Title of Invention	A PROCESS FOR PRODUCING DIACETONEACRYLAMIDE
Abstract	The invention relates to a method for carrying out reactions with participation of carbocations, whereby the initial most strongly exothermic phase of the reaction is carried out at high temperature (60 to 120 °C) and short residence time (1 to 30 seconds) in a microreactor and the subsequent less exothermic phases are carried out at optionally lower temperatures in two or more residence time units with longer residence times (1 to 30 seconds).

Title of Invention

A PROCESS FOR PRODUCING DIACETONEACRYLAMIDE

Abstract

The invention relates to a method for carrying out reactions with participation of carbocations, whereby the initial most strongly exothermic phase of the reaction is carried out at high temperature (60 to 120 °C) and short residence time (1 to 30 seconds) in a microreactor and the subsequent less exothermic phases are carried out at optionally lower temperatures in two or more residence time units with longer residence times (1 to 30 seconds).

Full Text	STEPWISE EXECUTION OF EXOTHERMIC REACTIONS WITH PARTICIPATION OF CARBOCATIONS Reactions which proceed with participation of carbocations, e.g. Ritter reactions, electrophilic addition reactions onto alkenes, or Friedel-Crafts alkylation reactions, generally proceed exothermically and mostly with little selectivity, and with high reaction rate. When strong acids are used in these reactions, corrosion problems also occur. For these reasons, a number of disadvantages arise when these reactions are carried out industrially: To permit control of generation of heat from the reaction, these reactions are normally executed at lower temperatures than would be necessary or advisable on chemical grounds. In order to control the reaction, attempts are also made to provide a high level of backmixing, but this can cause decomposition of previously formed product. The production-scale reaction is executed more slowly than the reaction rate would permit, so that the reaction can proceed in controlled fashion. The yields are mostly only moderate, sometimes by virtue of formation of byproducts and sometimes by virtue of incomplete conversion. Finally, there is always a high level of hazard because of the large amount of very reactive starting materials and intermediates. To avoid safety problems with highly exothermic reactions, and to achieve higher yields, the literature proposes carrying out these reactions in a microreactor. For example, WO 01/23328 describes the execution of Friedel-Crafts alkylation reactions of organic compounds in a microreactor, composed of a mixing element and optionally of a residence section. EP 1 500 649 discloses that in-situ quench reactions, such as the reaction of aryl bromides with butyllithium to give aryllithium compounds with subsequent reaction with an electrophile can be executed in a microreactor optionally with following residence time unit. The use of microreactors optionally with following residence time section is also known for other processes. Examples of these are the preparation of dihydropyrones (WO 02/068403), the coupling of organic compounds (WO 02/00577), the transfer of alkylidene groups to organic compounds (WO 02/00576), the acid-catalyzed homogenous cleavage of cumene hydroperoxide (Wp 01/30732), etc. In these processes, the entire reaction is executed in the microreader, and therefore it is generally only very fast reactions that are suitable for this purpose. Furthermore, the above processes achieve markedly smaller yields than would be possible theoretically. Thruput and selectivity of the processes described hitherto are also unsatisfactory. It was an object of the present invention to find a process which permits the execution of reactions with participation of carbocations with, in comparison with the prior art, increased thruput and increased yield and selectivity. Unexpectedly, this object could be achieved by dividing the reaction into a plurality of steps, where the most strongly exothermic phase of the reaction is executed at the highest temperature and shortest residence time, and the following, less exothermic phases are executed at optionally lower temperatures and longer residence times. The present invention therefore provides an improved process for the execution of reactions with participation of carbocations, which comprises carrying out the most strongly exothermic initial phase of the reaction at a high temperature and short residence time in a microreactor, and execution of the subsequent less exothermic phases at optionally lower temperatures in two or more residence time units with longer residence time. The inventive process is suitable for the execution of reactions with participation of carbocations. Examples of these reactions are Ritter reactions, electrophilic addition reactions onto alkenes, or Friedel-Grafts alkylation reactions, etc. It is preferable that the inventive process is used for Ritter reactions, where carbocations are reacted with a nitrite. Examples of a source used here for the carbocations are alcohols, alkenes, etc. It is particularly preferable that the process is used for the preparation of diacetoneacrylarnide via reaction of acrylonttrile with diacetone alcohol, acetone, or mesityl oxide, in the presence of sulfuric acid, and then hydrolysis. The invention executes the reactions with participation of carbocations in a plurality of phases. The first phase is the most strongly exothermic initial phase. This phase is executed at high temperature and short residence time in a microreactor. Suitable microreaders here are any of the familiar microreactors, as known from the literature, for example from DE 39 26 466 C2, US 5,534,328, DE 100 40 100, WO 96/30113, EP 0 688 242, EP 1 031 375, or else publications from Mikrotechnik Mainz GmbH, Germany, or from "Microreactors; Wolfgang Ehrfeld. Volker Hessel Holger Lowe; Wiley-VHC; ISBN 3-527-29590-9; Chapter 3 Micromixers", or else commercially available microreactors, for example from Institut for Mikrotechnik, Mainz GmbH, Cellular Process Chemistry GmbH or Mikroglass AG. Microreactors whose use is preferred comprise a mixing module and a heat-exchange module. The mixing modules used preferably have the design of static mixers, based on various functional principles. By way of example, these can be T-type mixers, microjet reactors, substream injection mixers, Y-or V-type mixers, interdigital mixers, rectangular mixers, slot mixers, triangular multilamination mixers, caterpillar mixers, cyclone micromixers, or combinations of these. It is preferable that the inventive process uses cyclone micromixers or T-type mixers. The mixing module is combined with a heat-exchange module which comprises from one to a plurality of micro-heat-exchangers. Examples of suitable micro-heat-exchangers are micro-crossflow heat-exchangers, crossfiow heat-exchangers with crossmixing, or stacked countercurrent heat-exchangers, etc. It is preferable to use crossfiow heat-exchangers. The microreactors used optionally have a thermostatable mixing site. The invention mixes the appropriate starting materials for the reaction in the microreactor, and the residence time of the reaction mixture in the microreactor in this phase is short. A short residence time here preferably means, as a function of the respective reaction executed and temperature, from 1 to 30 sec, preferably from 3 to 20 sec. The reaction temperature is highest in this phase and, as a function of the reaction executed and of the temperature of the coolant, is from 60 to 120"C. If the reactions executed are Ritter reactions, the residence time in the microreactor is preferably from 5 to 20 sec, the reaction temperature being from 70 to11O'C. In the particularly preferred Ritter reaction for the preparation of diacetoneacrylamide via reaction of aoylonitrile with diacetone alcohol, acetone, or mesityl oxide, in the presence of sulfuric acid, and then hydrolysis, the residence time in the microreactor is from 5 to 20 sec and the reaction temperature is from 70 to 110°C, preferably from 75 to 100°C. Following the first phase of the reaction, the reaction mixture is transferred to a first residence time unit, in which the reaction mixture continues to react in a phase which is then less exothermic, the result being an increase in the yields of the desired end product. Suitable residence time units are known by way of example from EP 1 157 738 or EP 1 188 476. However, the residence time unit can also be a simple residence time section, such as a capillary, a heat-exchanger, such as a spiral heat-exchanger, a plate heat-exchanger, or an optionally thermostatable loop reactor, or else a simple stirred tank, or a stirred-tank cascade. It is preferable to use a heat-exchanger, a stirred tank, a stirred-tank cascade, or a thermostatabie loop reactor. The residence time in this residence time unit is longer than the residence time in the microreactor, and is from 1 minute to 30 minutes. The reaction temperature in this phase is the same as in the microreactor or lower by from 5 to 30°C. In the case of the Ritter reaction preferably executed for the preparation of diacetoneacrylamide via reaction of acrylonitrile with diacetone alcohol, acetone or mesityl oxide, in the presence of sulfuric acid, and then hydrolysis, the reaction temperature in the residence time unit is from 60 to 100°C, and the residence time is from 1 to 20 minutes. Following this first residence time unit, there is another residence time unit and optionally further residence time units. There is preferably one further following residence time unit. It is particularly preferable that this is a simple stirred tank or a stirred-tank cascade. In this second residence time unit, the final afterreaction then takes place, the result being another increase in yield. The residence time in this unit is the longest here and is from 1 to 10 hours. The reaction temperature in this unit is, in contrast, the lowest, and is from 30 to 70°C. This staged temperature profile and the staged residence times permit, particularly in the preparation of diacetoneacrylamide, a marked yield increase as far as above 78% (crude yield), compared with about 61 % (crude yield) for a conventional procedure. Alongside the higher achievable yield through the inventive conduct of the reaction, the reaction proceeds faster and more selectively, while avoiding the risk posed by high-energy starting materials or intermediates. Example 1: Use of a spiral heat-exchanger for the first residence time unit: A reaction solution with a stoichiometric molar ratio of acrylonitrile (AN) to diacetone alcohol (DiAOH) to H2S04 = 1.0:1.0:2.4 had a residence time of 12 s at 90°C in the microreactor (composed of a mixing module made from Hastelloy and of a heat-exchange module), 100 s at 90°C in the spiral heat-exchanger, and two hours at 50°C in the continuous stirred tank. The total yield of diacetoneacrylamide was 78%, based on ACN, the proportions of the final conversion being 74% in the first 12 s, 21% in the following 100 s, and 5% in the remaining 2 h. Examples 2-6: Execution was analogous to example 1. Table 1 shows starting materials used, residence times, temperatures, and yields: Table 1 (Table 1 Removed) Example 7: The reaction led to a final yield of 73.5%, using a stoichiometric ratio of AN to DiaOH to H2SO4 = 1.0:1.0:2.2 and a residence time distribution, with 90°C for 12 s in the microreactor, with 65°C for 960 s in the first continuous stirred tank and with 55°C for 10 800 s in the second continuous stirred tank. Example 8-10: Execution was analogous to example 7. Table 2 shows the starting materials used, residence times, temperatures, and yields: (Table 2 Removed) CLAIMS 1. An improved process for the execution of reactions with participation of carbocations, which comprises carrying out the most strongly exothermic initial phase of the reaction at a high temperature and short residence time in a microreactor, and execution of the subsequent less exothermic phases at optionally lower temperatures in two or more residence time units with longer residence time. 2. The process as claimed in claim 1, wherein, for the initial phase, microreactors are used which have a mixing module from the group of the T-type mixers, microjet reactors, substream injection mixers, Y- or V-type mixers, interdigital mixers, rectangular mixers, slot mixers, triangular multilamination mixers, caterpillar mixers, cyclone micromixers, or combinations of these, and a heat- exchange module which has from one to a plurality of microheat-exchangers from the group of the micro-crossflow heat-exchangers, crossflow heat- exchangers with crossmixing, or stacked countercurrent heat-exchangers. 3. The process as claimed in claim 1 or 2, wherein the residence time in the microreactor is from 1 to 30 seconds and the reaction temperature is from 60 to 120°C. 4. The process as claimed in claim 1 or 2, wherein there is, following the microreactor, a first residence time unit, composed of a capillary, of a heat- exchanger of anoptionally the rmostatable loop.reactorof a stirred tank.or of a stirred-tank cascade. 5. The process as claimed in any of claims 1 to 4, wherein the residence time in the first residence time unit following the microreactor is from 1 to 30 minutes, and the reaction temperature is the same as in the microreactor or is lower by from 5 to 30 °C. 6. The process as claimed in any of claims 1.to 5, wherein a stirred-tank or a stirred-tank cascade is used as second residence time unit. 7. The process as claimed in any of claims 1 to 6, wherein the residence time in the second residence time unit is from 1 to 10 hours, and the reaction temperature is from 60 to 100°C. 8. The process as claimed in any of claims 1 to 7, wherein a Ritter reaction is executed as reaction with participtation of carbocations. 9. The process as claimed in any of claims 1 to 8, wherein, as reaction with participation of carbocations, the reaction of acrylonitrile with diacetone alcohol, acetone, or mesityl oxide, in the presence of sulfuric acid, and then hydrolysis to give diacetoneacrylamide, is executed.

Full Text

STEPWISE EXECUTION OF EXOTHERMIC REACTIONS WITH PARTICIPATION OF
CARBOCATIONS
Reactions which proceed with participation of carbocations, e.g. Ritter reactions, electrophilic addition reactions onto alkenes, or Friedel-Crafts alkylation reactions, generally proceed exothermically and mostly with little selectivity, and with high reaction rate. When strong acids are used in these reactions, corrosion problems also occur. For these reasons, a number of disadvantages arise when these reactions are carried out industrially:
To permit control of generation of heat from the reaction, these reactions are normally executed at lower temperatures than would be necessary or advisable on chemical grounds.
In order to control the reaction, attempts are also made to provide a high level of backmixing, but this can cause decomposition of previously formed product.
The production-scale reaction is executed more slowly than the reaction rate would permit, so that the reaction can proceed in controlled fashion.
The yields are mostly only moderate, sometimes by virtue of formation of byproducts and sometimes by virtue of incomplete conversion.
Finally, there is always a high level of hazard because of the large amount of very reactive starting materials and intermediates.
To avoid safety problems with highly exothermic reactions, and to achieve higher yields, the literature proposes carrying out these reactions in a microreactor.
For example, WO 01/23328 describes the execution of Friedel-Crafts alkylation reactions of organic compounds in a microreactor, composed of a mixing element and optionally of a residence section.
EP 1 500 649 discloses that in-situ quench reactions, such as the reaction of aryl bromides with butyllithium to give aryllithium compounds with subsequent reaction with an electrophile can be executed in a microreactor optionally with following residence time unit.
The use of microreactors optionally with following residence time section is also known for other processes. Examples of these are the preparation of dihydropyrones (WO 02/068403), the coupling of organic compounds (WO 02/00577),
the transfer of alkylidene groups to organic compounds (WO 02/00576), the acid-catalyzed homogenous cleavage of cumene hydroperoxide (Wp 01/30732), etc.
In these processes, the entire reaction is executed in the
microreader, and therefore it is generally only very fast reactions that are suitable for this purpose. Furthermore, the above processes achieve markedly smaller yields than would be possible theoretically. Thruput and selectivity of the processes described hitherto are also unsatisfactory.
It was an object of the present invention to find a process which permits the execution of reactions with participation of carbocations with, in comparison with the prior art, increased thruput and increased yield and selectivity.
Unexpectedly, this object could be achieved by dividing the reaction into a plurality of steps, where the most strongly exothermic phase of the reaction is executed at the highest temperature and shortest residence time, and the following, less exothermic phases are executed at optionally lower temperatures and longer residence times.
The present invention therefore provides an improved process for the execution of reactions with participation of carbocations, which comprises carrying out the most strongly exothermic initial phase of the reaction at a high temperature and short residence time in a microreactor, and execution of the subsequent less exothermic phases at optionally lower temperatures in two or more residence time units with longer residence time.
The inventive process is suitable for the execution of reactions with participation of carbocations.
Examples of these reactions are Ritter reactions, electrophilic addition reactions onto alkenes, or Friedel-Grafts alkylation reactions, etc.
It is preferable that the inventive process is used for Ritter reactions, where carbocations are reacted with a nitrite. Examples of a source used here for the carbocations are alcohols, alkenes, etc.
It is particularly preferable that the process is used for the preparation of diacetoneacrylarnide via reaction of acrylonttrile with diacetone alcohol, acetone, or mesityl oxide, in the presence of sulfuric acid, and then hydrolysis.
The invention executes the reactions with participation of carbocations in a plurality of phases.
The first phase is the most strongly exothermic initial phase.
This phase is executed at high temperature and short residence time in a microreactor.
Suitable microreaders here are any of the familiar microreactors, as known from the literature, for example from DE 39 26 466 C2, US 5,534,328, DE 100 40 100, WO 96/30113, EP 0 688 242, EP 1 031 375, or else publications from Mikrotechnik Mainz GmbH, Germany, or from "Microreactors; Wolfgang Ehrfeld. Volker Hessel Holger Lowe; Wiley-VHC; ISBN 3-527-29590-9; Chapter 3 Micromixers", or else commercially available microreactors, for example from Institut for Mikrotechnik, Mainz GmbH, Cellular Process Chemistry GmbH or Mikroglass AG.
Microreactors whose use is preferred comprise a mixing module and a heat-exchange module.
The mixing modules used preferably have the design of static mixers, based on various functional principles. By way of example, these can be T-type mixers, microjet reactors, substream injection mixers, Y-or V-type mixers, interdigital mixers, rectangular mixers, slot mixers, triangular multilamination mixers, caterpillar mixers, cyclone micromixers, or combinations of these.
It is preferable that the inventive process uses cyclone micromixers or T-type mixers.
The mixing module is combined with a heat-exchange module which comprises from one to a plurality of micro-heat-exchangers.
Examples of suitable micro-heat-exchangers are micro-crossflow heat-exchangers, crossfiow heat-exchangers with crossmixing, or stacked countercurrent heat-exchangers, etc.
It is preferable to use crossfiow heat-exchangers.
The microreactors used optionally have a thermostatable mixing site.
The invention mixes the appropriate starting materials for the reaction in the microreactor, and the residence time of the reaction mixture in the microreactor in this phase is short.
A short residence time here preferably means, as a function of the respective reaction executed and temperature, from 1 to 30 sec, preferably from 3 to 20 sec.
The reaction temperature is highest in this phase and, as a function of the reaction executed and of the temperature of the coolant, is from 60 to 120"C.
If the reactions executed are Ritter reactions, the residence time in the microreactor is preferably from 5 to 20 sec, the reaction temperature being from 70 to11O'C.
In the particularly preferred Ritter reaction for the preparation of diacetoneacrylamide via reaction of aoylonitrile with diacetone alcohol, acetone, or mesityl oxide, in the presence of sulfuric acid, and then hydrolysis, the residence time in the microreactor is from 5 to 20 sec and the reaction temperature is from 70 to 110°C, preferably from 75 to 100°C.
Following the first phase of the reaction, the reaction mixture is transferred to a first residence time unit, in which the reaction mixture continues to react in a phase which is then less exothermic, the result being an increase in the yields of the desired end product.
Suitable residence time units are known by way of example from EP 1 157 738 or EP 1 188 476. However, the residence time unit can also be a simple residence time section, such as a capillary, a heat-exchanger, such as a spiral heat-exchanger, a plate heat-exchanger, or an optionally thermostatable loop reactor, or else a simple stirred tank, or a stirred-tank cascade. It is preferable to use a heat-exchanger, a stirred tank, a stirred-tank cascade, or a thermostatabie loop reactor.
The residence time in this residence time unit is longer than the residence time in the microreactor, and is from 1 minute to 30 minutes. The reaction temperature in this phase is the same as in the microreactor or lower by from 5 to 30°C.
In the case of the Ritter reaction preferably executed for the preparation of diacetoneacrylamide via reaction of acrylonitrile with diacetone alcohol, acetone or mesityl oxide, in the presence of sulfuric acid, and then hydrolysis, the reaction temperature in the residence time unit is from 60 to 100°C, and the residence time is from 1 to 20 minutes.
Following this first residence time unit, there is another residence time unit and optionally further residence time units.
There is preferably one further following residence time unit. It is particularly preferable that this is a simple stirred tank or a stirred-tank cascade.
In this second residence time unit, the final afterreaction then takes place, the result being another increase in yield.
The residence time in this unit is the longest here and is from 1 to 10 hours.
The reaction temperature in this unit is, in contrast, the lowest, and is from 30 to 70°C.
This staged temperature profile and the staged residence times permit, particularly in the preparation of diacetoneacrylamide, a marked yield increase as far as above 78% (crude yield), compared with about 61 % (crude yield) for a conventional procedure.
Alongside the higher achievable yield through the inventive conduct of the reaction, the reaction proceeds faster and more selectively, while avoiding the risk posed by high-energy starting materials or intermediates.
Example 1:
Use of a spiral heat-exchanger for the first residence time unit: A reaction solution with a stoichiometric molar ratio of acrylonitrile
(AN) to diacetone alcohol (DiAOH) to H2S04 = 1.0:1.0:2.4 had a residence time of 12 s
at 90°C in the microreactor (composed of a mixing module made from Hastelloy and of
a heat-exchange module), 100 s at 90°C in the spiral heat-exchanger, and two hours at
50°C in the continuous stirred tank.
The total yield of diacetoneacrylamide was 78%, based on ACN, the
proportions of the final conversion being 74% in the first 12 s, 21% in the following
100 s, and 5% in the remaining 2 h.
Examples 2-6:
Execution was analogous to example 1. Table 1 shows starting materials used, residence times, temperatures, and yields:
Table 1

(Table 1 Removed)
Example 7:
The reaction led to a final yield of 73.5%, using a stoichiometric ratio of AN to DiaOH to H2SO4 = 1.0:1.0:2.2 and a residence time distribution, with 90°C for 12 s in the microreactor, with 65°C for 960 s in the first continuous stirred tank and with 55°C for 10 800 s in the second continuous stirred tank.
Example 8-10:
Execution was analogous to example 7. Table 2 shows the starting materials used, residence times, temperatures, and yields:

(Table 2 Removed)

CLAIMS
1. An improved process for the execution of reactions with participation of
carbocations, which comprises carrying out the most strongly exothermic initial
phase of the reaction at a high temperature and short residence time in a
microreactor, and execution of the subsequent less exothermic phases at
optionally lower temperatures in two or more residence time units with longer
residence time.
2. The process as claimed in claim 1, wherein, for the initial phase, microreactors
are used which have a mixing module from the group of the T-type mixers,
microjet reactors, substream injection mixers, Y- or V-type mixers, interdigital
mixers, rectangular mixers, slot mixers, triangular multilamination mixers,
caterpillar mixers, cyclone micromixers, or combinations of these, and a heat-
exchange module which has from one to a plurality of microheat-exchangers
from the group of the micro-crossflow heat-exchangers, crossflow heat-
exchangers with crossmixing, or stacked countercurrent heat-exchangers.
3. The process as claimed in claim 1 or 2, wherein the residence time in the
microreactor is from 1 to 30 seconds and the reaction temperature is from 60
to 120°C.
4. The process as claimed in claim 1 or 2, wherein there is, following the
microreactor, a first residence time unit, composed of a capillary, of a heat-
exchanger of anoptionally the rmostatable loop.reactorof a stirred tank.or of
a stirred-tank cascade.
5. The process as claimed in any of claims 1 to 4, wherein the residence time in
the first residence time unit following the microreactor is from 1 to 30 minutes,
and the reaction temperature is the same as in the microreactor or is lower by
from 5 to 30 °C.
6. The process as claimed in any of claims 1.to 5, wherein a stirred-tank or a
stirred-tank cascade is used as second residence time unit.
7. The process as claimed in any of claims 1 to 6, wherein the residence time in
the second residence time unit is from 1 to 10 hours, and the reaction
temperature is from 60 to 100°C.
8. The process as claimed in any of claims 1 to 7, wherein a Ritter reaction is
executed as reaction with participtation of carbocations.
9. The process as claimed in any of claims 1 to 8, wherein, as reaction with
participation of carbocations, the reaction of acrylonitrile with diacetone alcohol, acetone, or mesityl oxide, in the presence of sulfuric acid, and then hydrolysis to give diacetoneacrylamide, is executed.

Documents:

9148-delnp-2007-Abstract-(23-06-2014).pdf

9148-delnp-2007-abstract.pdf

9148-delnp-2007-Claims-(23-06-2014).pdf

9148-delnp-2007-claims.pdf

9148-delnp-2007-Correspondence Others-(07-01-2014).pdf

9148-delnp-2007-Correspondence Others-(23-06-2014).pdf

9148-delnp-2007-correspondence-others.pdf

9148-delnp-2007-description (complete).pdf

9148-delnp-2007-form-1.pdf

9148-delnp-2007-Form-2-(23-06-2014).pdf

9148-delnp-2007-form-2.pdf

9148-delnp-2007-Form-3-(07-01-2014).pdf

9148-delnp-2007-form-3.pdf

9148-delnp-2007-form-5.pdf

9148-delnp-2007-GPA-(23-06-2014).pdf

9148-delnp-2007-gpa.pdf

9148-delnp-2007-pct-210.pdf

9148-delnp-2007-pct-304.pdf

9148-delnp-2007-Petition-137-(23-06-2014).pdf

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Patent Number

262840

Indian Patent Application Number

9148/DELNP/2007

PG Journal Number

39/2014

Publication Date

26-Sep-2014

Grant Date

18-Sep-2014

Date of Filing

27-Nov-2007

Name of Patentee

DSM FINE CHEMICALS AUSTRIA NFG GMBH & CO.KG

Applicant Address

ST.-PETER-STRASSE 25, A-4021 LINZ, AUSTRIA.

Inventors:

#	Inventor's Name	Inventor's Address
1	POCHLAUER, PETER	AM POSTLINGBERG 5, A-4020 LINZ, AUSTRIA.
2	KOTTHAUS, MARTINA	HANRIEDERSTRASSE 22, A-4020 LINZ, AUSTRIA
3	VORBACH, MARTIN	RAMSAUERSTRASSE 36, A-4020 LINZ, AUSTRIA
4	DEAK, MARTIN	KAUFFMANN-STRASSE 1/7, A-6845 HOHENEMS, AUSTRIA
5	ZICH, THOMAS	MELICHARSTRASSE 13, A-4020 LINZ, AUSTRIA
6	MARR, ROLF	NEUE WELT HOHE 33, A-8042 GRAZ, AUSTRIA

PCT International Classification Number

B01J 19/00

PCT International Application Number

PCT/EP2006/003859

PCT International Filing date

2006-04-26

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	A 873/2005	2005-05-23	Austria