WO2009147008A1 - Procédé de séparation de produits secondaires polymères à partir du 1,4-butine-diol - Google Patents

Procédé de séparation de produits secondaires polymères à partir du 1,4-butine-diol Download PDF

Info

Publication number
WO2009147008A1
WO2009147008A1 PCT/EP2009/055968 EP2009055968W WO2009147008A1 WO 2009147008 A1 WO2009147008 A1 WO 2009147008A1 EP 2009055968 W EP2009055968 W EP 2009055968W WO 2009147008 A1 WO2009147008 A1 WO 2009147008A1
Authority
WO
WIPO (PCT)
Prior art keywords
butynediol
catalyst
catalysts
hydrogenation
stream
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2009/055968
Other languages
German (de)
English (en)
Inventor
Rudolf Erich Lorenz
Patric MÜLLER
Robert Schlosser
Gerd Schäfer
Bernd Gagel
Rolf Pinkos
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of WO2009147008A1 publication Critical patent/WO2009147008A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol

Definitions

  • the invention relates to a process for the purification of a 1, 4-butynediol-containing material stream, which was obtained by reacting formaldehyde with acetylene in the presence of a catalyst by separation of impurities in the form of polymeric by-products and catalyst components and a process for the preparation of 1, 4- Butenediol and 1, 4-butanediol by hydrogenation of the purified 1, 4-butynediol, which comprises the separation of polymeric by-products.
  • DE-A 19 41 633 and DE-A 20 40 501 disclose general hydrogenation processes which can be used inter alia for 1,4-butynediol.
  • cuprene deposits on the catalyst and inhibits the contact of butynediol with the catalyst surface, with the result that the reaction slows down.
  • Catalyst components such as copper, bismuth and / or SiO 2 also deposit on catalyst and thus change the catalyst activity and selectivity.
  • disadvantages here include an increase in the pressure loss and an increased formation of undesired by-products, which adversely affect the efficiency of the process. If the catalyst is heavily soiled, it must be be removed and washed. This measure is usually done about six to seven times during the life of the catalyst. However, this has the further disadvantage that the purification of the catalyst results in a large amount of wastewater, which, because of its content of heavy metals, is correspondingly expensive to clean.
  • WO 2007/028716 A1 describes a process for the purification of 1,4-butynediol. According to this method, separation is possible. However, here the phase separation described in the process proves to be disadvantageous in a calming zone within which a period of one to five hours is waited for.
  • Butindiol which was obtained by synthesis of formaldehyde and acetylene in the presence of a catalyst to allow.
  • the solid contained should be reduced to such an extent that the purified 1, 4-butynediol can then be fed directly to a hydrogenation, in which by hydrogenation of 1,4-butenediol or 1, 4-butynediol in high selectivity and with good catalyst life can be won.
  • 1,4-butynediol is understood as meaning 1, 4-butynediol prepared from acetylene and formaldehyde, customary catalysts which have not been purified by distillation, for example, and generally from 10 to 70% by weight of butynediol , preferably 30 to 60% by weight of butynediol, 0.2 to 4% by weight of propynol 0.1 to 2% by weight of formaldehyde and 1 to 2000 ppm, preferably 3 to 500 ppm, particularly preferably 10 to 200 ppm Cuprene and catalyst components as well as ⁇ 0.1% contains other contaminant traces.
  • the disk separators used for the process according to the invention are known in their basic structure and their mode of operation and are described, for example, in “Solid-Liquid Filtration and Separation Technology", A. Rushton, 2nd edition 2000, WILEYVCH Verlag, pages 312-313 and in “Handbuch der mechanical solid-liquid separation ", Klaus Luckert, 2004 Vulkan-Verlag GmbH, pages 350-351 described.
  • the disclosure of this document is incorporated by reference in its entirety (incorporated by reference). They are usually used for the separation of liquid and solid materials, such. in the concentration of sludge.
  • a rotor that rotatably supports a plurality of conical plates axially spaced apart from each other and a stator that contains a dirt collecting space in which the rotor is disposed.
  • the plates increase the clarification area and reduce the sedimentation height, thus reducing the time for deposition.
  • the plates attached to the rotor rotate at high speed and thus a centrifugal field is generated, which is utilized for deposition.
  • an acceleration factor This is defined as the ratio of the centrifugal acceleration generated in the plate separator in the outer diameter of the plate to the gravitational acceleration. For plate separators, this acceleration factor is usually around 6000 to 12000, so they are classified as ultracentrifuges.
  • the cuprene contained are filamentous polymers, which presumably consist of highly condensed aromatic systems. Because of this threadlike structure formed in the attempted separation processes quickly larger, networked structures, which could be due to their stability, other separation experiments such as the flotation and filtration failed. Even when using a plate separator, a failure had to be expected in the case of this difficult-to-handle material system. Thus, in this apparatus, the plates are arranged at a very small distance, it is usually less than 0.5mm, often less than 0.3mm.
  • a rapid caking of the cuprene and the other solid impurities contained had been expected, which should lead a short time later with increasing growth to disruption in the separation process. Contrary to this expectation, however, the technical 1,4-butynediol could be successfully and permanently depleted to a high degree of solids.
  • the technical 1,4-butynediol obtained in the synthesis stage by reaction of formaldehyde and acetylene is passed directly into the plate separator for separation of the solid.
  • the Tellerseparator is preferably operated with an acceleration factor of 6000 to 12000, more preferably 8000 to 9000 and the plate angle range of the plate in Tellerseparator is 45 ° to 55 ° (measured on the horizontal).
  • the distances between the individual plates in the plate separator used in the method according to the invention are preferably less than 0.6 mm, more preferably less than 0.5 mm and also distances of less than 0.3 mm may be particularly recommended.
  • a further significant advantage of the process according to the invention is that both the technical 1,4-butynediol to be purified and the 1,4-butynediol depleted of solids and withdrawn via the shaft of the plate separator can be continuously supplied or removed ,
  • the solids content in the feed of the plate separator is usually about 50 to 2000 ppm and it can be achieved by means of the inventive method, a depletion of solids from 80Gew .-% to 98Gew .-%, preferably 90Gew .-% to 95Gew .-%.
  • the pulp separator a stream is fed, which contains 100 ppm of solids, this means, for example, that in the case of depletion of 95% corresponding 95 ppm of solid are deposited and the remaining 5 ppm in the Substance stream (also referred to as "clear run") substantially freed from the solid material is withdrawn via the shaft of the plate separator.
  • the solids-rich phase removed at intervals contains predominantly the cuprene as well as considerable amounts of copper, bismuth or SiC "2 -containing undesired catalyst components Combustion supplied, but can be treated previously, for example by distillation, to remove residual amounts of 1, 4-butynediol and due to the process of the invention.
  • the phase largely freed from cuprene and unwanted catalyst constituents and discharged via the shaft of the plate separator (clarified water) is preferably fed directly to the hydrogenation to 1,4-butenediol or 1,4-butanediol.
  • the present invention furthermore relates to a process for the hydrogenation of 1,4-butynediol to 1,4-butenediol and preferably to 1,4-butanediol in which purified 1,4-butynediol is used according to the process of the invention.
  • the hydrogenation of 1,4-butynediol is known per se and is preferably carried out in the liquid phase on fixed and / or suspended catalysts.
  • the hydrogenation can be carried out up to 1, 4-butanediol, but also only up to 1, 4-butenediol.
  • catalysts which are capable of hydrogenating C-C triple and double bonds to single bonds. They usually contain one or more elements of the I., VI, VII or VIII subgroup of the Periodic Table of the Elements, preferably the elements copper, chromium, molybdenum, manganese, rhenium, iron, ruthenium, cobalt, nickel, platinum and palladium. Particular preference is given to using catalysts which have at least one
  • Element selected from copper, chromium, molybdenum, iron, nickel, platinum and palladium.
  • the metal content of these catalysts is generally between 0.1 to 100 wt .-%, preferably 0.2 to 95 wt .-%, particularly preferably 0.5 to 95 wt .-%.
  • the catalyst preferably additionally contains at least one element selected from the elements of II., III., IV. And VI. Main group, the II, III, IV and V subgroups of the Periodic Table of the Elements and the lanthanides as a promoter for increasing activity.
  • the promoter content of the catalyst is generally up to 5 wt .-%, preferably 0.001 to 5 wt .-%, particularly preferably 0.01 to 3 wt .-%.
  • catalysts precipitation, carrier, or Raney type catalysts can be used, the preparation of which is described for example in Ullmanns, Encyclopedia of Industrial Chemistry, 4th Edition, 1977, Volume 13, pages 558-665.
  • carrier materials aluminum oxides, titanium oxides, zirconium dioxide, silicon dioxide, clays, for example montmorillonites, silicates such as magnesium or aluminum silicates, zeolites and activated carbons can be used.
  • Preferred support materials are aluminas, titanium dioxides, silica, zirconia and activated carbons.
  • Diver- It is also possible to use mixtures of various carrier materials as carriers for catalysts which can be used in the process according to the invention.
  • catalysts can be used either as shaped catalyst bodies, for example as spheres, cylinders, rings, spirals, or in the form of powders.
  • Raney type catalysts are Raney nickel, Raney copper, Raney cobalt, Raney nickel / molybdenum, Raney nickel / copper, Raney nickel / chromium, Raney nickel / chromium / iron or Rhenium sponge suitable.
  • Raney nickel / molybdenum catalysts can be prepared, for example, by the method described in US Pat. No. 4,153,578. However, these catalysts are also marketed, for example, by the company Degussa, 63403 Hanau, Germany.
  • a Raney nickel-chromium-iron catalyst is sold, for example, under the trade name Catalyst Type 11 112 W® by Degussa.
  • precipitated or supported catalysts these are reduced at the beginning of the reaction at 150 to 500 0 C in hydrogen or hydrogen / inert gas stream. This reduction can be carried out directly in the synthesis reactor. If the reduction is carried out in a separate reactor, the catalysts can be surface-passivated at 30 ° C. with oxygen-containing gas mixtures before being removed. The passivated catalysts can be activated in this case in the synthesis reactor before use in a nitrogen / hydrogen stream at 180 ° C or used without activation.
  • the catalysts can be used in a fixed bed or in suspension.
  • the reactor is operated not in the usual trickle mode, but in an upward direct flow of liquid and gas so that the liquid and not the gas is present as a continuous phase.
  • Suspended catalysts are used with a particle size generally of 0.1-500 .mu.m, preferably 0.5 to 200 .mu.m, particularly preferably 1 to 100 .mu.m.
  • the use of packed bubble columns will also work with an upward direct flow of liquid and gas such that the liquid and not the gas will be in a continuous phase.
  • the ratio of gas leaving the reaction vessel to the amount of gas supplied is 0.99: 1 to 0.4: 1 when using fixed bed reactors and when using packed bubble columns with a catalyst suspended in the reaction medium.
  • the ratio to be maintained in the packed bubble columns in the case of fixed bed reactors and catalysts suspended in the reaction medium can be adjusted in a simple manner by metering the appropriate amount of hydrogen either as a fresh gas or technically preferably recirculating recycle gas and only supplemented by chemical consumption and exhaust gas-related hydrogen loss by fresh hydrogen.
  • the molar ratio of hydrogen to 1,4-butynediol in the reactor is at least 3: 1, preferably between 4: 1 and 100: 1.
  • the process according to the invention is carried out on fixed-bed catalysts with cycle gas operation, i. the gas leaving the reactor is recycled in the circulation, optionally after addition of fresh hydrogen, via a compressor in the reactor. It is possible to lead the entire cycle gas quantity or a subset thereof via a propulsion jet compressor.
  • the cycle gas compressor is replaced by a low-cost nozzle.
  • the compression work is introduced via the likewise circulated liquid. The required pressure increase of the liquid for operating the jet compressor is about 3 to 5 bar.
  • Jet nozzle reactors For carrying out the process according to the invention with a catalyst suspended in the reaction medium, jet nozzle reactors, stirred tanks and bubble columns with packings which have a packing surface area of at least 500, preferably 1000 to 2000 m 2 / m 3 are suitable. Jet nozzle reactors can be used in various designs if they can ensure the high mass transfer from the gas phase to the liquid with the suspended catalyst particles which is essential for the invention by a sufficiently high energy input, which experience has shown is above 2 kW / m 3 . Particularly suitable are jet nozzle reactors which are equipped with a momentum exchange tube. An industrially widespread design of a jet nozzle reactor is, for example, the reactor described in EP-A 0 419 419. At values for the energy input of 3 to 5 kW / m 3 , with this reactor a separation of the gas phase is still possible in simple separators, without having to use additional apparatus such as foam centrifuges or cyclones.
  • Stirring containers are only suitable for carrying out the method according to the invention if the energy input is in a range from 2 to 10 kW / m 3 .
  • Jet nozzle reactors with suspended catalysts require volume-related energy inputs of more than 2 kW / m 3 , preferably 3 - 5 kW / m 3 .
  • 1, 4-butanediol is used in large quantities in the art, for example in THF production or as a diol component in polyesters.
  • the arithmetic mean depletion was 96.7% for the case of addition of 250 L / h at a mean feed concentration of 123 ppm.
  • the arithmetic mean depletion was 87.5% for the case of addition of 350 L / h at a mean feed concentration of 95 ppm.
  • aqueous solution based on the butynediol content was added in an amount of 100 g / h in the reactor.
  • a temperature of 140 0 C. was hydrogenated at a hydrogen pressure of 200 bar and a liquid circulation 800 ml / h was 2 weeks.
  • the hydrogenation was carried out analogously to the comparative example, with the difference that the prepurified according to the invention 1, 4-butynediol was used.
  • the average increase in n-butanol was about 0.04% per day. After removal of the catalyst, no deposits were found.
  • the yield of 1,4-butanediol, based on butynediol used, was 98.3% by weight at the beginning and decreased by 0.04% by weight each day.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention a pour objet un procédé de purification de 1,4-butine-diol, caractérisé en ce que le 1,4-butine-diol est envoyé en continu dans une centrifugeuse à plateau qui est actionnée à un facteur d'accélération de 6000 à 12000, et en ce que le butine-diol purifié est retiré en continu. L'invention a également pour objet un procédé d'hydrogénation du 1,4-butine-diol en 1,4-butène-diol et en 1,4-butane-diol, en utilisant le 1,4-butine-diol purifié.
PCT/EP2009/055968 2008-05-29 2009-05-18 Procédé de séparation de produits secondaires polymères à partir du 1,4-butine-diol Ceased WO2009147008A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP08157205 2008-05-29
EP08157205.9 2008-05-29

Publications (1)

Publication Number Publication Date
WO2009147008A1 true WO2009147008A1 (fr) 2009-12-10

Family

ID=41211712

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2009/055968 Ceased WO2009147008A1 (fr) 2008-05-29 2009-05-18 Procédé de séparation de produits secondaires polymères à partir du 1,4-butine-diol

Country Status (1)

Country Link
WO (1) WO2009147008A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4118207A (en) * 1976-12-06 1978-10-03 United States Steel Corporation Rotating disc particulate separator
DD272644A1 (de) * 1984-05-25 1989-10-18 Buna Chem Werke Veb Verfahren zur katalysatoraktivitaetserhoehung bei der butindiol-1,4-hydrierung
US5068468A (en) * 1990-10-19 1991-11-26 Basf Aktiengesellschaft Hydrogenation of acetylenic alcohols
WO1999054021A1 (fr) * 1998-04-16 1999-10-28 Helford Design Ltd. Separateur couche limite
EP1661626A1 (fr) * 2004-11-26 2006-05-31 MAHLE Filtersysteme GmbH Séparateur à disques
WO2007028716A1 (fr) * 2005-09-06 2007-03-15 Basf Se Procede de separation de sous-produits polymeriques du 1,4-butindiol

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4118207A (en) * 1976-12-06 1978-10-03 United States Steel Corporation Rotating disc particulate separator
DD272644A1 (de) * 1984-05-25 1989-10-18 Buna Chem Werke Veb Verfahren zur katalysatoraktivitaetserhoehung bei der butindiol-1,4-hydrierung
US5068468A (en) * 1990-10-19 1991-11-26 Basf Aktiengesellschaft Hydrogenation of acetylenic alcohols
WO1999054021A1 (fr) * 1998-04-16 1999-10-28 Helford Design Ltd. Separateur couche limite
EP1661626A1 (fr) * 2004-11-26 2006-05-31 MAHLE Filtersysteme GmbH Séparateur à disques
WO2007028716A1 (fr) * 2005-09-06 2007-03-15 Basf Se Procede de separation de sous-produits polymeriques du 1,4-butindiol

Similar Documents

Publication Publication Date Title
EP2121549B1 (fr) Procédé de preparation de 1,4-butanediol
EP0934239B1 (fr) Procede de preparation de 1,4-diol de butane par hydrogenation catalytique de 1,4-diol de butine
EP2417087B1 (fr) Procédé de production de 1,6-hexanediol par hydrogénation d'oligoesters et de polyesters
EP2417088B1 (fr) Procédé de production de 1,6-hexanediol
US7605292B2 (en) Method for the separation of polymeric by-products from 1,4-butynediol
EP2158192A1 (fr) Procédé de fabrication de -caprolactone
EP2429983A2 (fr) Procédé de préparation d'amines aromatiques
US7572941B2 (en) Method for the separation of polymeric by-products from 1,4-butynediol
EP2883857A1 (fr) Procédé de fabrication d'acide adipique ou d'au moins un de ses dérivés
EP1765751B1 (fr) Procede de production de 1,6-hexanediol d'une purete superieure a 99,5 %
WO2019048276A1 (fr) Procédé pour réguler l'hydrogénation catalytique de 1,4-butynediol par l'intermédiaire de la teneur en co et/ou ch4 du flux de gaz résiduaires
WO2002048128A2 (fr) Procede de production de tetrahydrofurane
EP2771330B1 (fr) Procede de preparation d'oxyde de rose cis
WO1999001206A1 (fr) Separation de catalyseurs en suspension par filtration a contre-courant sur une membrane
DE19737190A1 (de) Verfahren zur Herstellung von 1,3-Propandiol durch Hydrieren von Hydroxypropionaldehyd

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09757391

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09757391

Country of ref document: EP

Kind code of ref document: A1