the region of the first bed to 185 ° C, in the region of the bed of the second stage oxidation catalyst to 220 ° C. the Reactor was fed with evaporated ethanol, evaporated water, air and nitrogen.
- the composition of the gas stream was 1, 6 vol .-% ethanol, 10 vol .-% H2O, 6 vol .-% 0 2 , balance N 2 .
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2010800548798A CN102770403A (zh) | 2009-12-04 | 2010-12-03 | 由生物乙醇制备乙醛和/或乙酸 |
RU2012125832/04A RU2012125832A (ru) | 2009-12-04 | 2010-12-03 | Получение ацетальдегида и/или уксусной кислоты из биоэтанола |
BR112012013208A BR112012013208A2 (pt) | 2009-12-04 | 2010-12-03 | processo para a preparação de ácido acético |
US13/513,755 US20120245382A1 (en) | 2009-12-04 | 2010-12-03 | Producing acetaldehyde and/or acetic acid from bioethanol |
EP10787745A EP2507199A2 (de) | 2009-12-04 | 2010-12-03 | Herstellung von acetaldehyd und/oder essigsäure aus bioethanol |
ZA2012/04912A ZA201204912B (en) | 2009-12-04 | 2012-07-02 | Producing acetaldehyde and/or acetic acid from bioethanol |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP09178015 | 2009-12-04 | ||
EP09178015.5 | 2009-12-04 |
Publications (2)
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WO2011067363A2 true WO2011067363A2 (de) | 2011-06-09 |
WO2011067363A3 WO2011067363A3 (de) | 2011-10-13 |
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PCT/EP2010/068793 WO2011067363A2 (de) | 2009-12-04 | 2010-12-03 | Herstellung von acetaldehyd und/oder essigsäure aus bioethanol |
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US (1) | US20120245382A1 (de) |
EP (1) | EP2507199A2 (de) |
CN (1) | CN102770403A (de) |
BR (1) | BR112012013208A2 (de) |
RU (1) | RU2012125832A (de) |
WO (1) | WO2011067363A2 (de) |
ZA (1) | ZA201204912B (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102010040923A1 (de) | 2010-09-16 | 2012-03-22 | Basf Se | Verfahren zur Herstellung von Acrylsäure aus Ethanol und Formaldehyd |
Families Citing this family (1)
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CN111454140B (zh) * | 2020-06-04 | 2021-10-01 | 中国科学技术大学 | 一种光催化氧化乳酸制备醋酸的方法 |
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DE1097969B (de) | 1954-03-26 | 1961-01-26 | Knapsack Ag | Verfahren zur Herstellung von Aldehyden durch Dehydrierung von primaeren aliphatischen Alkoholen |
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GB1301145A (en) | 1969-05-13 | 1972-12-29 | Nat Distillers Chem Corp | Preparation of carboxylic acids |
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2010
- 2010-12-03 RU RU2012125832/04A patent/RU2012125832A/ru not_active Application Discontinuation
- 2010-12-03 EP EP10787745A patent/EP2507199A2/de not_active Withdrawn
- 2010-12-03 BR BR112012013208A patent/BR112012013208A2/pt not_active Application Discontinuation
- 2010-12-03 CN CN2010800548798A patent/CN102770403A/zh active Pending
- 2010-12-03 US US13/513,755 patent/US20120245382A1/en not_active Abandoned
- 2010-12-03 WO PCT/EP2010/068793 patent/WO2011067363A2/de active Application Filing
-
2012
- 2012-07-02 ZA ZA2012/04912A patent/ZA201204912B/en unknown
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EP0427508A1 (de) | 1989-11-06 | 1991-05-15 | Nippon Shokubai Co., Ltd. | Verfahren zur Herstellung von Acrylsäure |
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EP0614872A1 (de) | 1993-03-12 | 1994-09-14 | Nippon Shokubai Co., Ltd. | Verfahren zur Entfernung von festen organischen Stoffen |
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EP1041062A2 (de) | 1999-03-31 | 2000-10-04 | Nippon Shokubai Co., Ltd. | Verfahren zur Reinigung von (Meth)acrylsäure |
WO2003055835A1 (fr) | 2001-12-27 | 2003-07-10 | Mitsubishi Chemical Corporation | Procede d'oxydation catalytique en phase vapeur et procede pour produire de la (meth)acroleine ou de l'acide (meth)acrylique |
WO2003057653A1 (fr) | 2001-12-28 | 2003-07-17 | Mitsubishi Chemical Corporation | Procede d'oxydation catalytique en phase vapeur |
DE10325487A1 (de) | 2003-06-04 | 2004-12-23 | Basf Ag | Verfahren zur thermischen Behandlung der Vorläufermasse einer katalytischen Aktivmasse |
DE10325488A1 (de) | 2003-06-04 | 2004-12-23 | Basf Ag | Verfahren zur Herstellung von katalytisch aktiven Multielementoxidmassen, die wenigstens eines der Elemente Nb und W sowie die Elemente Mo, V und Cu enthalten |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102010040923A1 (de) | 2010-09-16 | 2012-03-22 | Basf Se | Verfahren zur Herstellung von Acrylsäure aus Ethanol und Formaldehyd |
US8507721B2 (en) | 2010-09-16 | 2013-08-13 | Basf Se | Process for preparing acrylic acid from ethanol and formaldehyde |
Also Published As
Publication number | Publication date |
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US20120245382A1 (en) | 2012-09-27 |
WO2011067363A3 (de) | 2011-10-13 |
BR112012013208A2 (pt) | 2016-03-01 |
EP2507199A2 (de) | 2012-10-10 |
RU2012125832A (ru) | 2014-01-10 |
CN102770403A (zh) | 2012-11-07 |
ZA201204912B (en) | 2013-09-25 |
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