EP1703957A1 - Procede de fabrication d'un produit de reaction chimique au moyen d'un reacteur a lit solide - Google Patents
Procede de fabrication d'un produit de reaction chimique au moyen d'un reacteur a lit solideInfo
- Publication number
- EP1703957A1 EP1703957A1 EP05700003A EP05700003A EP1703957A1 EP 1703957 A1 EP1703957 A1 EP 1703957A1 EP 05700003 A EP05700003 A EP 05700003A EP 05700003 A EP05700003 A EP 05700003A EP 1703957 A1 EP1703957 A1 EP 1703957A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- reaction
- reaction product
- reactants
- particle
- bed
- 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- Withdrawn
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/18—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns
- B01D15/1892—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns the sorbent material moving as a whole, e.g. continuous annular chromatography, true moving beds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
- B01J8/0257—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical in a cylindrical annular shaped bed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0285—Heating or cooling the reactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
- B01J2208/00212—Plates; Jackets; Cylinders
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- the present invention relates to a method for producing a chemical reaction product from one or more reactants by contact with a heterogeneous catalyst in a fixed bed reactor.
- a typical P-CAC apparatus (“preparative continuous annular chromatography”) consists of an annular, ie annular, particle bed, which is packed into the space (annular gap) between two concentric cylinders. With the particle bed rotating around its own At the upper end of the axis, feed solution with the mixture to be separated and one or more eluents are continuously fed in. Such procedures are known from the prior art (see, for example, EP-A-371.648). P-CAC apparatuses were used exclusively for chromatographic separation used by mixtures of substances.
- the applicant of the present invention first described the use of such a continuously operating annular chromatograph as the reaction medium, the particle bed being divided into two or more zones which comprise at least one reaction zone and at least one separation zone, which are separated from one another by separating layers made of membranes, non-porous inert materials or electrically non-conductive materials.
- a chemical product formed in a reaction zone under the action of a catalyst is subsequently purified chromatographically in at least one separation zone from starting materials and any by-products as well as from catalyst and is obtained in essentially pure form from the reactor / chromatograph.
- this type of "reactive chromatography” is also relatively material and cost-intensive, especially since different particle bed materials are used for reaction and separation zones, but at least different (with metals, metal complexes or enzymes) coated bed material for reaction and Separation zones, often also different solvents or eluents, and one or more separation layers must be provided.
- the apparatus and thus also the financial expenditure increase further.
- the aim of the present invention was therefore to provide a process for the synthesis of chemical products and separation of reactants, products and by-products in a chromatographic fixed bed of a continuously operated annular chromatograph while reducing the process engineering, apparatus, financial and material expenditure in comparison to the AT described above.
- A-405.026 as the closest prior art.
- the solution according to the invention of the above objective consists in a process for producing at least one chemical reaction product by means of chemical reaction of one or more reactants, optionally dissolved in one or more solvents, which are fed in as a feed stream by contact with a heterogeneous catalyst in a continuously operated particle bed Fixed-bed reactor, a continuous annular chromatograph (CAC) filled with the particle bed being used as the fixed-bed reactor " , in which the at least one reaction product is formed and purified and the at least one purified reaction product and any by-products and / or non- reacted reactants are withdrawn in each case at a different, predetermined angle of rotation position of the annular chromatograph, with the characteristic according to the invention that only one type of particle material in a single particle bed is used simultaneously as a catalyst for formation and as a chromatography medium for cleaning the at least one reaction product in the particle bed.
- CAC continuous annular chromatograph
- This procedure with a single particle bed as the reaction and separation medium, with a suitable choice of the process parameters (bed material, flow rate, temperature, pressure), as will be explained in more detail later, eliminates the need for several different bed materials and the separating layers to be arranged between them.
- Chromatography media have the inherent property of having different levels of affinity for different materials in order to pass them through due to their resulting different flow rates to be able to separate the chromatography bed.
- Such a method according to the invention also allows the annular chromatograph to be operated continuously, the reaction equilibrium being shifted towards the at least one end product by the constant removal of the reaction product, as a result of which the reactant (s) is preferably converted into reaction product (s) / be, which is preferably an essentially quantitative implementation results.
- Unreacted reactants and / or by-products are preferably returned to the reaction cycle and reused in the chemical reaction. This ensures efficient use of the chemicals used.
- the catalyst material is evenly distributed in or on the particle material. Due to the rotation of the annular chromatograph and the continuous feeding of the reactants, there is complete contact between the reactants and the catalyst and thus an efficient mixing of these components. This ensures high sales.
- the particle material consists entirely of catalyst material. This increases the contact surface and time between the reactants and the catalyst, which in turn leads to better conversion.
- an ion exchange resin is filled in as particle material in further preferred embodiments, certain molecules can be retained in the resin.
- a zeolite can also be used as the particle material in order to further increase the separation performance, as will be explained in more detail later.
- the reaction parameters can be sensitively controlled by heating or cooling the reaction / separation medium, it being possible to create several zones of different temperatures.
- a continuous temperature gradient can be generated in the particle bed by heating and / or cooling.
- the setting of different temperatures can be important where a certain reaction temperature has to be maintained, but the chromatographic separation from the temperature can also be influenced, which is why different temperature zones are within the scope of the invention.
- the properties of most zeolites are temperature dependent.
- Some zeolites for example, have a catalytic effect above 150 ° C, while below, ie with a higher crystal water content, they show a separation effect similar to that of a chromatography gel.
- the catalyst action can be used primarily in the upper, hotter bed areas and then, in particular in the lower, cooler areas, especially the separating action of the respective zeolite, without the need for an expensive coating of the particle material.
- At least one reactant preferably all reactants to promote the reaction rate, is dissolved in a solvent, and in some embodiments the solvent can simultaneously serve as an eluent. In still other embodiments, at least one of the reactants itself acts as a solvent, which further simplifies the reaction procedure and saves costs.
- a multivalent reaction partner is used as the reactant, which can form several different reaction products by reaction with the other reactant.
- the method is preferably regulated by controlling the operating parameters such that one of the possible reaction products is preferably obtained. It is particularly preferred that essentially only this one reaction product is obtained.
- acetic acid and glycerol are added as reactants and essentially only triacetin is obtained as the preferred reaction product, ie mono- and diacetin are further reacted with acetic acid and do not occur as by-products.
- the reactants are phenol and acetone
- FIG. 1 schematically shows an embodiment of the present invention, namely an annular chromatograph with a chromatography bed 1 in an annular column made of material which is inert towards the components of the reactants and solvents and which rotates about an axis 3, and a temperature jacket 2.
- Reference number 1 designates the particulate fixed bed, which is usually accommodated in a hollow cylinder-shaped container, for example made of glass or stainless steel, and rotates about an axis 3 during operation.
- This particle bed acts according to the present invention both as a reaction catalyst and as a separation medium, these two functions can be performed either simultaneously or - for example in the case of controlled temperature control via the height of the fixed bed - in succession.
- Such a temperature control can be carried out, for example, using temperature control jackets, which are designated in FIG. 1 by the reference numerals 2a and 2b.
- a zeolite is used as the particle material, which - as mentioned at the beginning - has an increased catalytic effect at higher temperatures and an increased separation effect at lower temperatures, this effect can be exploited by different local temperature selection in the particle bed.
- the upper heating jacket 2a of Fig. 1 is heated with a high temperature heating medium, e.g. operated above 150 ° C, while the lower temperature jacket 2b from a medium of lower temperature, e.g. 60 to 80 ° C, is flowed through.
- the scope of the invention also includes conditions where three or more temperature control jackets 2 are provided one below the other, which makes it possible to provide a plurality of “hot reaction zones” which may be separated from one another by zones of lower temperature, but all of these differ from the prior art Zones exist in the same particle bed.
- the number of temperature control jackets is not particularly limited. In practice, however, a number of one to a maximum of three jackets, usually one or two, is preferred in order to keep the reaction procedure relatively simple and thus to keep costs down.
- the area covered by the temperature jacket i.e. their relative height to the total height of the particle bed can be chosen freely by a person skilled in the art. Processes are preferred according to the invention in which a continuous temperature gradient is established in the fixed bed of catalyst / separating medium in order to exclude side reactions, which are often difficult to predict, and are often difficult to predict as a result of excessively abrupt changes in temperature.
- particle material e.g. essentially inert material can be used which has been coated with at least one substance which is active as a catalyst and / or as separation medium, or for example a material which is active as separation medium and which has been coated with a catalyst component, or vice versa.
- a mixture of separation and catalyst materials can also be used.
- only one type of particle material is used to ensure maximum homogeneity, to maximize the performance of the method and to reduce costs, which furthermore particularly preferably consists entirely of catalyst / separation medium.
- ion exchange resins or zeolites are used in particular.
- Processes are preferred according to the invention in which the at least one reactant is supplied dissolved in a solvent, since this effectively avoids local concentration fluctuations and leads to more complete conversion. It is further preferred that the solvent also functions as an eluent, which saves costs by reducing the outlay for chemicals and equipment. In the case of reactions of several reactants, one of them can particularly preferably (as far as this is possible) serve as a solvent at the same time.
- the invention includes reactions in which at least one reactant is converted to at least one end product, the particle bed acting on the one hand as a catalyst for the reaction (s) and on the other hand as a separation medium for purifying the at least one end product. Pre-cleaning of one or more reactants is also possible. This means that the at least one reactant first has to pass through a separation zone before it enters a reaction zone and is eventually cleaned in a second separation zone if necessary. This can be achieved, for example, by arranging a heating jacket only at the middle of the particle bed.
- reactions in which only one reactant is reacted are, for example, decomposition or rearrangement reactions, in which a desired end product can be produced in the same fixed bed by using a process according to the present invention and, moreover, by-products can be purified.
- the invention is particularly suitable for reactions of polyvalent reactants in which more than one reaction product is thus possible.
- the method according to the invention using a preparative annular chromatograph - where different substances are withdrawn from outlets arranged at different angular positions - enables the (likewise purely obtainable) by-products to be returned to the Feed to be reacted (and cleaned) again in the particle bed.
- reactions of this type can also be optimized by means of the method of the present invention such that essentially only the desired end product is obtained at all, as a result of which the recycling of by-products, which is naturally associated with apparatus expenditure, can be completely dispensed with.
- the annular chromatograph was filled 21.4 cm high with a bed made from 569.4 g of Dowex 50 WX8 TM ion exchange resin (Dow Chemical Company; strongly acidic cation exchange resin based on sulfonated polystyrene / divinylbenzene) with a particle size of 200 to 400 Mesh passed.
- a feed mixture of 1004.9 g acetic acid and 564.3 g glycerin was used and pure acetic acid was used as the eluent.
- the feed mixture was fed at a rate of 0.6 ml / min and the eluent flow rate was 25 ml / min.
- the annular chromatograph rotated at a speed of 707 h, which resulted in a width of the feed band of 3.4 cm.
- Hoses were connected to 28 of the 90 outlets and bundled into groups of four. Each group of tubes was combined in a glass container so that seven fractions were obtained.
- the operating conditions were the same as in Example 1, except that the eluent flow rate was 45 ml / min.
- the width of the feed band was 2.5 cm.
- the resulting concentration profile is shown in Fig. 2.2.
- the eluent acetic acid is not shown in order to get a better overview of the products.
- the product peaks are shifted to smaller angles, which can be assumed as a result of the higher linear velocity and the shorter residence time at a higher eluent flow rate.
- the triacetin fractions contained less water and less diacetin.
- the supply of acetic acid as an eluent at a higher flow rate had several effects.
- the water on the ion exchange resin was displaced more quickly, which led to better regeneration of the chromatographic bed.
- acetic acid was also a reactant, higher flow rates shifted the chemical balance towards the products.
- a shown in Fig. 2.2 The further negative factor was the further dilution of the product. This effect led to the lower maximum of the triacetin peak.
- the advantages of better regeneration of the column and the shift in chemical equilibrium outweighed.
- the parameters in this example were the same as in the previous examples, except that the eluent flow rate was 65 ml / min.
- the width of the feed band was 1.8 cm.
- the measured concentration profile is shown in Fig. 2.3.
- Example 1.2 The concentration of impurities in the triacetin fractions, namely diacetin and water, was also higher than in Example 1.2.
- the shorter residence time offered less opportunity for the reaction and the separation of the products. If there is less time for the reaction to take place, the shift in chemical equilibrium caused by a higher flow rate of acetic acid may have no effect.
- Another important parameter is the speed of rotation. Increasing the speed of rotation resulted in the feed feed components being shifted to larger angles and being exposed to a wider area of the resin bed. Contact with a larger proportion of the regenerated resin could lead to a better separation of the components, but also to a dilution, since the resin was saturated with eluent. Furthermore, the dwell time had to be long enough to allow a better separation.
- Figure 2.7 shows a concentration profile for the same conditions as in Example 1.4, except that the rotation speed was increased to 807h. As expected, the peaks are shifted towards larger angles. However, no triacetin fractions with a purity above 90% were removed and the total yield of triacetin was 80.3%, compared to 96.9% in Example 1.4. This means that the dilution effect mentioned in Example 1.4 already outweighed the possibility of better separation of the products. The dilution of the products is even more evident in Example 1.6.
- the rotation speed was further increased to 907h.
- the resulting concentration profile is shown in Fig. 2.8.
- the peaks were shifted further to larger angles and the maximum of the triacetin peak was lower than in the previous examples. Together with the broadening of the peak compared to the previous examples, the lower maximum was a clear sign of the dilution of the products. This means that an eluent flow rate of 55 ml / min was too high to observe the effect of better separation at increased rotation speeds because the residence time was too short. As a result, only the dilution of the products could be observed.
- the aim of this example as well as examples 2.2 and 2.3 is to determine the effect of the eluent flow rates on the purity of bisphenol A.
- the eluent flow rate should be minimized for economic reasons, but had to be high enough to enable regeneration of the chromatography bed.
- amberlyst 31 TM resin (Rohm & Haas Company; strongly acidic cation exchange resin based on sulfonated polystyrene / divinylbenzene) with a particle size of 550 to 700 ⁇ m was used to produce bisphenol A from acetone and phenol.
- the height of the resin bed was 21.5 cm.
- Pure acetone was used as the feed and pure phenol as the eluent.
- the eluent was fed at a rate of 15 ml / min and the feed at 1.6 ml / min. A higher feed flow rate could be used in this case because acetone is not as viscous as glycerin and the width of the feed band was 2.0 cm.
- the annular chromatograph rotated at a speed of 707 hours. Seven fractions were withdrawn as in the synthesis of triacetin. The results are shown in Fig. 3.1. The eluent phenol has been omitted for clarity. As shown in Fig. 3.1, acetone was almost completely converted to bisphenol A and water.
- the bisphenol A peak was relatively broad and occurred very late. As in the case of triacetin, water was particularly difficult to displace from the resin, but in this case there was practically no water at small angles. Because there is only one reaction, less water was generated than in the production of triacetin. As a result, the column could be regenerated more easily. However, bisphenol A was fairly diluted because a relatively large amount of phenol was required to regenerate the bed.
- Fig. 3.3 shows the concentration profile.
- the peak of bisphenol A is much more pointed than before and the position is hardly shifted compared to example 2.2 because less bisphenol A was generated.
- Fig. 3.3 shows a strong peak of unreacted acetone. Under these conditions, the effect of high linear velocity dominated, which left less time for the reaction and separation, since small amounts of water also appeared in the bisphenol A fractions. On the other hand, the shift in chemical equilibrium no longer played a role. In contrast to the previous examples, no fraction of pure bisphenol A could be obtained.
- Fig. 3.4 shows the total yield of bisphenol A, based on acetone, as a function of the eluent flow rate.
- the dependence of the amount of bisphenol A produced per unit of time on the eluent flow rate is shown in FIG. 3.5.
- the overall yield decreases continuously.
- the production of pure bisphenol A shows a clear maximum because of the two strong effects mentioned above. At low flow rates, column regeneration was not as good as at higher speeds, and the chemical balance can still be shifted towards the products. Beyond the production maximum, an increase in the eluent flow rate, and thus an increase in the linear speed, offered less time for the reaction and separation.
- the production of pure bisphenol A did not decrease as quickly at high flow rates as the production of pure triacetin. However, since there were only two products here, the separation of bisphenol A and water was much easier than the separation of similar products such as triacetin and diacetin.
- the next step was to examine the influence of the speed of rotation on the concentration profile. It was decided to use an eluent flow rate of 25 ml / min and a feed inflow rate of 1.6 ml / min. Bisphenol A production at this eluent flow rate is to the left of the maximum shown in Fig. 3.5. The concentration profile for a rotation speed of 707h is shown in Fig. 3.6.
- Fig. 3.6 shows that large amounts of pure bisphenol A were still present, but an acetone peak began to appear at 40 °.
- the increase in rotational speed meant that the components of the bands derived from the acetone used were shifted to larger angles and were therefore exposed to a larger section of the resin bed.
- contact with more of the resin could result in better separation of the components, but also dilution because the resin was saturated with the eluent, as in the case of triacetin.
- Fig. 3.6 shows that the regeneration of the column was complete and the residence time was still long enough to allow high conversions of the acetone. There was therefore sufficient scope for increasing the speed of rotation.
- Fig. 3.7 shows the resulting concentration profile. The amount of unreacted acetone was slightly less than in the previous case.
- FIG. 4.1 An advantage of the larger retention angle can be seen from FIG. 4.1.
- the feed band hits a large amount of the resin in a wide section of the column before it reaches the outlets. There are several ways to react and separate the products. However, the large amount of eluent required must be taken into account.
- the eluent flow rate was increased to 115 ml / min, while all other conditions were the same as in the previous examples. Two eluent pumps were required to achieve this flow rate.
- the resulting concentration profile is shown in Fig. 4.3.
- the methyl acetate peak is shifted again and there is only one methyl acetate fraction above 50%.
- the influence of the short dwell time still had no effect and was compensated for by the better regeneration.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT0004204A AT413338B (de) | 2004-01-15 | 2004-01-15 | Verfahren zur herstellung eines chemischen reaktionsprodukts mittels festbettreaktor |
PCT/AT2005/000002 WO2005068042A1 (fr) | 2004-01-15 | 2005-01-13 | Procede de fabrication d'un produit de reaction chimique au moyen d'un reacteur a lit solide |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1703957A1 true EP1703957A1 (fr) | 2006-09-27 |
Family
ID=34715929
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP05700003A Withdrawn EP1703957A1 (fr) | 2004-01-15 | 2005-01-13 | Procede de fabrication d'un produit de reaction chimique au moyen d'un reacteur a lit solide |
Country Status (4)
Country | Link |
---|---|
US (1) | US7686958B2 (fr) |
EP (1) | EP1703957A1 (fr) |
AT (1) | AT413338B (fr) |
WO (1) | WO2005068042A1 (fr) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101389389B (zh) * | 2005-09-07 | 2012-10-24 | 美国海德能公司 | 具有rfid标签供电的流量计和电导率计的逆渗透过滤设备 |
WO2020092755A2 (fr) * | 2018-10-31 | 2020-05-07 | Repligen Corporation | Résines de chromatographie incompressibles emballées et leurs procédés de fabrication |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3971842A (en) * | 1974-08-08 | 1976-07-27 | Atlantic Richfield Company | Continuous displacement chromatographic separation |
US5470479A (en) * | 1994-06-23 | 1995-11-28 | Westinghouse Electric Corporation | Continuous, steady-state, chromatographic separation of gadolinium isotopes |
AT405026B (de) * | 1997-12-09 | 1999-04-26 | Prior Eng Ag | Annularchromatograph |
-
2004
- 2004-01-15 AT AT0004204A patent/AT413338B/de not_active IP Right Cessation
-
2005
- 2005-01-13 US US10/586,065 patent/US7686958B2/en not_active Expired - Fee Related
- 2005-01-13 EP EP05700003A patent/EP1703957A1/fr not_active Withdrawn
- 2005-01-13 WO PCT/AT2005/000002 patent/WO2005068042A1/fr active Application Filing
Non-Patent Citations (1)
Title |
---|
See references of WO2005068042A1 * |
Also Published As
Publication number | Publication date |
---|---|
US7686958B2 (en) | 2010-03-30 |
WO2005068042A1 (fr) | 2005-07-28 |
ATA422004A (de) | 2005-07-15 |
AT413338B (de) | 2006-02-15 |
US20080132722A1 (en) | 2008-06-05 |
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