WO1999001206A1 - Separation de catalyseurs en suspension par filtration a contre-courant sur une membrane - Google Patents

Separation de catalyseurs en suspension par filtration a contre-courant sur une membrane Download PDF

Info

Publication number
WO1999001206A1
WO1999001206A1 PCT/EP1998/003588 EP9803588W WO9901206A1 WO 1999001206 A1 WO1999001206 A1 WO 1999001206A1 EP 9803588 W EP9803588 W EP 9803588W WO 9901206 A1 WO9901206 A1 WO 9901206A1
Authority
WO
WIPO (PCT)
Prior art keywords
membrane
catalyst
reaction mixture
suspended
butanediol
Prior art date
Application number
PCT/EP1998/003588
Other languages
German (de)
English (en)
Inventor
Klemens Massonne
Erich Schubert
Georg Krug
Rolf Pinkos
Michael Karcher
Gerd Kaibel
Original Assignee
Basf Aktiengesellschaft
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 Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU85379/98A priority Critical patent/AU8537998A/en
Publication of WO1999001206A1 publication Critical patent/WO1999001206A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/06—Tubular membrane modules
    • B01D63/069—Tubular membrane modules comprising a bundle of tubular membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/147—Microfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/06—Tubular membrane modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/06—Tubular membrane modules
    • B01D63/061—Manufacturing thereof
    • 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 preparation of 1,4-butanediol by continuous catalytic hydrogenation of 2-butyne-1,4-diol over a suspended catalyst.
  • the invention also relates to a process for separating suspended catalysts from a liquid reaction mixture by crossflow filtration.
  • 1,4-butanediol is used in large quantities, for example in the production of THF or as a diol component in polyesters.
  • 2-butyn-1,4-diol is hydrogenated in the liquid phase over a suspended catalyst, often Raney nickel or a fixed bed catalyst, with hydrogen at high pressures.
  • the temperature during the hydrogenation is, for example, about 150 ° C.
  • the catalyst must be separated from the liquid reaction mixture, which is problem-free in the case of fixed bed catalysts. Different devices and methods have been used to separate the suspended catalyst.
  • DD-A-219 184 describes a process for the catalytic hydrogenation of 2-butyn-1,4-diol, in which the catalyst is continuously separated off in a sedimentation vessel and is returned as a recycle stream to the stirred reactor used. The gas is introduced for reduction by a hollow stirrer. In a second stage, the reaction is continued on a fixed bed catalyst until conversion is high.
  • DD-A-298 504 describes a process for working up nickel catalyst-loaded hydrogenation products for the production of aniline.
  • the suspended nickel catalyst is separated by centrifugal separation Separate the reaction mixture and, if necessary, return it to the reaction.
  • No. 4,182,919 describes a process for reactions in systems with suspended catalysts.
  • the reactor is equipped with a filter with which the catalyst in the reactor can be separated.
  • the filter is arranged in the reactor in such a way that its surface is swept by the stirred reaction mixture, which is to prevent excessive deposition of the powdery catalyst on the surface of the filter medium.
  • the filter can be designed in the manner of a pocket, a cylinder, a spiral tube, plate or the like.
  • a flexible filter medium is preferably used. It is stated that when a solid filter material, such as ceramic and sintered metals, is used, the filtering speed decreases after a longer reaction time and it is necessary to wash the filter back. This means that the direction of flow in the filter must be reversed in order to remove deposited particles. For this, the course of the reaction must be interrupted. It is also explained that the effect of backwashing is relatively small for rigid filter media, so that the filtering performance drops considerably. Backwashing often has to take place in relatively short periods of time.
  • a disadvantage of using sedimentation to separate the catalyst is the need to prepare large sedimentation vessels, which, as essential parts of the plant, cause high investment costs.
  • fine catalyst particles that sediment only slowly are not separated. This leads to a constant loss of catalyst of the smallest, generally most active particles and, as a result, to high catalyst costs.
  • centrifuges in addition to the removal of very fine particles, also has the disadvantage that the additional apparatus is due to its movements are susceptible to wear and correspondingly high operating costs.
  • the separation of suspended catalysts by filtration generally has the disadvantage that a filter cake is built up on the filter medium, which continuously deteriorates the filter performance and is not suitable for stable, continuous operation.
  • the arrangement of filter media in stirred reactors in the area of high turbulence does not lead to a solution to the problem, since regular backwashing is required to maintain the filter performance, which means an interruption of continuous operation.
  • the flow conditions on a filter cartridge installed in a stirred tank are not precisely defined, which makes it difficult to design a system.
  • Crossflow filtration has been proposed to solve the deposit problems in conventional filter media.
  • the suspension to be filtered continuously flows over a filter membrane, so that a covering layer build-up due to retained particles can be avoided.
  • the suspension flows transversely to the direction of filtration.
  • the principle of crossflow filtration is generally described in S. Ripperger, Chem.-Ing.-Tech. 60 (1988) No. 3, pages 155 to 161.
  • the filter membranes used are predominantly membranes made of polymers, for example made of cellulose acetate, polyamide, polypropylene, polyvinylidene, fluoride or polytetrafluoroethylene.
  • Such a cross-flow filtration method is described in DE-A-28 04 225.
  • the catalyst-containing solution is passed over a polyamide filter membrane having a mean pore size of 10 nm at a speed of at least 1 m / s.
  • the butynediol synthesis is carried out by continuous Reaction of acetylene with formaldehyde in aqueous solution carried out on heavy metal catalysts suspended in the reaction mixture.
  • the catalytic hydrogenation of 2-butyn-1,4-diol to 1,4-butanediol is carried out at temperatures above 100 ° C., generally 140 to 160 ° C., at a pressure of more than 20 bar.
  • polymer membranes only have a temperature resistance up to about 80 ° C and show a poor chemical resistance. For example, they can swell in the presence of certain solvents and thus change their structure. The mechanical strength of the membranes under pressure is often insufficient.
  • the reaction mixture is also agitated mechanically (for example by stirring) and mechanically heavily loaded (for example by pumping in a circuit).
  • the catalyst particles are ground into an ever finer powder over time.
  • an incomplete separation of the catalyst leads to a loss of expensive catalyst
  • solid parts remaining in the product stream can lead to contamination in subsequent parts of the system, for example in distillation columns. As a result, these parts of the system often have to be cleaned, causing downtimes of the entire system and thus loss of productivity.
  • the desired product should be kept as pure as possible.
  • the object of the present invention is to provide a process for separating suspended catalysts from a liquid reaction mixture which avoids the disadvantages described above and ensures that the catalyst is retained as completely as possible.
  • the process should also be able to be carried out under conditions which prevail in the catalytic hydrogenation of 2-butyne-1,4-diol to 1,4-butanediol.
  • the object is achieved according to the invention by providing a process for separating suspended catalysts from a liquid reaction mixture by cross-flow filtration of the catalyst-containing reaction mixture on a membrane in which the membrane is composed of inorganic material and has an average pore diameter of less than 1000 nm.
  • membranes made of inorganic material with an average pore diameter of less than 1000 nm for separating suspended catalysts from a liquid reaction mixture, in particular a reaction mixture from the catalytic hydrogenation of 2-butyne-1,4-diol to 1.4 -Butanediol are suitable because they guarantee a high separation performance with a long service life and reliable operation of the system.
  • the hydrogenation catalysts customary for this reaction are used as catalysts. They usually contain one or more elements of L, VI. , VII. Or VIII. Subgroup of the Periodic Table of the Elements, preferably copper, chromium, molybdenum, manganese, rhenium, iron, ruthenium, cobalt, nickel, platinum and / or palladium. Catalysts containing at least one element selected from copper, chromium, molybdenum, iron, nickel, platinum and palladium are particularly preferably used.
  • the metal content of these catalysts is generally between 0.1 to 100% by weight, preferably 0.2 to 95% by weight, particularly preferably 0.5 to 95% by weight.
  • 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. Subgroup 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% by weight, preferably 0.001 to 5% by weight, particularly preferably 0.01 to 3% by weight.
  • Raney-type catalysts can be used as catalysts, the production of which is described, for example, in Ulimann, Encyclomann die der Technischen Chemie, 4th edition, 1977, volume 13, pages 558 to 665.
  • Raney-type catalysts They are preferably Raney-type catalysts.
  • Examples of such catalysts are Raney nickel, Raney copper, Raney cobalt, Raney nickel / molybdenum, Raney nickel / copper, Raney nickel / chromium, Raney nickel / chromium / iron or rhenium sponge.
  • Raney nickel / molybdenum catalysts can be produced, for example, by the process described in US Pat. No. 4,153,578. These catalysts are also sold, for example, by Degussa, 63403 Hanau, Germany.
  • a Raney nickel-chromium-iron catalyst is sold, for example, by Degussa under the trade name catalyst type 11 112 W® .
  • Suspended catalysts are generally used with a particle size of 0.1 to 500 ⁇ m, preferably 0.5 to 200 ⁇ m, particularly preferably 1 to 100 ⁇ m.
  • the mechanical stress during the reaction by stirring and pumping the reaction mixture reduces the particle size of the catalyst over time.
  • the catalyst particles are exposed to particularly high mechanical loads, so that the comminution proceeds faster.
  • the size reduction usually makes it difficult to separate the catalyst from the reaction mixture.
  • the average pore diameter of the membrane is less than 1000 nm, preferably 10 to 100 nm, in particular 20 to 50 nm.
  • the membrane can also be constructed from any inorganic material.
  • the membrane is preferably constructed from ceramic material. Examples of substances from which the ceramic can be constructed are aluminum oxide, zirconium oxide and titanium dioxide.
  • the membrane is particularly preferably composed of aluminum oxide / zirconium oxide. Suitable membranes are offered, for example, by Membraflow under the name Membralox ® .
  • the membrane can have any suitable geometry.
  • the membrane is preferably used in the form of cylindrical tubes.
  • the inner diameter is preferably 4 to 6 mm and the length of the tube 0.85 to 1.02 m.
  • the catalyst-containing reaction mixture flows along the membrane at a flow rate of preferably at least 1.5 m / s, particularly preferably 1 to 5 m / s, in particular 2 to 4 m / s.
  • the membranes made of an inorganic material described above can be used in a variety of reaction mixtures with suspended catalyst. They are preferably used to separate suspended catalyst-containing reaction mixtures from the catalytic hydrogenation of 2-butyn-1,4-diol to 1,4-butanediol.
  • the catalytic hydrogenation is preferably carried out at temperatures in the range from 20 to 300 ° C., preferably 60 to 220 ° C., particularly preferably 120 to 180 ° C., especially 140 to 160 ° C. Temperatures above 100 ° C. are generally preferred.
  • the pressure is 1 to 200 bar, preferably 3 to 150 bar, particularly preferably 5 to 100 bar, in particular 20 to 100 bar. Work is often carried out at a pressure of more than 20 bar.
  • values of the liquid-side volume-related mass transfer coefficient k L a of 0.1 to 1 s "1 are preferably used.
  • the mass transfer coefficient is preferably 0.2 to 1 s " 1 .
  • the reaction can be carried out in a variety of reactors.
  • the hydrogenation is carried out in a stirred reactor in which the membrane is arranged in a separate pumping circuit.
  • the hydrogenation can also be carried out in a bubble column or a jet nozzle reactor, the membrane being arranged in the liquid circuit.
  • the membrane made of inorganic material used in accordance with the invention must also withstand pressure stress.
  • An absolutely tight separation of the permeate side and retentate side of the filter membrane must be achieved to ensure complete separation of the catalyst.
  • the housing of the filter membrane is preferably made of metallic materials, since it has to withstand the reactor pressure. Since the linear thermal expansion coefficients of metallic materials differ greatly from those of ceramic materials, filter material and housing cannot be firmly connected, as this would lead to a breakage of the brittle filter material.
  • the membrane is mounted in a special way in the metal housing, as indicated in a cross-sectional view in FIG. 2.
  • sealing ring Insert ring as an assembly aid
  • the special design of the filter unit, as shown in FIG. 2 for one side of the tubular ceramic membrane, ensures reliable operation even when the temperature fluctuates.
  • the catalytic hydrogenation of 2-butyne-1,4-diol is possible with high space-time yields and selectivities with a filter performance that is constant over time. Neither an interruption of the process for cleaning purposes or for backwashing, nor a double execution of the filtration unit for mutual operation is required. As a result, the availability of the corresponding production plant is high and the investment costs are low. By fully retaining the catalyst, it is used optimally and the catalyst costs are kept low.
  • the apparatus consists of a 40 liter pressure reactor with a hollow shaft gassing stirrer and thermostatted double jacket as well as a pressure maintenance device.
  • a pump circuit with a circulating pump is located on the reactor.
  • a tubular heat exchanger with an area of 0.17 m 2 and the filtration unit according to the invention are arranged one after the other on the pressure side of the circulation pump.
  • the constant filter performance was shown by an unchanged transmembrane pressure above the filter membrane of between 490 and 520 mbar.
  • the liquid reaction discharge contained (calculated anhydrous) during the entire time between 93.5 and 93.7% by weight of 1,4-butanediol.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé pour séparer des catalyseurs en suspension contenus dans un mélange de réaction liquide, par filtration à contre-courant de ce mélange sur une membrane, laquelle est constituée d'un matériau inorganique et présente un diamètre de pore moyen inférieur à 1000 nm. Ces membranes s'utilisent pour séparer des catalyseurs en suspension dans des mélanges de réaction contenant des catalyseurs et provenant de l'hydrogénation catalytique de 2-butin-1,4-diol pour donner du 1,4-butandiol.
PCT/EP1998/003588 1997-06-30 1998-06-15 Separation de catalyseurs en suspension par filtration a contre-courant sur une membrane WO1999001206A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU85379/98A AU8537998A (en) 1997-06-30 1998-06-15 Separation of suspended catalysts by cross-flow filtration on a membrane

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1997127715 DE19727715A1 (de) 1997-06-30 1997-06-30 Verfahren zur Herstellung von 1,4-Butandiol
DE19727715.2 1997-06-30

Publications (1)

Publication Number Publication Date
WO1999001206A1 true WO1999001206A1 (fr) 1999-01-14

Family

ID=7834064

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1998/003588 WO1999001206A1 (fr) 1997-06-30 1998-06-15 Separation de catalyseurs en suspension par filtration a contre-courant sur une membrane

Country Status (3)

Country Link
AU (1) AU8537998A (fr)
DE (1) DE19727715A1 (fr)
WO (1) WO1999001206A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9555374B2 (en) 2009-04-29 2017-01-31 Basf Se Method for conditioning catalysts by means of membrane filtration

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003516852A (ja) * 1999-12-17 2003-05-20 ワーナー・ランバート・リサーチ・アンド・ディベロップメント・アイルランド・リミテッド 発火触媒を除去するための装置
EP1283742A1 (fr) * 2000-05-19 2003-02-19 Inocermic Gesellschaft für Innovative Keramik mbH Module de separation et son procede de production

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2804225A1 (de) * 1978-02-01 1979-08-02 Huels Gaf Chemie Gmbh Verfahren zur erzeugung einer katalysatorfreien butindiolloesung
US4182919A (en) * 1977-03-31 1980-01-08 Toyo Soda Manufacturing Co., Ltd. Process for reaction in catalyst suspension system
EP0177912A1 (fr) * 1984-10-12 1986-04-16 BASF Aktiengesellschaft Procédé pour la préparation d'alcane-diols
DE3727276A1 (de) * 1986-08-20 1988-02-25 Toshiba Ceramics Co Vorrichtung zur herstellung von estern
US4756821A (en) * 1986-02-10 1988-07-12 Institut Francais Du Petrol Method for the liquid phase hydrotreatment of heavy hydrocarbons in the presence of a dispersed catalyst
WO1991016294A1 (fr) * 1990-04-14 1991-10-31 Hoechst Aktiengesellschaft Procede de recuperation d'un catalyseur
EP0504839A1 (fr) * 1991-03-19 1992-09-23 Hoechst Aktiengesellschaft Procédé de séparation des catalyseurs de suspensions par filtration
EP0571762A1 (fr) * 1992-05-25 1993-12-01 Degussa Ag Procédé pour séparer une solution de travail exempte de catalyseur d'une circulation d'hydrogénation du procédé anthraquinone pour la préparation d'eau oxygénée
WO1997046306A1 (fr) * 1996-06-04 1997-12-11 Rhodia Fiber And Resin Intermediates Procede de filtration d'un melange reactionnel triphasique

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4182919A (en) * 1977-03-31 1980-01-08 Toyo Soda Manufacturing Co., Ltd. Process for reaction in catalyst suspension system
DE2804225A1 (de) * 1978-02-01 1979-08-02 Huels Gaf Chemie Gmbh Verfahren zur erzeugung einer katalysatorfreien butindiolloesung
EP0177912A1 (fr) * 1984-10-12 1986-04-16 BASF Aktiengesellschaft Procédé pour la préparation d'alcane-diols
US4756821A (en) * 1986-02-10 1988-07-12 Institut Francais Du Petrol Method for the liquid phase hydrotreatment of heavy hydrocarbons in the presence of a dispersed catalyst
DE3727276A1 (de) * 1986-08-20 1988-02-25 Toshiba Ceramics Co Vorrichtung zur herstellung von estern
WO1991016294A1 (fr) * 1990-04-14 1991-10-31 Hoechst Aktiengesellschaft Procede de recuperation d'un catalyseur
EP0504839A1 (fr) * 1991-03-19 1992-09-23 Hoechst Aktiengesellschaft Procédé de séparation des catalyseurs de suspensions par filtration
EP0571762A1 (fr) * 1992-05-25 1993-12-01 Degussa Ag Procédé pour séparer une solution de travail exempte de catalyseur d'une circulation d'hydrogénation du procédé anthraquinone pour la préparation d'eau oxygénée
WO1997046306A1 (fr) * 1996-06-04 1997-12-11 Rhodia Fiber And Resin Intermediates Procede de filtration d'un melange reactionnel triphasique

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9555374B2 (en) 2009-04-29 2017-01-31 Basf Se Method for conditioning catalysts by means of membrane filtration

Also Published As

Publication number Publication date
DE19727715A1 (de) 1999-01-07
AU8537998A (en) 1999-01-25

Similar Documents

Publication Publication Date Title
DE60109678T2 (de) Nachrüstreaktor mit Gas-Flüssigkeitsejektor und Monolithkatalysator
EP0934239B1 (fr) Procede de preparation de 1,4-diol de butane par hydrogenation catalytique de 1,4-diol de butine
EP2424647B1 (fr) Procédé de exfiltration et conditionnement de catalyseurs par filtration sur membrane
DE3245318C3 (de) Verfahren zur Durchführung von Druckreaktionen mit suspendierten Katalysatoren
EP0572812B1 (fr) Procédé de préparation de 1,3-propanediol par hydrogénation de la hydroxypropionaldéhyde
DE69817356T2 (de) Verfahren zur herstellung von 1,3-propandiol durch hydrierung von 3-hydroxypropanal
DE4418931C2 (de) Verfahren zur Abtrennung katalysatorfreier Arbeitslösung aus dem Hydrierkreislauf des Anthrachinonverfahrens zur Herstellung von Wasserstoffperoxid
EP1318128B1 (fr) Procédé pour l'hydrogénation de composés carbonylés oléfiniquement insaturés
EP1926695B1 (fr) Procede de separation de produits secondaires polymeres contenus dans le compose 1,4-butyndiol
EP1926696B1 (fr) Procede de separation de sous-produits polymeriques du 1,4-butindiol
EP0776887B1 (fr) Procédé continu pour la préparation de 4-amino-2,2,6,6-tetramethylpiperidine
WO2003066571A1 (fr) Procede de production d'amines
DE60225148T2 (de) Verfahren zur herstellung von flüssigen kohlenwasserstoffen
DE3229905A1 (de) Festbett-katalysator
WO1999001206A1 (fr) Separation de catalyseurs en suspension par filtration a contre-courant sur une membrane
EP0571762A1 (fr) Procédé pour séparer une solution de travail exempte de catalyseur d'une circulation d'hydrogénation du procédé anthraquinone pour la préparation d'eau oxygénée
EP1523464B1 (fr) Procede d'hydrogenation continue de citronellal en citronellol
EP4234527B1 (fr) Procédé d'hydratation des aldéhydes en c9 en au moins deux étages d'hydratation
EP4234525B1 (fr) Procédé d'hydratation des aldéhydes en au moins deux étages d'hydratation
DE19936208A1 (de) Kontinuierliches Verfahren zur Herstellung von 2-Phenylethanol aus Styroloxid
DE10231944A1 (de) Verfahren zur kontinuierlichen Hydrierung von Citral zu Citronellal
WO1999019292A1 (fr) Procede continu de preparation d'amines aromatiques
WO2009147008A1 (fr) Procédé de séparation de produits secondaires polymères à partir du 1,4-butine-diol
DE10235552A1 (de) Verfahren zur Durchführung einer heterogen katalysierten Reaktivdestillation in Suspensionsfahrweise

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AU BG BR BY CA CN CZ GE HU IL JP KR KZ LT LV MX NO NZ PL RO RU SG SI SK TR UA US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
NENP Non-entry into the national phase

Ref country code: JP

Ref document number: 1999506219

Format of ref document f/p: F

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA