WO2016079227A1 - Réacteur pour réactions sous pression avec un liquide corrosif et procédé de production de peroxyde d'hydrogene à l'aide du réacteur - Google Patents

Réacteur pour réactions sous pression avec un liquide corrosif et procédé de production de peroxyde d'hydrogene à l'aide du réacteur Download PDF

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Publication number
WO2016079227A1
WO2016079227A1 PCT/EP2015/077068 EP2015077068W WO2016079227A1 WO 2016079227 A1 WO2016079227 A1 WO 2016079227A1 EP 2015077068 W EP2015077068 W EP 2015077068W WO 2016079227 A1 WO2016079227 A1 WO 2016079227A1
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Prior art keywords
reaction vessel
gap
vessel
reactor
liquid
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PCT/EP2015/077068
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German (de)
English (en)
Inventor
Robert Jahn
David BOLZ
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Evonik Degussa Gmbh
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Publication of WO2016079227A1 publication Critical patent/WO2016079227A1/fr

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    • 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
    • B01J19/0006—Controlling or regulating processes
    • B01J19/002—Avoiding undesirable reactions or side-effects, e.g. avoiding explosions, or improving the yield by suppressing side-reactions
    • 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
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/04—Pressure vessels, e.g. autoclaves
    • B01J3/046—Pressure-balanced vessels
    • 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
    • B01J8/0005—Catalytic processes under superatmospheric pressure
    • 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
    • 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
    • B01J2208/00539—Pressure
    • 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
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00054—Controlling or regulating the heat exchange system
    • B01J2219/00056—Controlling or regulating the heat exchange system involving measured parameters
    • B01J2219/00065—Pressure measurement
    • 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
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00162—Controlling or regulating processes controlling the pressure
    • 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
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00182—Controlling or regulating processes controlling the level of reactants in the reactor vessel
    • 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
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00191—Control algorithm
    • B01J2219/00193—Sensing a parameter
    • B01J2219/00195—Sensing a parameter of the reaction system
    • B01J2219/002—Sensing a parameter of the reaction system inside 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00191—Control algorithm
    • B01J2219/00193—Sensing a parameter
    • B01J2219/00195—Sensing a parameter of the reaction system
    • B01J2219/00202—Sensing a parameter of the reaction system at the reactor outlet
    • 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
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00191—Control algorithm
    • B01J2219/00193—Sensing a parameter
    • B01J2219/00204—Sensing a parameter of the heat exchange system
    • 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
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00245—Avoiding undesirable reactions or side-effects
    • B01J2219/00256—Leakage
    • 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
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00245—Avoiding undesirable reactions or side-effects
    • B01J2219/00268—Detecting faulty operations
    • 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
    • Y02P20/141—Feedstock

Definitions

  • the invention is directed to a reactor in which pressure reactions can be carried out safely in a corrosive liquid, as well as to a process for the preparation of
  • Hydrogen peroxide by reacting hydrogen and oxygen over a noble metal-containing catalyst, which is carried out in this reactor under pressure.
  • Hydrogen peroxide is currently produced by the technical anthraquinone process.
  • the reaction is carried out in an aqueous or alcoholic solvent.
  • the reaction In order to achieve good space-time yields and selectivities for hydrogen peroxide, the reaction must be carried out under pressure and with the addition of bromide or iodide and with the addition of acid.
  • reaction mixture used in the direct synthesis of hydrogen peroxide is therefore highly corrosive and leads to pitting corrosion and stress corrosion cracking in metallic materials such as stainless steel or Hastelloy alloys, which are used industrially in the manufacture of pressure vessels.
  • Hydrogen peroxide is therefore needed for a pressure reactor in which the reaction with the corrosive liquid reaction medium can be implemented without the corrosion resulting in damage to pressure-retaining parts of the reactor.
  • WO 2005/108285 proposes to carry out the direct synthesis of hydrogen peroxide in a stainless steel reactor in order to avoid corrosion of stainless steel in such a way that no part of the surface is permanently in contact with the gas phase present in the reactor.
  • This concept requires devices which ensure a complete wetting of the inner surface of the reactor with liquid, which can be achieved only with some technical effort, especially in reactors in which a fixed bed with a catalyst bed is arranged.
  • a mistake in design or operation of the reactor unnoticed to damage the pressure vessel by pitting corrosion or
  • Reactor made of a corrosion-resistant duplex stainless steel with a PREN number of more than 34 use.
  • coatings are not suitable for the direct synthesis of hydrogen peroxide, since hydrogen peroxide can diffuse through the coating and decomposition at the Interface of the coating and container wall can lead to a detachment of the coating from the container wall.
  • Reactors are also known from the prior art in which a reaction vessel made of a corrosion-resistant material is arranged within a pressure vessel and the space between the pressure vessel and the reaction vessel is filled with a barrier medium under pressure, such as a gas or a barrier liquid.
  • a barrier medium under pressure such as a gas or a barrier liquid.
  • GB 1 068,757 describes a pressure reactor with an outer pressure vessel, a reaction vessel made of corrosion-resistant material arranged inside this pressure vessel, a liquid filling the space between pressure vessel and reaction vessel, and a pressure equalization vessel between this liquid and the interior of the reaction vessel.
  • the outer pressure vessel and the reaction vessel disposed inside each consist of an upper part and a lower part, which are interconnected via flanges whose
  • Diameter corresponds to the largest reactor cross-section.
  • DE 1 542 005 describes a pressure reactor with an outer pressure vessel, a reaction vessel made of corrosion-resistant material, which is arranged inside this pressure vessel and which does not bear against the wall of the pressure vessel, of a liquid which separates the space between
  • Pressure vessel and reaction vessel fills, as well as arranged above the highest point of the reactor pressure equalization vessel for this liquid, which brings the liquid with respect to the interior of the reaction vessel to a slight overpressure by the hydrostatic pressure.
  • the reaction vessel is installed as a whole and the pressure vessel must have a correspondingly large opening. If corrosion damage occurs to the reaction vessel, open the pressure vessel and remove the reaction vessel.
  • FIG. 9 a pressure reactor for the treatment of organic wastes with supercritical water, which has an outer pressure vessel and a reaction vessel of corrosion-resistant material arranged in the interior of this pressure vessel. The space between the pressure vessel and reaction vessel is filled with water and monitored by a device for measuring the pH or the conductivity, whether from the
  • Reaction vessel substance passes through a hole or a crack of the reaction vessel in the space between the pressure vessel and the reaction vessel.
  • the outer pressure vessel is made up of several parts which are interconnected by flanges whose diameter corresponds to the largest cross section of the reaction vessel.
  • DE 44 43 078 describes a pressure reactor for oxidations in supercritical water, which comprises an outer pressure tube and an inner reaction tube of corrosion-resistant material and in which the annular gap between the two tubes is filled with a non-corrosive barrier liquid. Between the annular gap and the inner reaction tube is a pressure compensation through gaps, holes or slots and a purge flow of barrier fluid is passed through these openings from the annular gap in the reaction tube.
  • No. 6,939,521 describes a fluoropolymer reactor with a heat exchanger jacket for reacting corrosive materials under pressure.
  • the fluoropolymer reactor comprises an outer pressure vessel and a reaction vessel disposed therein, which may be fluoropolymer, or is a metal vessel internally coated with fluoropolymer or in which is a fluoropolymer insert.
  • the space between the pressure vessel and the reaction vessel is flowed through by cooling or heating fluid.
  • the reactor may include a pressure compensation device for pressure equalization between reaction vessels and
  • baffles may be welded, which may touch the inner wall of the pressure vessel.
  • the document also describes monitoring the liquid in the space to detect a leak.
  • Reaction vessel must be introduced as a whole in the pressure vessel.
  • the pressure vessel must therefore have a flange with a diameter larger than the diameter of the reaction vessel. In the event of corrosion damage to the reaction vessel, this flange must be opened and the reaction vessel lifted out of the pressure vessel.
  • reaction vessels with a large cross-section and an inner diameter of more than 1.5 m are required. In the above construction, the pressure vessel is expensive and expensive to produce by the required large flange.
  • a reactor comprising an outer pressure vessel having a plurality of protrusions on the inner wall and a disposed therein, with the outer wall on the elevations of the outer container supporting the reaction vessel and in the a barrier liquid in
  • Gap between the outer pressure vessel and the reaction vessel allows pressure relief of the reaction vessel and a proof of corrosion damage to the reaction vessel.
  • the invention accordingly provides a reactor for pressure reactions with a corrosive liquid comprising
  • an outer pressure vessel having a plurality of protrusions on the inner wall of the pressure vessel, b) a disposed within the outer pressure vessel reaction vessel whose outer wall is supported on the elevations of the outer pressure vessel, whereby between the inner wall of the outer pressure vessel and the outer wall of the
  • Reaction vessel forms at least one gap-shaped gap
  • the invention also provides a process for the preparation of hydrogen peroxide by reacting hydrogen and oxygen in the presence of a noble metal-containing
  • the reactor according to the invention comprises an outer pressure vessel having a plurality of elevations on the inner wall of the pressure vessel, and one inside the outer
  • Pressure vessel arranged reaction vessel whose outer wall is supported on the elevations of the outer pressure vessel, so that between the inner wall of the outer pressure vessel and the outer wall of the reaction vessel forms at least one gap-shaped gap.
  • the elevations on the inner wall of the pressure vessel may have any geometric shape.
  • punctiform or linear elevations are suitable, the elevations preferably being in the form of elongate ribs.
  • the outer pressure vessel and the reaction vessel have a substantially cylindrical shape and the elevations are designed as extending substantially parallel to the cylinder axis ribs.
  • the distance between the elevations is preferably selected so that the weight forces of the reaction vessel and its contents are discharged to the outer pressure vessel via the elevations, so that the stresses in the material of the
  • the elevations are designed so that the distance between two elevations at any point more than 1200 mm, more preferably not more than 1000 mm.
  • the elevations are preferably carried out separately, so that forms a continuous gap-shaped gap between the inner wall of the outer pressure vessel and the outer wall of the reaction vessel.
  • the outer pressure vessel may additionally be on the Inner wall also have one or more circumferential ribs through which between the inner wall of the outer pressure vessel and the outer wall of the reaction vessel, two or more respective contiguous gap-shaped spaces are formed.
  • the gap-shaped intermediate space preferably has a gap width of 0.5 to 50 mm, more preferably 1 to 30 mm, between the inner wall of the outer pressure vessel and the outer wall of the reaction vessel.
  • the elevations on the inner wall of the pressure vessel preferably have a substantially uniform height, so that the gap-shaped intermediate space has a substantially constant gap width between the inner wall of the outer pressure vessel and the outer wall of the reaction vessel.
  • the reactor according to the invention also comprises at least one line for the supply of
  • Educts in the reaction vessel and at least one conduit for the removal of products from the reaction vessel are preferably designed so that the educts do not come into contact with the material of the outer pressure vessel in the supply to the reaction vessel and the products in the removal from the reaction vessel.
  • the reactor according to the invention further comprises at least one line for the supply of
  • Barrier liquid in the gap-shaped intermediate space and at least one conduit for the removal of barrier liquid from the gap-shaped gap If the reactor has more than one gap-shaped gap between the inner wall of the outer pressure vessel and the outer wall of the reaction vessel, then it is preferable for each of these
  • the lines for the supply of barrier liquid in the gap-shaped intermediate space and for the removal of barrier liquid from the gap-shaped intermediate space are preferably designed so that they allow a flow through the entire gap-shaped gap with barrier liquid.
  • the lines for supplying barrier liquid and for removing barrier liquid are therefore preferably arranged at opposite ends of the gap-shaped intermediate space.
  • the outer pressure vessel and the reaction vessel have a substantially cylindrical shape and the elevations are designed as ribs extending substantially parallel to the cylinder axis
  • the barrier liquid can be distributed between the ribs via a ring-shaped annular conduit with nozzles.
  • the distance between parallel ribs may be selected to be smaller than the gap width and at the supply point for barrier liquid, a channel surrounding the reactor circumference, whose width is greater than the gap width, so that the channel as a distributor for
  • Barrier liquid acts in the parallel channels between the ribs.
  • the reactor according to the invention additionally comprises a device for pressure equalization between the interior of the reaction vessel and the gap-shaped intermediate space.
  • the device may include measuring points for measuring pressure in the interior of the reaction vessel and in the gap-shaped intermediate space, and devices for changing the pressure in the gap-shaped intermediate space, such as a pump for sealing liquid for increasing the pressure and a pressure-retaining valve for sealing liquid.
  • the pressure compensation device comprises a pressure equalization line between the interior of the reaction vessel and the gap-shaped gap.
  • the device for pressure equalization comprises a siphon line whose upper end is open to the interior of the reaction vessel and whose lower end is open to the gap-shaped intermediate space.
  • siphon line refers to a line which is shaped so that even if no liquid flows through the line and the ends of the lines are open to a gas space in the line liquid over the entire cross section of the line remains and a free gas passage prevented by the line.
  • the upper end of the siphon line is opened at a point at the upper end of the reaction vessel to the interior of the reaction vessel, so that a pressure equalization between the barrier liquid and one at the upper end of the
  • Reaction vessel gas volume is carried out. More preferably, the reactor comprises at least one line for supplying barrier liquid to the upper end of the gap-shaped intermediate space, at least one conduit for supplying barrier liquid to the lower end of the gap-shaped intermediate space and at least one conduit for removing barrier liquid from the gap-shaped intermediate space at the opening of the siphon line to the interior of the reaction vessel.
  • the execution of the pressure compensation as a siphon line allows in
  • the reactor according to the invention also comprises a device for detecting a reactant fed to the reaction vessel and / or a product discharged from the reaction vessel in the barrier liquid.
  • the device is preferably connected to the conduit for the removal of barrier fluid from the gap-shaped gap.
  • a physical parameter of the barrier liquid is preferably measured, for example the light permeability or, in the case of an aqueous or aqueous barrier liquid, the conductivity, the redox potential or the pH.
  • a measuring device used for this purpose is preferably arranged either in the line for the removal of sealing liquid from the gap-shaped intermediate space or in a bypass line to this line.
  • the reactor has one with at least one line for the supply of
  • the reaction vessel is composed of segments and the outer pressure vessel and the reaction vessel each have openings through which the segments can be introduced into the reaction vessel and removed from the reaction vessel.
  • the openings are arranged at the upper end of the reactor and closed by a common pressure-retaining lid made of corrosion-resistant material.
  • the segments can be assembled in the reaction vessel via sealing strips, from which they can be used at a later time
  • the segments are in
  • Reaction vessel assembled by welding.
  • the reactor according to the invention can be additional within the reaction vessel
  • internals such as internals for the distribution of gas, internals for the distribution of liquid, internals for supporting a fixed catalyst bed, and coolers, for example in the form of coils or plate coolers.
  • the internals are preferably designed so that they pass through openings in the outer pressure vessel and reaction vessel in the
  • Reaction vessel can be introduced and optionally assembled there.
  • the reactor according to the invention allows pressure reactions with a corrosive liquid using materials that are not permanently corrosion resistant, wherein a
  • the outer pressure vessel can be constructed from an inexpensive and optimized for mechanical resistance steel.
  • a material can be used which is not permanently resistant to the corrosive liquid and in which the inner container can Oberkorrod Schlieren by pitting or stress corrosion cracking. During operation of the reactor is a corroding of the inner
  • Pressure vessel on which the outer wall of the reaction vessel is supported allows for corrosion damage to the reaction vessel easy repair by removing or cutting out the fürkorrod convinced container part and inserting or welding a replacement part, wherein by supporting the spare part on the elevations of the inner wall of the pressure vessel in a simple manner the original geometry of the reaction vessel is restored.
  • catalyst it is possible to use all catalysts known for the direct synthesis of hydrogen peroxide known from the prior art and containing one or more noble metals. Particularly suitable catalysts are known from EP-A 1 038 833, page 3, line 10 to page 4, line 14, from US 6,168,775, column 5, line 65 to column 6, line 64 and WO 2005/00961 1, page 34, line 19 to page 42, line 20 known.
  • the catalytically active component of the catalyst contains one or more noble metals in pure form or in the form of alloys.
  • Preferred noble metals are the platinum metals, in particular palladium, and gold.
  • elements from the series Rh, Ru, Ir, Cu and Ag can be present.
  • Particularly preferred catalysts contain as catalytically active metals at least 80 wt .-% palladium and 0 to 20 wt .-% platinum.
  • supported catalysts are used, in which the catalytically active noble metals or are on the surface of a support material.
  • oxidic or silicate support materials are used, in particular alumina, silica, titania, zirconia and zeolites.
  • carbon-based supports such as activated carbon supports can also be used.
  • Support material can be used in the form of powders, extrudates, granules or moldings with channels.
  • the catalyst used is a noble metal supported catalyst which is arranged in the reaction vessel in the form of a fixed bed.
  • the size of the particles in the fixed bed can be in wide ranges, in particular in the range of 0, 1 to 10 mm. A smaller particle size leads to a high pressure drop, too large particle size decreases the catalytically active surface. Particle sizes in the range of 0.1 to 5 mm, preferably 1 to 3 mm, lead to high productivity.
  • the reaction takes place in an aqueous or alcoholic solvent.
  • an alcohol from the series methanol, ethanol, n-propanol and n-butanol and more preferably methanol is used.
  • Particularly preferred as the solvent is methanol with a
  • the reaction takes place with the addition of 10 -6 to 10 -2 mol / kg of bromide and / or iodide and 0.0001 to 0.5 mol / kg acid.
  • 10 -5 to 10 -3 mol / l bromide and / or iodide is added, more preferably 10 -5 to 5 ⁇ 10 4 mol / l, wherein the bromide is preferred. If the concentration of bromide and / or iodide is above the preferred range, then the stability of the
  • Bromide and / or iodide can be added to the reaction medium in the form of an alkali metal or alkaline earth metal salt, preferably as NaBr or Nal. Likewise, HBr or Hl can also be added.
  • acids are preferably added which have a pK a value of less than 3 and preferably a pK a value of less than 2. Particularly suitable are mineral acids such as sulfuric acid, phosphoric acid and nitric acid. Equally applicable are also in the medium soluble sulfonic acids and phosphonic acids.
  • the acid concentration is in the range of 0.0001 to 0.5 mol / l, and preferably in the range of 0.001 to 0, 1 mol / l. If the acid concentration is higher, the liquid phase becomes undesirably corrosive; if it is lower, then the hydrogen peroxide selectivity may decrease. Lower acid concentrations are preferred in view of the further use of the hydrogen peroxide solution formed.
  • the reaction takes place at a temperature of 0 to 90 ° C, preferably 20 to 50 ° C, and a pressure of 0.5 to 10 MPa, preferably 0.5 to 6 MPa.
  • the reaction is preferably carried out with a hydrogen and oxygen-containing gas mixture whose composition is chosen so that the gas mixture is not
  • the gas mixture contains, in addition to hydrogen and oxygen, one or more inert gases, preferably nitrogen and / or carbon dioxide, more preferably carbon dioxide.
  • the hydrogen content in the gas mixture is preferably limited to a maximum of 6% by volume, more preferably at most 5% by volume. In particular, the hydrogen content is in the range of 3 to 5% by volume.
  • the oxygen content in the gas mixture may be stoichiometric or superstoichiometric and is preferably in the range of 10 to 50% by volume, especially 15 to 45% by volume. Hydrogen and oxygen are preferably fed separately to the reactor.
  • Oxygen can be supplied both in pure form, as well as in the form of air or oxygen-enriched air. Preferably, oxygen is used in pure form.
  • the residual gas obtained at the outlet of the reactor can be wholly or partly recycled to the reactor in order to reduce the cost of recovering unreacted hydrogen.
  • the reactor is preferably operated as a packed bubble column by a fixed bed is placed in the reaction vessel with a noble metal-supported catalyst, below the fixed bed solvent or reaction medium is fed, above the fixed bed liquid reaction mixture with formed
  • Hydrogen peroxide is removed, so that above the fixed bed, a gas space with a gas-liquid phase interface is formed above the packed bed, and below the packed bed hydrogen and oxygen are separated from each other in the form of bubbles dispersed.
  • aqueous or alcoholic solvent used for the reaction of hydrogen and oxygen is particularly preferably used without the addition of bromide, iodide or acid as a barrier liquid. This has the advantage that on the one hand
  • Barrier liquid that enters the reaction vessel does not interfere with the implementation and on the other hand, leakage can be detected by simply changing the conductivity, pH or redox potential by passing into the barrier fluid bromide or iodide ions or acid.
  • the inventive method is carried out in a reactor according to the invention, the device for pressure equalization between the interior of the
  • Siphon considerably comprises and the reaction is carried out so that forms a gas space above a liquid reaction mixture in the reaction vessel and the upper end of the
  • Siphon line is open to the gas space. This allows a simple one hand
  • a reactor which has a circulation circuit for barrier liquid, the aqueous or alcoholic solvent without addition of bromide, iodide or acid is used as a barrier liquid and during the implementation of the circulation circuit is continuously supplied blocking liquid.
  • Reaction medium because of its content of acid and of bromide and / or iodide compared to the materials commonly used for the production of pressure vessels, such as stainless steel material number 1 .4571 or the nickel alloy material number 2.4819, is so corrosive that it comes to pitting corrosion. This problem can not be overcome by coating the reactor surface with a corrosion-resistant polymer, such as polypropylene,
  • Reaction vessel to the point where actually occurs due to corrosion leakage of the reaction vessel. It also allows easy repair of damaged by localized pitting corrosion reaction vessel.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un réacteur qui comporte un récipient extérieure sous pression dont la paroi intérieure est pourvue d'une pluralité de saillies et un récipient de réaction qui est disposé à l'intérieur et dont la paroi extérieure est en appui sur les saillies du récipient extérieur et dans lequel un fluide formant barrière, situé dans l'espace intermédiaire entre le récipient extérieur sous pression et le récipient de réaction, permet de décompresser le récipient de réaction et d'indiquer la corrosion du récipient de réaction ; le réaction est approprié à des réactions sous pression avec un liquide corrosif et est utilisé pour la réaction de l'hydrogène et de l'oxygène en peroxyde d'hydrogène dans un solvant aqueux ou alcoolique avec addition de bromure et/ou d'iodure et d'acide.
PCT/EP2015/077068 2014-11-20 2015-11-19 Réacteur pour réactions sous pression avec un liquide corrosif et procédé de production de peroxyde d'hydrogene à l'aide du réacteur WO2016079227A1 (fr)

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EP14194156 2014-11-20
EP14194156.7 2014-11-20

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WO2016079227A1 true WO2016079227A1 (fr) 2016-05-26

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PCT/EP2015/077068 WO2016079227A1 (fr) 2014-11-20 2015-11-19 Réacteur pour réactions sous pression avec un liquide corrosif et procédé de production de peroxyde d'hydrogene à l'aide du réacteur

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3282459A (en) * 1964-10-02 1966-11-01 Allis Chalmers Mfg Co Pressure vessel having concentric casings
WO1991002232A1 (fr) * 1989-08-11 1991-02-21 Adil Zafer Zaim Cuve anti-fuite
DE4311417A1 (de) * 1993-04-07 1994-10-13 Walter Ludwig Behaelter Stahl Vorrichtung für chemische Flüssigkeiten
US5975335A (en) * 1998-06-15 1999-11-02 Witenhafer; Donald E. Chemical reaction vessel
EP1308416A1 (fr) * 2001-10-30 2003-05-07 Degussa AG Synthèse directe de péroxyde d'hydrogène et sa intégration dans des procédés d'oxidation
DE102004040297A1 (de) * 2003-08-19 2005-04-28 Toshiba Kk Behandlungseinrichtung und Behandlungsverfahren für organischen Abfall
US6939521B1 (en) * 1997-11-21 2005-09-06 Honeywell International Inc. Fluoropolymer reactor with heat exchange jacket
WO2005108285A1 (fr) * 2004-05-11 2005-11-17 Degussa Ag Procede destine a la synthese directe de peroxyde d'hydrogene

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3282459A (en) * 1964-10-02 1966-11-01 Allis Chalmers Mfg Co Pressure vessel having concentric casings
WO1991002232A1 (fr) * 1989-08-11 1991-02-21 Adil Zafer Zaim Cuve anti-fuite
DE4311417A1 (de) * 1993-04-07 1994-10-13 Walter Ludwig Behaelter Stahl Vorrichtung für chemische Flüssigkeiten
US6939521B1 (en) * 1997-11-21 2005-09-06 Honeywell International Inc. Fluoropolymer reactor with heat exchange jacket
US5975335A (en) * 1998-06-15 1999-11-02 Witenhafer; Donald E. Chemical reaction vessel
EP1308416A1 (fr) * 2001-10-30 2003-05-07 Degussa AG Synthèse directe de péroxyde d'hydrogène et sa intégration dans des procédés d'oxidation
DE102004040297A1 (de) * 2003-08-19 2005-04-28 Toshiba Kk Behandlungseinrichtung und Behandlungsverfahren für organischen Abfall
WO2005108285A1 (fr) * 2004-05-11 2005-11-17 Degussa Ag Procede destine a la synthese directe de peroxyde d'hydrogene

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