Classifications

• • 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

Definitions

• the present invention relates to a continuous process for the preparation of a hydrogen peroxide solution in a medium comprising a water-miscible organic solvent by reaction of hydrogen and oxygen, and the use of the solution thus prepared for the epoxidation of olefins.
• WO 00/35894 describes the synthesis of hydrogen peroxide from hydrogen and oxygen on a palladium-containing catalyst with methanol as the solvent. The methanolic hydrogen peroxide solution formed is then used for the epoxidation of propylene.
• EP 0 978 316 discloses a process for producing hydrogen peroxide from the elements using a special catalyst on a sulfonic acid-functionalized activated carbon support.
• An example illustrates the batchwise production of a methanolic hydrogen peroxide solution starting from a gas mixture of 4% by volume of hydrogen, 4% by volume of oxygen and 92% by volume of nitrogen.
• a continuous process is described in which the gas mixture consisting of 3.6% hydrogen, 36.4% oxygen and 60% nitrogen is conducted in a single pass. The technical effect of using nitrogen is not discussed.
• the aim is to conduct the reaction continuously in order to be able to work at a constant pressure.
• an inert gas air is often used as an oxygen source in industrial processes, since air contains about 78% by volume of nitrogen.
• this procedure entails an enrichment of the inert gas in the reaction gas.
• the inert gas In order to prevent the inert gas concentration in the reaction gas from continuously increasing and reaching values at which the hydrogen peroxide synthesis comes to a standstill, the inert gas must be removed via an exhaust gas stream, e.g. B.
• DE 196 42 770 discloses a process for the preparation of hydrogen peroxide solutions by the continuous reaction of hydrogen and oxygen in water and / or -C 3 alkanols. It is pointed out that the reaction gas can be circulated.
• the present invention has for its object to provide a process for the synthesis of hydrogen peroxide in a water-miscible organic medium from the elements hydrogen and oxygen in the presence of a sufficient amount of an inert gas to the fire and explosion hazard from organic solvents in contact with oxygen gas ban, to provide that the hydrogen gas used optimally uses.
• This object is achieved by a process for the continuous preparation of a hydrogen peroxide solution in a medium which comprises a water-miscible organic solvent, in which
• a liquid stream is passed through the reaction zone and comprises a water-miscible organic solvent
• the organic solvent used is explosive in an oxygen-rich atmosphere
• the advantage of the method according to the invention lies in the safe preparation of a hydrogen peroxide solution in the organic solvent.
• the hydrogen peroxide solutions obtained can advantageously be used directly for the epoxidation of olefins without concentration and / or complex cleaning.
• a “water-miscible organic solvent” is to be understood as meaning one which dissolves at least 10% by weight of water or is at least 40% by weight soluble in water.
• the organic solvent can be used in combination with up to 50% by weight of water, e.g. B. with 1 to 20 wt .-% water.
• the liquid stream preferably contains 50 to 100% by weight of the organic solvent, in particular 80 to 100% by weight.
• Technical solvents with a purity of more than 85% by weight, in particular more than 90% by weight, are suitable.
• alcohols with 1 to 4 carbon atoms preferably methanol, ethanol, n-propanol or isopropanol, ketones with 3 to 5 carbon atoms, preferably acetone, butanone or methyl isopropyl ketone, alkanediols with 2 to 4 carbon atoms, preferably ethylene glycol or propylene glycol, dialkyl ether with a total of 2 to 6 carbon atoms such as diisopropyl ether, alkanediol monoalkyl ether with a total of 3 to 8 carbon atoms, preferably methyl glycol, ethyl glycol, butyl glycol, propylene glycol monomethyl ether or propylene glycol monoethyl ether, alkanediol dialkyl ether with a total of 4 to 10 carbon atoms, preferably ethylene glycol diethyl ether, cyclic ethers with 4 to 6 carbon atoms and 1 to 2 to 2
• Suitable catalysts are all noble metal-containing catalysts known to the person skilled in the art which catalyze the conversion of hydrogen and oxygen to hydrogen peroxide, preferably those whose active component contains at least one metal from the platinum group, in particular palladium. If appropriate, they can contain admixtures of other metals such as rhodium, iridium, ruthenium, gold, copper, cobalt, tungsten, molybdenum, tin, rhenium or of non-metals such as phosphorus or boron.
• the catalysts can be applied to metallic or non-metallic, porous or non-porous supports, the deposition of the noble metal onto the support preferably being carried out without current, for example by impregnating or wetting the support. gers with a solution containing the noble metal salt and a reducing agent.
• the carriers can have suitable shapes such as sheets, wires, grids, nets, fabrics or moldings such as Raschig rings, saddle bodies, wire spirals, wire mesh rings or monoliths, as described in DE-A 196 42 770.
• Metallic supports are preferably made of high-alloy stainless steels.
• Non-porous supports are preferred among the non-metallic supports, such as preferably mineral materials, plastics or a combination of both.
• Suitable mineral materials are natural and synthetic minerals, glasses or ceramics.
• Suitable plastics are natural or synthetic polymers.
• Suitable reaction zones are pressure-resistant reactors, preferably tubular reactors and particularly preferably tube-bundle reactors.
• the temperature in the reaction zone can be regulated by an external cooling circuit and / or by an internal cooling system.
• the catalyst is preferably arranged in the form of one or more catalyst beds.
• the beds expediently rest on suitable holding members, e.g. B. perforated sheets.
• the reaction is possible in both the swamp and giant mode.
• the gas stream and the liquid stream are passed from bottom to top through the catalyst bed, the liquid stream generally forming the coherent phase and the gas being in the form of discrete gas bubbles.
• the trickle mode the gas stream and the liquid stream are passed in cocurrent from top to bottom through the catalyst bed, the gas phase generally being coherent and the liquid phase flowing in a pulsating manner or in the form of small streams or as a laminar flow.
• the catalyst can be present as a suspension catalyst. This can e.g. B. by filtration or decanting from the liquid discharge from the reaction zone.
• gases are understood to be received echsel Titan under the conditions of hydrogen peroxide synthesis with any of the components, ie, hydrogen, oxygen, the organic medium, the catalyst or the hydrogen peroxide solution, an undesired W.
• gases include nitrogen and carbon dioxide and the noble gases such as helium, neon, argon or mixtures thereof. Nitrogen is preferably used.
• the gas stream passed through the reaction zone contains the inert gas in such an amount that the volume ratio of the inert gas to oxygen at any point in the reaction zone is at least 2.5: 1, preferably at least 3.5: 1.
• the presence of the inert gas prevents an explosive reaction of the organic solvent with oxygen, even with an unintentional ignition.
• the amount of inert gas required in individual cases can depend on the organic solvent used, the pressure and the temperature and can be determined, if necessary, using appropriate ignition tests.
• the proportion of hydrogen in the gas phase is preferably not more than 4% by volume at any point in the reaction zone.
• the molar ratio of oxygen to hydrogen is preferably at least 2: 1, e.g. B. 2: 1 to 100: 1 and particularly preferably at least 4: 1. Molar ratios of at least 2: 1 lead to higher selectivities.
• the total pressure of the gas stream is generally 1 to 300 bar, preferably 10 to 200 bar and particularly preferably 30 to 150 bar.
• the reaction temperature is generally 0 to 25 80 ° C, preferably 5 to 60 ° C and particularly preferably 25 to 55 ° C.
• the noble metal-containing catalyst consumes hydrogen and oxygen to form
• the gas stream 40 can be deducted. If necessary, the gas stream is cooled in order to remove part of the heat of reaction. If desired, the withdrawn liquid stream can also be passed through the reaction zone several times in order to obtain higher hydrogen peroxide concentrations than in a single pass.
• the amount of hydrogen and oxygen consumed is supplemented by adding essentially pure oxygen and essentially pure hydrogen to the gas stream. It is a critical feature of the invention to use the essentially pure gases as the hydrogen or oxygen source, so that no significant amounts of inert gases are introduced into the gas stream via the supplemented hydrogen and oxygen. "Essentially pure" is intended to indicate that technical gases, which may contain minor amounts of foreign gases, can also be used.
• the supplemented hydrogen and oxygen gas generally has a purity of at least 97% by volume, in particular at least 99% by volume, particularly preferably at least 99.5% by volume. The addition can take place in the recycle gas stream or at one or more points in the reaction zone.
• inert gas cushion inert gas cushion
• hydrogen and oxygen and optionally inert gas are added in a consumption-controlled manner.
• the composition of the gas stream and / or the depleted gas stream is analyzed continuously or periodically, the composition is compared with a predetermined composition and hydrogen, oxygen and / or inert gas is added in accordance with the comparison.
• a small amount of gas is taken from it continuously or periodically and examined by means of gas analysis.
• Various measurement methods such as gas chromatography, thermal conductivity measurement, gas density measurement, mass spectroscopy, sound velocity measurement and magnetomechanical measurement methods are available for gas analysis.
• the amount of gas for analysis can be removed at any point in the gas recirculation circuit, for example after the depleted gas stream has left the reaction zone or before the gas stream containing fresh gases has reentered it.
• the acid concentration is usually at least 10 -4 mol / 1, preferably 10 ⁇ 3 to 10 ⁇ 2 mol / 1.
• the liquid stream fed to the reaction zone usually still contains small amounts of halides, such as bromide or chloride, or pseudohalides in concentrations of, for. B. 1 to 1000 ppm, preferably 3 to 300 ppm.
• halides such as bromide or chloride
• pseudohalides in concentrations of, for. B. 1 to 1000 ppm, preferably 3 to 300 ppm.
• hydrobromic acid which combines the functions of acid and halide, is particularly preferred, usually in concentrations of 1 to 2000 ppm, preferably 10 to 500 ppm.
• the solution of hydrogen peroxide in an organic solvent which may also contain water and which is prepared by the process according to the invention can be used without isolating the hydrogen peroxide for the epoxidation of olefins, such as propylene in particular, but also ethylene, cyclohexene, cyclooctene, 2-butene, 1 -Oc-, allyl chloride, isoprene and the like. a. be used. If necessary, the solutions can be neutralized before the epoxidation step by adding bases or using ion exchangers.
• olefins such as propylene in particular, but also ethylene, cyclohexene, cyclooctene, 2-butene, 1 -Oc-, allyl chloride, isoprene and the like.
• olefins such as propylene in particular, but also ethylene, cyclohexene, cyclooctene, 2-butene, 1
• epoxidation of olefins by means of the hydrogen peroxide solution prepared according to the invention is carried out on suitable catalysts, for. B. on titanium silicalite catalysts, as described in EP-A-100 119.
• suitable catalysts for. B. on titanium silicalite catalysts, as described in EP-A-100 119.
• the hydrogen peroxide solution depleted in the epoxidation step can expediently be returned to the hydrogen peroxide synthesis process according to the invention, with stabilizers removed before the epoxidation step possibly being replaced again.
• FIG. 1 The invention is illustrated in more detail by the attached FIG. 1 and the following examples.
• the pressure reactor 1 which is z. B. is a cooled double-walled tube, a liquid stream is fed via line 6, which contains a water-miscible organic solvent u.
• a gas flow is fed to the pressure reactor 1 via the line 8 Contains hydrogen, oxygen and an inert gas.
• the two-phase, gaseous-liquid mixture leaving the pressure reactor 1 passes via line 9 into a separator 2.
• the liquid fraction obtained there is partly discharged via line 11 as a 5 H 2 O 2 solution and partly via line 10, the liquid pump 3 and line 7 are returned to the pressure reactor 1.
• the gaseous fraction obtained in the separator 2 is fed back into the pressure reactor 1 via the line 12, the membrane compressor 4 and the line 8.
• the device 5 continuously analyzes the composition of the gas stream occurring at the separator 2.
• the gas analysis device 5 provides an electronic measurement signal which controls the metering of hydrogen gas, oxygen gas and inert gas via lines 13, 14 and 15.
• Net rolls were used as carriers, which were wound from two layers of wire mesh measuring 3 x 17 mm to form cylinders with a diameter of 3 mm and a height of 3 mm.
• the 25 wire mesh consisted of 100 ⁇ m thick wires made of steel 1.4539.
• the carrier was degreased for 90 minutes at 40 ° C. in an ultrasonic bath with an aqueous surfactant solution and etched for 60 minutes at 60 ° C. in a circulation apparatus with 10% hydrochloric acid.
• a mixture was poured into the coating reactor, which contained 1600 ml of water, 96 g of sodium hypophosphite, 216 g of ammonium chloride and 320 ml of 25% ammonia, and the mixture was heated to 60 ° C. with circulation (400 l / h).
• the activated balls were placed in the coating reactor described above. After adding a solution of 85.2 g sodium hypophosphite, 192.2 g ammonium chloride and 259 ml 25% ammonia
• reactor 1 An apparatus as shown in Fig. 1 was used. 700 ml of catalyst were introduced into reactor 1, which was designed as a double-walled metal tube (diameter 21 mm, length 2.00 m).
• the feed consisted of a solution of 121 ppm hydrogen bromide in methanol.
• the solution was pumped through the plant at a constant rate of 1000 ml / h.
• the liquid was circulated at a circulation speed of 150 l / h.
• the system was brought to a pressure of 50 bar by supplying nitrogen with the aid of a pressure maintaining valve.
• the membrane compressor 4 was switched on and set to a gas circulation of 10400 Nl / h.
• a gas flow of 44 Nl / h was drawn off into the gas analysis device 5, which consisted of a thermal conductivity detector and an oxygen analyzer and which allowed the hydrogen and oxygen contents of the gas mixture to be determined continuously.
• the metering valve for oxygen was controlled so that the gas stream contained 19% oxygen after passing through the reaction zone.
• the hydrogen metering valve was then also controlled in such a way that the gas stream contained 3% hydrogen after passing through the reaction zone.
• These two flows were continuously controlled together with the mass flow meter for nitrogen so that the gas flow after passing through the reaction zone and thus also the gas cycle contained 3% hydrogen and 19% oxygen.
• the liquid emerging from the reaction tube was separated from the circulating gas in separator 2 and conveyed out of the system. The hydrogen peroxide content in the liquid discharge was continuously monitored by titrations.
• the pressure reaction was run continuously for 72 hours. After 17 hours, the hydrogen conversion and hydrogen peroxide content in the liquid discharge were constant. A content of 7% by weight of hydrogen peroxide and 1.4% by weight of water in the discharge was measured. A selectivity of 72% was calculated from the amount of hydrogen consumed.
• FIG. 1 An apparatus as shown in FIG. 1 was used, but the gas flow to the gas analysis device 5 was withdrawn immediately before the reactor inlet.
• the double jacket reactor 1 of the apparatus was charged with the catalyst B.
• a solution of 120 mg / l hydrogen bromide in methanol was trickled over the catalyst bed at a rate of 1000 ml / h.
• a mixture of 3.5% hydrogen, 19% oxygen and 77.5% nitrogen was produced at a rate of 10400 Nl / h pumped from top to bottom in a circle over the catalyst bed.
• the composition of the gas mixture was regulated as described in Example 1.
• the product mixture emerging from the reaction tube was separated from the gases under pressure in a separator and conveyed out of the system in liquid form.
• the mass flow was balanced against the inflow.
• the hydrogen peroxide content in the liquid discharge was determined by titration.
• the amount of hydrogen consumed by the formation of hydrogen peroxide and water was calculated from the mass flows of gases introduced and from the exhaust gas flow.
• the selectivity based on hydrogen was calculated from the mass of the discharge stream, the content of hydrogen peroxide and the amount of hydrogen consumed.
• the space-time yield resulted from the amount of hydrogen peroxide formed per unit of time based on the volume of 700 ml of catalyst bed in the tubular reactor.

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• Chemical & Material Sciences (AREA)
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• Inorganic Chemistry (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Epoxy Compounds (AREA)
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• 2001
  • 2001-04-12 DE DE10118460A patent/DE10118460A1/de not_active Withdrawn
• 2002
  • 2002-04-11 CA CA002443203A patent/CA2443203A1/en not_active Abandoned
  • 2002-04-11 CN CNB028079442A patent/CN1226183C/zh not_active Expired - Fee Related
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  • 2002-04-11 AU AU2002254986A patent/AU2002254986A1/en not_active Abandoned
  • 2002-04-11 EP EP02724286A patent/EP1379464A2/de not_active Withdrawn
  • 2002-04-11 US US10/474,686 patent/US20040126312A1/en not_active Abandoned
  • 2002-04-11 WO PCT/EP2002/004052 patent/WO2002083550A2/de not_active Application Discontinuation
• 2003
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