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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/06—Halogens; Compounds thereof
  • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
  • B01J27/13—Platinum group metals
• • 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
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/18—Stationary reactors having moving elements inside
  • B01J19/1868—Stationary reactors having moving elements inside resulting in a loop-type movement
  • B01J19/1881—Stationary reactors having moving elements inside resulting in a loop-type movement externally, i.e. the mixture leaving the vessel and subsequently re-entering it
• • 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
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
• • 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
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/615—100-500 m2/g
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/635—0.5-1.0 ml/g
• • 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
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
• • 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
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/22—Halogenating
• • 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
  • B01J8/005—Separating solid material from the gas/liquid stream
  • B01J8/006—Separating solid material from the gas/liquid stream by filtration
• • 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
  • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
  • B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
  • B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
  • B01J8/222—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid in the presence of a rotating device only
• • 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
  • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
  • B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
  • B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
  • B01J8/224—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid the particles being subject to a circulatory movement
  • B01J8/228—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid the particles being subject to a circulatory movement externally, i.e. the particles leaving the vessel and subsequently re-entering it
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
  • C01B15/01—Hydrogen peroxide
  • C01B15/029—Preparation from hydrogen and oxygen
• • 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
  • B01J2208/00176—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles outside 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
• • 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
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/18—Details relating to the spatial orientation of the reactor
  • B01J2219/185—Details relating to the spatial orientation of the reactor vertical

Definitions

• the present invention relates to a supported metal catalyst, suitable for the direct manufacture of hydrogen peroxide from hydrogen and oxygen. It also relates to the process for manufacturing said catalyst as well as the process for manufacturing hydrogen peroxide using said catalyst.
• the low productivity of the catalytic manufacturing process of hydrogen peroxide directly from hydrogen and oxygen is an obstacle to its development. There are many attempts to improve this productivity. Mention may in particular be made of US 3,336 1 1 2, US 3,361,533, US 4,007,526, US 4,009,252, US 4,279,883 and US 4,335,092. These studies are mainly based on the general concept, namely stabilization hydrogen peroxide using a sequestering agent or decomposition inhibitor.
• US Pat. No. 4,379,778 discloses a process for the direct manufacture of hydrogen peroxide from hydrogen and oxygen in an aqueous medium comprising decomposition inhibitors, in the presence of a palladium-carbon catalyst previously treated with an aldehyde or a ketone and, preferably, also pretreated with a dilute solution of hydrochloric acid.
• US patents 5 1 28 1 14 and US 5 352 645 describe a method for preparing catalysts based on palladium or platinum-palladium supported on uniform microspheres, non-agglomerated and porous of silica, resistant to attrition by the use of ammonium citrate or urea as an additive and suitable for the direct manufacture of hydrogen peroxide.
• Example 1 2 of US Patent 5 1 28 1 14 describes the two-step preparation of a supported catalyst containing about 0.05% by weight of platinum and 1% by weight of palladium on porous silica microspheres. The support is first prepared by atomization of a mixture of Ludox AS 40 silica and urea, then calcined at 650 ° C under nitrogen.
• This support is then added to a solution of Pt and Pd, previously prepared by dissolving H 2 PtCI 6 and PdCI 2 in water, brought to a temperature between 60 and 70 ° C and acidified with concentrated HCl until '' to obtain a pH of about 1.2.
• the resulting mixture is stirred, then atomized and finally, the powder obtained is reduced under a stream of hydrogen at 300 ° C.
• Example 1 5 of US Patent 5,352,645 The preparation of the supported catalyst according to Example 1 5 of US Patent 5,352,645 is similar to that described in Example 1 2 of US Patent 5 1 28 1 1 4 with a difference.
• the resulting mixture instead of being atomized, is dried under vacuum at 1,00 ° C. overnight, then the dried solid is reduced under a stream of hydrogen at 1,00 ° C.
• Metallic crystallites of the order of 30 to 50 ⁇ were thus obtained.
• the Applicant Company has developed a supported catalyst based on at least one metal chosen from group M formed of palladium, platinum, ruthenium, rhodium, iridium, osmium, holmium and gold and, in particular, a supported bimetallic catalyst.
• the supported bimetallic catalyst generally consists of a metal from the majority group M and a metal from the minority group M.
• the majority metal represents approximately 0.1 to 10% by weight of the catalyst and preferably between 0.5 to 1% by weight.
• the minority metal represents approximately 0.001 to 0.1% by weight of the catalyst and preferably between 0.01 and 0.05%.
• the particularly preferred supported bimetallic catalyst consists of palladium as the majority metal and platinum as the minority metal.
• the present invention also relates to a supported plurimetallic catalyst made up of a majority group M metal and several minority group M metals.
• the preferred supported plurimetallic catalyst comprises palladium, as the majority metal, platinum and at least one metal from group M, as minority metals.
• the content of majority metal in the supported plimetallic catalyst is practically identical to that of the bimetallic catalyst and, each minority metal can be present in the catalyst in an amount representing approximately 0.001 to 0.1% by weight of the catalyst and preferably between approximately 0, 01 and 0.05%.
• the present invention further provides a monometallic catalyst supported with, preferably, platinum or gold as the metallic constituent of group M.
• the content of metallic constituent is generally between 0.1 and 10% by weight of the catalyst and preferably between 0.5 and 1% by weight.
• the supported metal catalyst according to the invention is preferably characterized by clusters of crystallized metal or metals of size between 0.1 and 20 ⁇ m and, preferably, between 1 and
• Silica, alumina, carbon and silicoaluminate may be suitable as a support. However, it is preferred to use silica and advantageously, silica particles of average size between 1 and 50 ⁇ m. It is also preferred to use silica with a BET specific surface greater than 200 m 2 / g and most often between 300 and 600 m 2 / g. The idrich microporous silica referenced 28.851 -9 has been found to be particularly advantageous.
• the level of iron (Fe) in the support chosen is preferably less than 0.001% by weight.
• a second subject of the invention is a process for the preparation of supported catalyst based on at least one metal from group M defined above.
• This process successively comprising a step of impregnating a solution based on one or more salt (s) of at least one metal, chosen from group M, on a support and, a reduction step is characterized in that that at the end of the reduction stage, the catalyst is subjected to a treatment with an acidic aqueous solution (A) comprising bromine and bromide ions.
• A acidic aqueous solution
• the concentration of bromide ions in the aqueous solution (A) can be between 20 and 200 mg / l and preferably between 20 and 100 mg / l.
• Bromine concentration can be between 20 and 200 mg / l and preferably between 20 and 100 mg / l.
• (Br 2 ) can be between 2 and 20 mg / l and preferably between 2 and 10 mg / l.
• the pH of the aqueous solution (A) is preferably between 1 and 3.
• the aqueous solution (A) can be prepared for example by dissolving an alkali or alkaline earth metal bromide in water, then by addition of bromine in the form of bromine water with a concentration advantageously close to 1% by weight and finally, the pH can be adjusted using an acid.
• the catalyst to be prepared comprises Pd
• the solution (A) is made acidic with sulfuric acid or phosphoric acid. Orthophosphoric acid (H 3 PO 4 ) is however preferred.
• the particularly preferred solution (A) comprises approximately 100 mg / l of NaBr, 10 mg / l of Br 2 and 10 g / l of orthophosphoric acid.
• the operation is generally carried out with a reduced amount of supported catalyst of between 5 and 50 g per liter of solution (A). An amount of catalyst close to 10 g per liter of solution (A) is preferred.
• the treatment temperature is generally between 10 and 80 ° C., and preferably between 40 and 60 ° C.
• the duration of treatment can vary within wide limits. This duration can be between 1 and 1 2 hours, and preferably between 4 and 8 hours.
• the catalytic solid is separated from the aqueous solution (A) by any known means, then dried at a temperature between 1 00 and 140 ° C and preferably close to 1 20 ° C. Drying at atmospheric pressure is most often used, for example using a ventilated oven.
• the impregnation of the support can be carried out by any known means.
• the impregnation step consists in bringing the chosen support into contact with a most concentrated aqueous solution possible salt (s) of at least one metal from group M so as to form a paste.
• This contacting can be carried out by adding the concentrated aqueous solution of metal salt (s), at room temperature, in a mixer containing the support.
• the duration of the mixing generally depends on the amount of support involved, but for productivity reasons it is preferred, after the addition of the metal solution, to mix for approximately 0.5 to 3 hours.
• the resulting paste is preferably filtered, then wrung and finally dried. To ensure maximum spin, it is recommended to carefully pack the filtered dough.
• the impregnated support is dried at a temperature preferably between 20 and 50 ° C.
• the drying is advantageously carried out under conditions favoring slow crystallization and, preferably, in the absence of agitation.
• the drying time generally depends on the temperature and the pressure. It is most often between 1 and 7 days. For information, in a vacuum oven heated to 40 ° C, it takes 48 hours to dry the impregnated and wrung out solid. Drying can also be carried out at room temperature for one week.
• a particular mode of preparation of the supported catalyst based on at least one group M metal successively comprises the following steps:
• step (c) reduction of the dried solid from step (b)
• step (d) treatment of the reduced solid from step (c) with an acidic aqueous solution (A), comprising bromine and bromide ions
• step (E) filtration of the solid treated in step (d) and drying at a temperature between 100 and 140 ° C.
• the preferred operating conditions for each stage of the preparation are the same as those described above.
• the experimental conditions already used in the prior art in particular US 5 1 28 1 14 and US 5 352 645, can be applied.
• Any known means for promoting the dissolution of metal salts, in order to obtain a concentrated aqueous solution for the impregnation step (a), can be used. Mention may in particular be made of the use of a few drops of acid, of slight heating and of agitation using ultrasound.
• the oven used for the reduction is first purged with nitrogen for a sufficient time, generally 1 5 and 60 minutes, then swept with hydrogen and then brought to a temperature between 250 and 350 ° C.
• the reduction time of the solid at the chosen temperature can be between 1 and
• a third object of the invention is the process for the direct manufacture of hydrogen peroxide from hydrogen and oxygen. This process is characterized in that the catalyst described above and prepared is used.
• the catalyst can be used both in a process for the direct manufacture of hydrogen peroxide in a tubular reactor and in a stirred reactor. It is particularly suitable for the process in which hydrogen and oxygen are injected into the aqueous reaction medium of the stirred reactor and oxygen is introduced into the continuous gas phase of the stirred reactor.
• the catalyst can advantageously be used in a process for the direct manufacture of hydrogen peroxide in which hydrogen and oxygen are injected into the lower part of the aqueous reaction medium and oxygen is introduced into the phase continuous gaseous gas of the stirred reactor such that the composition of this continuous gaseous phase is outside the flammability zone.
• the catalyst has proven to be very interesting when the stirred reactor is provided with several turbines arranged along a single vertical axis.
• the catalyst has proved particularly advantageous in a continuous process for the direct manufacture of hydrogen peroxide with recycling of reagents, such as hydrogen.
• Aldrich microporous silica (ref. 28,851 -9) having the following characteristics:
• Average particle size 25 ⁇ m BET surface 500 m 2 / g Pore volume 0.75 cm 3 / g
• Average pore diameter 60 ⁇ are placed in a glass beaker, stirred by a magnetic bar.
• the 50 cm 3 of metal salt solution prepared previously are then quickly added.
• After 1 hour 30 minutes of stirring at 25 ° C. a thick slurry is obtained which is filtered on a No. 3 frit and spun under vacuum for 2 hours 30 minutes.
• the filter cake is placed in a crystallizer on a glass cloth and dried 48 hours at 40 ° C in a vacuum oven.
• the dried solid is then reduced in a stream of 60 Nl / h of H 2 at 300 ° C for 1 h 30 then cooled to room temperature in 6 hours.
• the reduced solid is then treated at 40 ° C. for 5 hours with 2000 cm 3 of solution containing 100 mg / l of NaBr, 10 mg / l of Br 2 and 10 g / l of H 3 PO 4 .
• the resulting mixture is then filtered and the catalyst is dried for 24 hours in a ventilated oven at 120 ° C.
• the catalyst contains 0.7% Pd and 0.03% platinum by weight.
• Example 2 The procedure is as for Example 1 with the only difference that the reduced solid is used directly as a catalyst without treatment with the brominated aqueous solution.
• Example 3 After impregnating the silica as in Example 1, instead of filtering the slurry and wringing out the filtered paste, the slurry is dried in a rotary laboratory evaporator (Heidolph with a fluted glass flask of 500 cm 3 ). The flask rotates in an oil bath at 120 ° C. under vacuum of 40 mm Hg. After evaporation, the solid is reduced and then treated as described in Example 1.
• Example 3 The procedure is as described in Example 3 except that the solid after reduction is not treated with the brominated aqueous solution.
• Example 3 The procedure is as described in Example 3 except that after impregnation the slurry is left in ambient air for one week instead of drying in the rotary evaporator.
• Example 7 The procedure is as described in Example 1 except that the Pd is replaced by Au.
• a selected quantity of aqueous reaction medium and catalyst are introduced into a cylindrical reactor of total capacity, 1,500 cm 3 provided with 2 or 3 flanged turbines 45 mm in diameter, 4 vertical counter blades and a tubular cooling bundle. .
• the aqueous reaction medium is prepared by adding 1 2 g of H 3 PO 4 , 58 mg of NaBr and 5 mg of Br 2 in 1000 cm 3 of demineralized water.
• the reactor is pressurized by injecting a selected flow of oxygen into the continuous gas phase.
• the pressure remains constant thanks to a pressure regulator.
• the liquid medium is brought to the chosen temperature by circulation of thermostatically controlled water in the bundle of cooling tubes.
• Stirring is set at 1,900 rpm and selected flows of oxygen and hydrogen are injected into the liquid phase at the center of the lower turbine.
• the flow rate and the hydrogen content of the gas mixture leaving the pressure regulator are measured. After the end of the expected reaction time, the arrival of hydrogen and oxygen in the aqueous reaction medium is cut off and the injection of oxygen into the gaseous phase is continued until the hydrogen disappears in the latter. The oxygen supply is then cut off and the reactor is decompressed.
• the aqueous hydrogen peroxide solution is weighed and separated from the catalyst by filtration on a Millipore ' 8 filter.
• the selectivity for H 2 O 2 is defined as being the percentage of the number of moles of H 2 O 2 formed out of the number of moles of H 2 consumed.
• the conversion rate is defined as the percentage of the volume of H 2 consumed over the volume of H 2 introduced.
• the catalytic results for each test are summarized in the following

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• 1999
  • 1999-08-09 FR FR9910310A patent/FR2796312B1/fr not_active Expired - Fee Related
• 2000
  • 2000-06-07 AU AU55385/00A patent/AU764178B2/en not_active Ceased
  • 2000-06-07 JP JP2001510579A patent/JP4251809B2/ja not_active Expired - Fee Related
  • 2000-06-07 EP EP00940448A patent/EP1204477B1/fr not_active Expired - Lifetime
  • 2000-06-07 TR TR2002/00073T patent/TR200200073T2/xx unknown
  • 2000-06-07 WO PCT/FR2000/001552 patent/WO2001005501A1/fr not_active Ceased
  • 2000-06-07 EA EA200200172A patent/EA004475B1/ru not_active IP Right Cessation
  • 2000-06-07 BR BRPI0012222-0A patent/BR0012222B1/pt not_active IP Right Cessation
  • 2000-06-07 KR KR1020027000074A patent/KR100554927B1/ko not_active Expired - Fee Related
  • 2000-06-07 DE DE60043657T patent/DE60043657D1/de not_active Expired - Lifetime
  • 2000-06-07 PL PL00353747A patent/PL353747A1/xx not_active Application Discontinuation
  • 2000-06-07 NZ NZ516005A patent/NZ516005A/en unknown
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• 2001
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