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EP2205547A2 - Procede d'oxydation d'alcools cycloaliphatiques, de cetones cycloaliphatiques ou de leurs melanges avec de l'acide nitrique aqueux, et recuperation des acides dicarboxyliques - Google Patents

Procede d'oxydation d'alcools cycloaliphatiques, de cetones cycloaliphatiques ou de leurs melanges avec de l'acide nitrique aqueux, et recuperation des acides dicarboxyliques

Info

Publication number
EP2205547A2
EP2205547A2 EP08841083A EP08841083A EP2205547A2 EP 2205547 A2 EP2205547 A2 EP 2205547A2 EP 08841083 A EP08841083 A EP 08841083A EP 08841083 A EP08841083 A EP 08841083A EP 2205547 A2 EP2205547 A2 EP 2205547A2
Authority
EP
European Patent Office
Prior art keywords
column
reaction
nitric acid
mixture
cyclohexanone
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.)
Withdrawn
Application number
EP08841083A
Other languages
German (de)
English (en)
Inventor
Christian Miller
Thomas Jaworek
Manfred Stroezel
Günther Achhammer
Thomas Papkalla
Wilfried Berning
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
Priority claimed from DE200710050713 external-priority patent/DE102007050713A1/de
Priority claimed from DE102008009992A external-priority patent/DE102008009992A1/de
Application filed by BASF SE filed Critical BASF SE
Publication of EP2205547A2 publication Critical patent/EP2205547A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
    • C07C51/316—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with oxides of nitrogen or nitrogen-containing mineral acids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the present invention relates to a process for the oxidation of cycloaliphatic alcohols, cycloaliphatic ketones or mixtures thereof with aqueous nitric acid and workup of the dicarboxylic acids by distillation.
  • the synthesis of dicarboxylic acids can be carried out by oxidation of cycloaliphatic alcohols, cycloaliphatic ketones or mixtures thereof in aqueous nitric acid with the aid of oxygen-containing gases.
  • the present invention therefore an object of the invention to develop an improved method.
  • a temperature of 40 to 120 0 C, preferably 60 to 90 0 C, particularly preferably 70 to 80 ° C and a pressure of 1 to 2000 mbar, preferably 50 to 300 mbar, particularly preferably 100 to 200 mbar cycloaliphatic alcohols, cycloaliphati - See ketones or mixtures thereof are reacted with nitric acid in the presence of a catalyst in a fractionation, reaction and / or rectification.
  • the process according to the invention can be carried out batchwise or continuously, preferably continuously.
  • Suitable fractionation, reaction and / or rectification columns are as a rule those columns with or without, preferably with internals, containing 1 to 150, preferably 2 to 100, more preferably 3 to 50, in particular 4 and 20 theoretical plates (plates) contain.
  • the fractionation, reaction and / or rectification columns generally contain at least three (3), ie 3 to 20, preferably 3 to 10, particularly preferably 3 to 6, in particular 3 provided with internals segments which follow one another directly or preferably with Intermediate spaces are provided.
  • the individual segments can still be divided in themselves and contain various installations.
  • the intermediate spaces generally have a length ratio to the underlying segment of 0.01: 1 to 10: 1, preferably 0.1: 1 to 5: 1, particularly preferably 0.2: 1 to 1: 1.
  • the fractionation, reaction and / or rectification columns contain a sump and a head area, which usually contains no internals.
  • the distillation is a thermal separation process.
  • the separation of a liquid mixture is achieved by partial evaporation of the mixture and subsequent condensation of the mixture vapor.
  • the vapor over the boiling liquid mixture contains more low-boiling components than the liquid mixture.
  • the distillate is richer in lighter than the liquid mixture used.
  • the distillation process consists of evaporation and condensation. In the simplest case, the process consists of a simple discontinuous evaporation and the spatially separate condensation of the evaporated mixture vapor.
  • the basic principle of distillative separation is the different vapor pressures of the mixture components. The substances with the higher vapor pressure preferably remain in the vapor phase. Simple distillation thus results in an enrichment of the highly volatile component in the distillate.
  • additional side streams can be removed at different points between the head and the sump.
  • the lowest part of the column below the column internals is referred to as column bottom and the top part above the internals as column head.
  • the most important additional apparatuses for heating or for producing the vapor phase, an evaporator and for cooling or condensing the vapors one or more capacitors are needed.
  • some of the vapors in condensed form must be returned to the top of the column.
  • Koch Flexipak, Rombopak, or any other kind of packs and separating trays such as perforated trays, bubble trays, valve trays, dual-flow trays, tunnel trays in single or multi-flow design, preferably bell or tunnel trays, particularly preferably tunnel trays in the execution of Thormann® trays Company Montz.
  • Suitable dicarboxylic acids are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, heptanedioic acid, octanedioic acid, nonanedioic acid, decanedioic acid undecanedioic acid, dodecanedioic acid, preferably succinic acid, glutaric acid, adipic acid and dodecanedioic acid, particularly preferably adipic acid and dodecanedioic acid.
  • Suitable cycloaliphatic alcohols are cyclobutanol, cyclopentanol, cyclohexanol, cyclooctanol, caclononanol, cyclodecanol, cycloundecanol, cyclododecanol, preferably cyclobutanol, cyclopentanol, cyclohexanol and cyclododecanol, more preferably cyclohexanol and cyclododecanol.
  • Suitable catalysts are iron, cobalt, nickel, copper and vanadium, preferably cobalt, copper and vanadium, more preferably copper and vanadium.
  • nitric acid is aqueous nitric acid such as 20 to 98 wt .-%, preferably 30 to 80 wt .-%, more preferably 40 to 70 wt .-%, in particular 55 to 65 wt .-% nitric acid.
  • the process according to the invention can advantageously be carried out by dosing the aqueous nitric acid together with a catalyst via the feed (1) and / or feed (2) to the internals of the region (II) of a fractionation column (A) which acts as a reaction and rectification column.
  • a portion of the nitric acid can be added via the inlet (3) below the region (II) of the column or via the inlet (4) into the bottom of the column. It may also be advantageous via feeds (1) to (4) to recycle streams which optionally contain product and by-products, nitric acid, water and catalyst of different composition, to the column.
  • the number of addition points of cycloalkone (s), cycloalcohol (s) or mixtures thereof in the region (II) of the column is generally between 1 and infinity, ie 1 to 100, preferably 1 to 30, particularly preferably 1 to 8, in particular 1 and 3 additional points.
  • the addition can take place wholly or partly in the liquid phase or gas phase in the region of the internals (II). It is advantageous if cycloalkone (s), cycloalcohol (s) or mixtures thereof as finely divided as possible z. B. via nozzles, pipes with holes with suitable devices such as nozzles, liquid distributor, nozzle pipes with holes in the To bring in column.
  • nozzles in known embodiments such as single-component, two-component or multi-component nozzles, hollow cones, full cones, flat jet or glass jet nozzles from Lechler, Schlick, Spraying Systems or other manufacturers or any other kind of distributor constructions which are as fine as possible and even distribution of the liquid or gaseous educt mixture, such as nozzle distributors, perforated distributors with and without pres- sure, overflow distributors, perforated bottom distributors, perforated channel distributors with and without pre-distribution, distributors with drop-off fingers, sewer distributors. It may be advantageous to combine the metering with static mixing elements.
  • the reaction of the cycloalkanone (s), cycloalcohol (s) or mixtures thereof with the nitric acid take place.
  • the reaction products formed are generally removed from the reaction zone (II) continuously.
  • the resulting dicarboxylic acids are usually together with a portion of the nitric acid as high-boiling components in the bottom (D) of the fractionation and can be removed via the stream (8).
  • the desired nitric acid concentration in the reaction zone (II) of the column be set.
  • the withdrawal streams (7) and (8) it is also possible to adjust the concentration of the reaction product in the sump.
  • the low-boiling components of water and a portion of the nitric acid pass through the distillative effect in the upper region (I) of the column.
  • the column (A) usually consists of several zones with different functions. On the column internals of the reaction zone (II) described above is carried out essentially the reaction of the reactants with simultaneous removal by distillation of the resulting products. Above segment (II) are the distillation zones (I), which are equipped with separating elements such as fillers, packings or trays. In this zone, nitric acid is separated from water. Due to the thermodynamic boiling behavior, the nitric acid passes back into the region (II) of the column (A), while the water at the top of the column (E) is obtained in gaseous form, condensed in the condenser (C) and partly via the return flow (6) in the Column (A) fed and discharged in part via the withdrawal stream (7). In this way, an advantageous concentration profile can be set by the internal reflux in the column. A reflux ratio between 0: 1 and 100: 1, preferably between 0.1: 1 and 5: 1, should be set.
  • a suitable reflux ratio usually between 0.01 and 100 by adjusting the energy input through the evaporator (B) and capacitor (C) contains the withdrawn stream ( 7) more or less residual concentrations of nitric acid.
  • Other high-boiling components such as catalyst or reaction products, which could be entrained from zone (II) to zone (I) due to high gas velocity in parts of column (A), are also precipitated in zone (I) and back to the bottom Part of the column recycled.
  • a partial stream from the column can be taken off via the side take-off streams (14) and (15) in gaseous or liquid form.
  • a gaseous withdrawal is particularly advantageous when very highly concentrated nitric acid is used or when the bottom product is to contain very high concentrations of product. Then it can be deducted in a very pure concentration via a gaseous discharge nitric acid.
  • the gaseous stream (15) is condensed in a condenser (K), collected in the vessel (L) and withdrawn via the pump (M).
  • the nitric acid can also be carried out via the middle withdrawal of a dividing wall column. The reaction then takes place on the feed part of the dividing wall column, while in the extraction part, the nitric acid is concentrated and withdrawn.
  • zone (III) which, like the zone (I), are provided with separation elements acting by distillation, for example packing, packings or trays.
  • concentration of the reaction product is carried out so that in the bottom (D) of the column (A), the desired product concentration for further workup is achieved.
  • product concentrations between 0 and 90 wt .-%, preferably between 10 and 50 wt .-%, particularly preferably between 20 and 40 wt .-% can be achieved.
  • Excess nitric acid passes through the distillative effect again in the zone (II) of the column (A) and there can react again with the supplied Mattersedukt cycloalkone and cycloalkane.
  • the high-boiling reaction product from the bottom (D) of the column (A) can be withdrawn via the bottom stream (9) together with nitric acid by means of a pump (H).
  • a portion of the bottom stream (9) can be vaporized with an evaporator (B) and passed through the vapor line (10) in the column. This produces the vapor required for the distillation.
  • the resulting in the reaction in the zone (II) nitrogen oxides go as a volatile gas immediately in the gas phase over the zone (I) of the column up in the head (E) of the column (A).
  • the nitric oxide is not condensed in the condenser (C) of the column (A) with a suitable choice of the heat carrier temperature (temperature at which the NO at the selected pressure does not pass into the liquid phase, but remains gaseous) and comes together with other gases (especially nitrogen) to the vacuum pump (G).
  • the exhaust gas then contains nitrogen oxides such as nitrogen dioxide, oxygen and optionally nitrogen. Via the vacuum pump (G), the exhaust gas can then be wholly or partially recycled to the column (A). Suitable feed points were the feed streams (11), (12) and (13).
  • the nitrous gas enters zone (II) of the reactor.
  • nitric acid continuously forms, which in turn oxidizes the respective cyclo compound.
  • oxygen or oxygen-containing gases via the feed streams (16), (17) and / or (18), the oxidation of nitrogen monoxide to nitrogen dioxide can be accelerated.
  • the feed streams (11) and (16) which are located between zone (II) and zone (III) of the column (A)
  • the zone (III) or the bottom (D) of the column (A) that gases remain dissolved in the liquid product.
  • reaction trays with a long residence time and defined flow direction are combined with the nozzle lances and / or cooling or heating coils (Jl).
  • the heat transfer coils can be used for additional dissipation of the heat of reaction, or be used for startup and shutdown. However, this is generally not necessary if there is sufficient fluid content on the internals in the area of the reaction.
  • the liquid holdup should always be greater than the amount of liquid through which the heat of reaction liberated during the reaction can evaporate in a defined period of time (eg residence time). It is advantageous to finely disperse the starting material mixture and meter it in uniformly over the column bottom. This can be done, for example, that the nozzle lances holes are made with different bore diameters. It may be advantageous for the mixing, to provide the nozzle lances with static mixing elements.
  • fractionation columns which, with their internals, have from 1 to 150 theoretical plates, preferably from 2 to 100 theoretical plates, more preferably from 3 to 50 theoretical plates, in particular 4 and 20 theoretical plates. It has proven particularly advantageous if 1 to 5 theoretical plates, preferably 2 to 4 theoretical plates, in the reaction zone (III), 1 to 5 theoretical plates, preferably 2 to 4 theoretical plates, in the zone (II) and 1 to 10, preferably 2 to 7 theoretical plates, in the upper part of the column (I) above the feed stream (1) are provided.
  • the process according to the invention can in principle be applied to all chemical syntheses for the preparation of dicarboxylic acids starting from cycloalkanones and / or cycloalcohols with aqueous acid.
  • the process has special significance for the oxidation of cyclohexanone and cyclohexanol to adipic acid.
  • the products can be prepared with complete conversion of the cycloalkones and / or cycloalkanes in high selectivity with simultaneous removal of tion of excess nitrous gases, water and or nitric acid.
  • the experimental apparatus consisted of a heatable 2-liter reaction flask made of stainless steel, on which a distillation column (length: 1, 5 m, diameter: 50 mm) was placed.
  • the column was filled in the lower area (zone (III)) with 3 bubble-cap trays, in the middle area (zone (II)) with 5 bubble-cap trays and in the upper area (zone (I)) with 6 bubble-cap trays.
  • the feeding of the reaction solution (mixture of cyclohexanol and cyclohexanone) took place via a multi-hole insert tube on the 4th bubble cap (viewed from below).
  • the column was equipped with three thermocouples, so that except in the bottom (in the liquid) and at the top of the column (gas region before the condenser) in the reaction region (II), the temperature in the liquid phase could be measured.
  • the reactants were metered out of scales on storage tanks with a pump mass-current controlled in the column.
  • the evaporator (B) was heated by means of a thermostat.
  • the bottom stream (8) was conveyed out of the evaporator in a stand-controlled manner with a pump into a container standing on a balance.
  • the top stream of the column was in a condenser (C) at temperatures between 40 and 60 0 C, condensed out.
  • One part (7) of the condensate was pumped to a distillate tank standing on a balance, while the other part (6) was returned to the column.
  • the apparatus was equipped with a pressure control (F1) which was able to regulate a pressure of 50 to 300 mbar.
  • the temperature in the reaction zone (II) of the column was controlled by adjusting the heating power and the return amount to a predetermined temperature.
  • the nitric acid concentration was adjusted in the reaction area.
  • All incoming and outgoing streams were continuously recorded and registered with a PLS throughout the experiment.
  • the equipment was driven in 8-hour operation (stationarity). After about 4 hours, a stationary state arose.
  • the bottom temperature was 82 ° C.
  • the gas temperature before the condenser was 59 ° C. 551 g / h of crude product with 59.6% by weight of HNO 3, 5.2% by weight of adipic acid (ADS), 0.5% by weight of glutaric acid, traces ( ⁇ 0.1% by weight) of the column were used as the bottom stream of the column. %) of succinic acid and water.
  • ADS adipic acid
  • succinic acid and water At the top of the column 449 g / h of distillate were withdrawn consisting of water.
  • the nitrous gases were discharged in gaseous form via a torch.
  • the thus obtained HNO3 content on the reaction tray was about 56 wt .-%.
  • the bottom temperature was 77 ° C.
  • the gas temperature upstream of the condenser was 50 0 C.
  • the bottom stream from the column was 560 g / h of crude product with 59.0% by weight of HNO3, 6.2 wt .-% adipic acid (ADA), 0.4 wt .-% glutaric , 0.03 wt .-% of succinic acid and water.
  • ADA adipic acid
  • succinic acid 0.03 wt .-% of succinic acid and water.
  • At the top of the column 461 g / h distillate were withdrawn consisting of water.
  • the nitrous gases were discharged in gaseous form via a torch.
  • Example 2 In the apparatus described in Example 1, 1000 g / h of an aqueous nitric acid solution (37%) was continuously added to the 8th tray (from below) of the column. In this solution, a copper / vanadium catalyst was dissolved. On the 4th floor was continuously 23 g / h of a mixture of 40 wt .-% cyclohexanone and 60 wt .-% cyclohexanol pumped. It was set a system pressure of 126 mbar and a return flow of about 429 g / h. The temperature in the reaction zone (II) of the column was controlled by adjusting the heating power and the reflux amount to 71 0 C.
  • the thus obtained HNO3 content on the reaction tray was about 60 wt .-%.
  • the bottom temperature was 74 ° C.
  • the gas temperature before the condenser was 47 ° C. 553 g / h of crude product with 59.0% by weight of HNO 3, 5.8% by weight of adipic acid (ADS), 0.34% by weight of glutaric acid, 0.03% by weight of succinic acid were used as the bottom stream of the column as well as won water.
  • ADS adipic acid
  • succinic acid succinic acid
  • Example 2 1003 g / h of an aqueous nitric acid solution (37%) was continuously added to the 8th tray (from below) of the column. In this solution, a copper / vanadium catalyst was dissolved. On the 4th floor were continuously 23 g / h of a mixture of 15 wt .-% cyclohexanone and
  • Example 1 The apparatus described in Example 1 was equipped with additional heating elements in the bottom region of the column. In addition, all piping and fittings in the lower part of the column were accompanied by heating in order to avoid a loss of solids.
  • Example 1 The apparatus described in Example 1 was equipped with additional heating elements in the bottom region of the column. In addition, all piping and fittings in the lower part of the column were accompanied by heating in order to avoid a loss of solid by cooling and crystallization. 942 g / h of an aqueous nitric acid solution (37%) were added continuously to the 8th tray (from below) of the column. In this solution, a copper / vanadium catalyst was dissolved. 89 g / h of a mixture of 15% by weight of cyclohexanone and 85% by weight of cyclohexanol were continuously pumped onto the 4th bottom. It a system pressure of 125 mbar and a return flow rate of about 495 g / h was set.
  • the temperature in the reaction zone (II) of the column was controlled by adjusting the heating power and the reflux amount to 71 0 C.
  • the thus obtained HNO3 content on the reaction tray was about 57 wt .-%.
  • the bottom temperature was 75 ° C.
  • the gas temperature before the condenser was 47 ° C.
  • the bottom stream of the column was 420 g / h crude product with 43.5 wt .-% HNO3, 29.8 wt .-% adipic acid (ADS), 1, 6 wt .-% glutaric acid, 0.2 wt .-% of succinic acid as well as won water.
  • ADS adipic acid
  • the nitrous gases were discharged in gaseous form via a torch. It was ADS with a selectivity of 93.7% based on the mixture of cyclohexanone and cyclohexanol, glutaric acid with a selectivity of 5.6% based on the mixture of cyclohexanone and cyclohexanol and succinic acid with a selectivity of 0.8% based on the mixture obtained from cyclohexanone and cyclohexanol. The mixture of cyclohexanone and cyclohexanol was completely reacted.
  • Example 1 The apparatus described in Example 1 was equipped with additional heating elements in the bottom region of the column. In addition, all piping and fittings in the lower part of the column were accompanied by heating in order to avoid a loss of solid by cooling and crystallization.
  • the bottom temperature was 75 ° C.
  • the gas temperature before the condenser was 47 ° C.
  • the bottom stream of the column was 435 g / h crude product with 43.0 wt .-% HNO3, 31, 6 wt .-% adipic acid (ADS), 0.8 wt .-% glutaric acid, 0.2 wt .-% of succinic acid as well as won water.
  • ADS adipic acid
  • succinic acid 0.8 wt .-% glutaric acid
  • succinic acid as well as won water.
  • At the top of the column 551 g / h of distillate were withdrawn consisting of water.
  • the nitrous gases were discharged in gaseous form via a torch.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Procédé de production d'acides dicarboxyliques par oxydation d'alcools cycloaliphatiques, de cétones cycloaliphatiques ou de leurs mélanges avec de l'acide nitrique, par le fait qu'on effectue la transformation et la séparation des composants dans une colonne de fractionnement ou de rectification.
EP08841083A 2007-10-22 2008-10-21 Procede d'oxydation d'alcools cycloaliphatiques, de cetones cycloaliphatiques ou de leurs melanges avec de l'acide nitrique aqueux, et recuperation des acides dicarboxyliques Withdrawn EP2205547A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE200710050713 DE102007050713A1 (de) 2007-10-22 2007-10-22 Verfahren zur Oxidation von cycloaliphatischen Alkoholen, cycloaliphatischen Ketonen oder deren Gemische mit wässriger Salpetersäure und Aufarbeitung der Dicarbonsäuren
DE102008009992A DE102008009992A1 (de) 2008-02-19 2008-02-19 Verfahren zur Oxidation von cycloaliphatischen Alkoholen, cycloaliphatischen Ketonen oder deren Gemische mit wässriger Salpetersäure und Aufarbeitung der Dicarbonsäuren
PCT/EP2008/064160 WO2009053341A2 (fr) 2007-10-22 2008-10-21 Procédé d'oxydation d'alcools cycloaliphatiques, de cétones cycloaliphatiques ou de leurs mélanges avec de l'acide nitrique aqueux, et récupération des acides dicarboxyliques

Publications (1)

Publication Number Publication Date
EP2205547A2 true EP2205547A2 (fr) 2010-07-14

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP08841083A Withdrawn EP2205547A2 (fr) 2007-10-22 2008-10-21 Procede d'oxydation d'alcools cycloaliphatiques, de cetones cycloaliphatiques ou de leurs melanges avec de l'acide nitrique aqueux, et recuperation des acides dicarboxyliques

Country Status (3)

Country Link
US (1) US20100249452A1 (fr)
EP (1) EP2205547A2 (fr)
WO (1) WO2009053341A2 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108144320A (zh) * 2017-12-23 2018-06-12 天津市鹏翔科技有限公司 特殊精馏自平衡分相无泵回流控制方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2459690A (en) * 1945-05-02 1949-01-18 Union Oil Co Oxidation of cycloaliphatic hydrocarbons and alcohols
DE1159423B (de) * 1961-12-30 1963-12-19 Basf Ag Verfahren zur kontinuierlichen Herstellung von Adipinsaeure
NL298066A (fr) * 1962-09-18
DE1921533A1 (de) * 1969-04-26 1970-11-19 Inst De Cercetari Petrochim Verfahren und Vorrichtung fuer die Herstellung von Adipinsaeure
US3754024A (en) * 1971-02-04 1973-08-21 Ici Ltd Oxidation process
DE3035809A1 (de) * 1980-09-23 1982-05-06 Chemische Werke Hüls AG, 4370 Marl Verfahren zur kontinuierlichen herstellung von gesaettigten, aliphatischen polycarbonsaeuren in einem siedereaktor
DE10240816A1 (de) * 2002-08-30 2004-03-11 Basf Ag Oxidationsverfahren

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009053341A2 *

Also Published As

Publication number Publication date
WO2009053341A3 (fr) 2009-09-03
WO2009053341A2 (fr) 2009-04-30
US20100249452A1 (en) 2010-09-30

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