WO2000012471A1 - Verfahren zur nicht-oxidativen herstellung von formaldehyd aus methanol - Google Patents
Verfahren zur nicht-oxidativen herstellung von formaldehyd aus methanol Download PDFInfo
- Publication number
- WO2000012471A1 WO2000012471A1 PCT/EP1999/006135 EP9906135W WO0012471A1 WO 2000012471 A1 WO2000012471 A1 WO 2000012471A1 EP 9906135 W EP9906135 W EP 9906135W WO 0012471 A1 WO0012471 A1 WO 0012471A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- reactor
- cooler
- melt
- methanol
- formaldehyde
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D323/00—Heterocyclic compounds containing more than two oxygen atoms as the only ring hetero atoms
- C07D323/04—Six-membered rings
- C07D323/06—Trioxane
-
- 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
- C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/08—Polymerisation of formaldehyde
Definitions
- the invention relates to a process for the production of formaldehyde by dehydrogenation of methanol in the presence of a fluid catalyst at elevated temperature.
- the reaction temperature is 600 to 720 ° C. Both methods are described in Ulimann's Encykl. der Techn. Chemie, Vol. 11, pp. 693-694, 4th edition 1976, Verlag Chemie Weinheim. In both processes, formaldehyde is initially obtained in the form of an aqueous solution. Particularly when used for the production of formaldehyde polymers and oligomers, the formaldehyde obtained in this way has to be dewatered in a complex manner. Another disadvantage is that corrosive formic acid is formed as a by-product.
- DE-OS 2525174 describes a catalyst containing copper, zinc and sulfur
- US Pat. No. 4,045,609 describes a catalyst which contains copper, zinc and selenium.
- catalysts contain zinc and / or indium (EP 0 130 068), silver (US 2,953,602) or silver, copper and silicon (US 2,939,883). However, all of these catalysts do not allow economical production of formaldehyde by dehydrogenation of methanol.
- the object of the invention is therefore to provide a process for the preparation of formaldehyde by non-oxidative dehydrogenation which is ecologically and economically interesting, which allows high yields and selectivities and in particular the side effects caused by catalysts and carbon-containing by-products Reaction are caused, do not occur or occur only to a significantly reduced extent.
- Another object of the invention is to provide a process which enables the catalyst to be recovered in an economical manner.
- Another object of the invention is to provide an apparatus with which such processes can be carried out. This task is solved
- Claim 16 specifies an advantageous use of the formaldehyde produced by a process according to Claims 1 to 15.
- the invention further relates to a device for producing formaldehyde by catalyzed, non-oxidative dehydrogenation of methanol, in particular by the process according to one of claims 1 to 15, according to one or more of claims 17 to 20.
- Fig. 1 shows a conventional system in which methanol and carrier gas are first passed through a heat exchanger, then passed through the reactor, which also contains the catalyst, the product mixture is then passed through a cooler, then passed on to a heat exchanger for processing.
- Fig. 2 shows an apparatus for performing the method according to the invention with continuous cleaning of the molten salt of the cooler.
- the methanol and the carrier gas are passed in a preheated state through a molten salt which is located in a so-called bubble column, i.e. H. Gas is through the
- the catalytic reaction is carried out in the molten salt and / or in the gas space above the molten salt as a result of catalyst particles which may be entrained by the gas.
- the reaction product then arrives gaseous in the cooler through which a salt melt is passed as a falling film in countercurrent.
- the molten salt cools the product gas and absorbs catalyst residues and by-products, especially impurities.
- the molten salt is drained off at the lower part of the cooler and can then be wholly or partly drained off for cleaning and is then returned to the cooler via a heat exchanger after regeneration.
- a combination of bubble column reactor or falling film reactor and falling film cooler can also be used advantageously, in which salt melt is drawn off for cleaning at the bottom of the bubble column or falling film reactor, the cleaned one
- Salt melt is fed back into the falling film cooler and this melt flow is also fed to the reactor (see FIG. 3).
- 3 shows an apparatus for the process according to the invention with continuous cleaning of the molten salt, the salt circuits comprising the cooler and the reactor being coupled.
- a sodium salt melt is preferably used, which can be, for example, a low-melting eutectic made of sodium and lithium carbonate, which is discharged and regenerated continuously or discontinuously from the reaction apparatus or from which the disruptive impurities are continuously or discontinuously discharged and which melt
- Sodium as such can also be used as a melt.
- the melt in the cooler generally has a temperature of 200 to 350 ° C and is warmed up by the hot product gas stream.
- the temperature of the melt in the reactor to be heated is approximately 400 to 1100 ° C., preferably 750 to 950 ° C., in particular 600 to 850 ° C.
- other temperatures can also be set from case to case; the optimal temperatures can be determined by simple preliminary tests.
- the heat to be removed from the cooler can be used particularly advantageously for heating the methanol / carrier gas stream.
- the molten salt is in motion in the cooler and in the falling film reactor (e.g. falling film), impurities, e.g. B. sodium salts (z. B. carbonate), coke, etc. are taken up in the salt film and discharged continuously or discontinuously with the molten salt from the reactor system; Downtimes due to reactor fouling are significantly reduced.
- the salt melt is advantageously also continuously or discontinuously conveyed out of the reactor and from e.g. B. freed carbon-containing impurities and deposits of any kind and possibly used used melt.
- the temperature control of the melt is particularly preferably designed in such a way that catalyst evaporated in the reactor is recovered in the cooler and fed back to the first part of the installation, so that a closed salt circuit and thus is coupled via the salt streams
- Catalyst cycle is established (see. Fig. 3). Within the reactor, the reaction appears to take place in the melt or in part in the gas phase.
- the heat exchangers can be independent of one another or coupled, but it is advantageous to set a higher temperature in the reactor or dehydrogenation part than in the cooler.
- the product gases in the cooler preferably come into contact with one
- the melt can also be sprayed into the cooler or passed over fillings in the cooler.
- non-reducing gases such as nitrogen can also be used as carrier gas.
- Another advantage of the continuous or discontinuous procedure with bubble columns or falling film reactor is the simple metering or tracking of the primary catalyst or the molten salt. This results in a significantly longer operating time of the system, which is independent of the originally added catalyst starting material.
- the residence time in the reactor can e.g. B. by the height or length of the reactor, but also by the flow rate.
- the device for performing the above advantageously contains one or more heat exchangers for preheating the starting materials and the molten salt, a heated bubble column or falling film reactor or a combination of these reactor types for carrying out the catalyst evaporation and the dehydrogenation, a cooler with a salt circuit, which can be independent of the dehydrogenation reactor, heat exchanger for Cooling the product mixture, a device for separating the formaldehyde and a device for introducing the
- Methanol and possibly for tracking the primary catalyst or the salt mixtures used, as well as devices for discharging, cleaning and introducing the molten salt.
- a circulating gas stream which consists of by-products of the dehydrogenation, is carried as the carrier gas through the reactor and cooler.
- This circulating gas stream is obtained by, after separating off the formaldehyde, at least partially recycling the by-products of the dehydrogenation, primarily H 2 and CO, into the reactor using a suitable device.
- Suitable reactor materials are e.g. B. ceramic materials, such as corundum, but also carburizing, temperature and scale-resistant iron and Nickel based alloys. If combustion is used to heat the reactors and pipelines, the heat supplied to the process is preferably obtained by burning by-products of the dehydrogenation, primarily H 2 and CO.
- the formaldehyde can be separated off from the reaction mixture by methods known per se to those skilled in the art, for example by condensation or physical and chemical absorption or adsorption.
- a technically proven method is the formation of hemiacetals from formaldehyde and an alcohol.
- the hemiacetals are then thermally split, producing very pure formaldehyde vapor.
- Cyclohexanol is usually used as the alcohol because its boiling point is sufficiently far above that of the hemiacetal.
- the hemiacetals are usually cleaved in falling film or thin layer evaporators at temperatures from 100 to 160 ° C. (see, for example, US 2,848,500 or US 2,943,701 or JP-A 62/289540).
- the formaldehyde vapors released in the process still contain small amounts of impurities, which are usually caused by countercurrent washing with alcohol such as cyclohexanol hemiformal
- Trioxane can then e.g. B. condensed and cleaned if necessary before further use.
- salt melts to be used according to the invention are:
- Melts containing sodium or sodium compounds also in a mixture with further alkali metals and / or alkali metal or alkaline earth metal compounds.
- the above-mentioned mixtures provide formaldehyde yields of over 60% and low water concentrations of less than 5 mol% of H 2 O per mol of formaldehyde even at reaction temperatures of 600 to 1000 ° C. in a plant corresponding to FIGS. 2 and 3.
- the formaldehyde produced by the process according to the invention is suitable for all known areas of application, such as, for. B. for the production of polymers or condensation products such as polyoxymethylene, polyacetal, trioxane, phenolic resins, melamines, 1, 4-butanol, trimethylolpropane, neopentyl glycol and pentaerythritol but also for the production of methanolic formaldehyde solutions.
- formaldehyde is usually produced with a low water content by the process according to the invention, formaldehyde produced in this way is particularly suitable for the polymerization to polyoxymethylene, since anhydrous formaldehyde is to be used here, and the trimerization to trioxane.
- the thinning of the catalyst ie the decrease in the catalyst concentration, as frequently occurs in known processes, can be avoided, since it is possible set a constant catalyst concentration by metering in or working up and recycling.
- the reaction space was formed by a tube with a length of 40 mm, inner diameter 10 mm.
- the temperature of the reactor was 950 ° C, that of the cooler 750 ° C.
- Bubble column reactor both made of corundum, total length 450 mm, inner diameter 10 mm), a mixture of 52 mol% Na 2 CO 3 and 49 mol% Li 2 CO 3 with a melting point of approx. 510 ° C. was used.
- the molten salt was fed into the cooler from above and removed from the bottom of the reactor in liquid form (see FIG. 4).
- the template and the and the container for the melt were both heated to 600 ° C.
- the melt was circulated in the closed system by a gas stream (CO 2 ), so that there was approximately a melt flow of 11 / h through the reactor (film thickness 0.5 mm, film speed approximately 2 cm / s).
- the specified measured variables are calculated as follows:
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99941652A EP1109780A1 (de) | 1998-09-01 | 1999-08-21 | Verfahren zur nicht-oxidativen herstellung von formaldehyd aus methanol |
JP2000567505A JP2002523489A (ja) | 1998-09-01 | 1999-08-21 | メタノールからホルムアルデヒドを非−酸化的に製造する方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19839740.2 | 1998-09-01 | ||
DE1998139740 DE19839740A1 (de) | 1998-09-01 | 1998-09-01 | Verfahren zur nicht-oxidativen Herstellung von Formaldehyd aus Methanol |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2000012471A1 true WO2000012471A1 (de) | 2000-03-09 |
WO2000012471A8 WO2000012471A8 (de) | 2000-09-21 |
Family
ID=7879396
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1999/006135 WO2000012471A1 (de) | 1998-09-01 | 1999-08-21 | Verfahren zur nicht-oxidativen herstellung von formaldehyd aus methanol |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1109780A1 (de) |
JP (1) | JP2002523489A (de) |
DE (1) | DE19839740A1 (de) |
WO (1) | WO2000012471A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3620446A1 (de) | 2018-09-05 | 2020-03-11 | Rheinisch-Westfälische Technische Hochschule (RWTH) Aachen | Verfahren zur herstellung von dimethoxymethan |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102005006692A1 (de) * | 2005-02-15 | 2006-08-24 | Bayer Materialscience Ag | Verfahren zur Herstellung von Di-und Polyaminen der Diphenylmethanreihe |
CN104689765A (zh) * | 2015-03-24 | 2015-06-10 | 江苏凯茂石化科技有限公司 | 一种带膨胀节的甲醛氧化器 |
KR102665875B1 (ko) * | 2022-06-23 | 2024-05-13 | 아주대학교산학협력단 | 촉매반응장치 및 촉매반응장치용 버블러의 제조방법 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1645451A1 (de) * | 1964-08-01 | 1970-10-29 | Stamiearbon N V | Verfahren zur Herstellung makromolekularer Polyoxymethylese |
DE2820034A1 (de) * | 1977-05-06 | 1978-12-14 | Ici Ltd | Waermeaustauschverfahren |
EP0294684A2 (de) * | 1987-06-06 | 1988-12-14 | Hoechst Aktiengesellschaft | Verfahren zur Herstellung von Formaldehyd |
EP0691338A1 (de) * | 1994-07-06 | 1996-01-10 | Hoechst Aktiengesellschaft | Verfahren zur Herstellung von Trioxan |
DE19814285A1 (de) * | 1997-06-02 | 1998-12-03 | Hoechst Ag | Verfahren zur Herstellung von Formaldehyd aus Methanol |
DE19814281A1 (de) * | 1997-06-02 | 1998-12-24 | Hoechst Ag | Verfahren zur nicht oxidativen Herstellung von Formaldehyd aus Methanol |
DE19814284A1 (de) * | 1997-06-02 | 1999-01-07 | Hoechst Ag | Verfahren zur nicht oxidativen Herstellung von Formaldehyd aus Methanol |
-
1998
- 1998-09-01 DE DE1998139740 patent/DE19839740A1/de not_active Withdrawn
-
1999
- 1999-08-21 JP JP2000567505A patent/JP2002523489A/ja active Pending
- 1999-08-21 EP EP99941652A patent/EP1109780A1/de not_active Withdrawn
- 1999-08-21 WO PCT/EP1999/006135 patent/WO2000012471A1/de not_active Application Discontinuation
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1645451A1 (de) * | 1964-08-01 | 1970-10-29 | Stamiearbon N V | Verfahren zur Herstellung makromolekularer Polyoxymethylese |
DE2820034A1 (de) * | 1977-05-06 | 1978-12-14 | Ici Ltd | Waermeaustauschverfahren |
EP0294684A2 (de) * | 1987-06-06 | 1988-12-14 | Hoechst Aktiengesellschaft | Verfahren zur Herstellung von Formaldehyd |
EP0691338A1 (de) * | 1994-07-06 | 1996-01-10 | Hoechst Aktiengesellschaft | Verfahren zur Herstellung von Trioxan |
DE19814285A1 (de) * | 1997-06-02 | 1998-12-03 | Hoechst Ag | Verfahren zur Herstellung von Formaldehyd aus Methanol |
DE19814281A1 (de) * | 1997-06-02 | 1998-12-24 | Hoechst Ag | Verfahren zur nicht oxidativen Herstellung von Formaldehyd aus Methanol |
DE19814284A1 (de) * | 1997-06-02 | 1999-01-07 | Hoechst Ag | Verfahren zur nicht oxidativen Herstellung von Formaldehyd aus Methanol |
Non-Patent Citations (1)
Title |
---|
J SAUER ET AL: "The Catalyzed Dehydrogenation of Methanol to Formaldehyd at High Temperatures: New Insights by Modelling of Transport Phenomena and Reaction", CHEMICAL ENGINEERING AND TECHNOLOGY, no. 18, 1 January 1995 (1995-01-01), pages 284- 291, XP002077501 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3620446A1 (de) | 2018-09-05 | 2020-03-11 | Rheinisch-Westfälische Technische Hochschule (RWTH) Aachen | Verfahren zur herstellung von dimethoxymethan |
Also Published As
Publication number | Publication date |
---|---|
DE19839740A1 (de) | 2000-03-02 |
JP2002523489A (ja) | 2002-07-30 |
EP1109780A1 (de) | 2001-06-27 |
WO2000012471A8 (de) | 2000-09-21 |
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