EP0776316A4 - Installation et procede de production de peroxyde d'hydrogene a partir de l'hydrogene et de l'oxygene - Google Patents

Installation et procede de production de peroxyde d'hydrogene a partir de l'hydrogene et de l'oxygene

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Publication number
EP0776316A4
EP0776316A4 EP95929511A EP95929511A EP0776316A4 EP 0776316 A4 EP0776316 A4 EP 0776316A4 EP 95929511 A EP95929511 A EP 95929511A EP 95929511 A EP95929511 A EP 95929511A EP 0776316 A4 EP0776316 A4 EP 0776316A4
Authority
EP
European Patent Office
Prior art keywords
hydrogen
oxygen
aqueous medium
reaction
medium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP95929511A
Other languages
German (de)
English (en)
Other versions
EP0776316A1 (fr
Inventor
Harold A Huckins
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Princeton Advanced Technology Inc
Original Assignee
Labko Oy AB
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US08/509,841 external-priority patent/US5641467A/en
Application filed by Labko Oy AB filed Critical Labko Oy AB
Publication of EP0776316A1 publication Critical patent/EP0776316A1/fr
Publication of EP0776316A4 publication Critical patent/EP0776316A4/fr
Withdrawn legal-status Critical Current

Links

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
    • 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
    • B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
    • 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
    • B01J19/0053—Details of the reactor
    • B01J19/0066—Stirrers
    • 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
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B01J19/243—Tubular reactors spirally, concentrically or zigzag wound
    • 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
    • B01J3/044—Pressure vessels, e.g. autoclaves in the form of a loop
    • 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
    • B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
    • 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
    • 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
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00094—Jackets
    • 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
    • B01J2219/00121—Controlling the temperature by direct heating or cooling
    • 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

Definitions

  • the present invention relates to a method and apparatus for producing hydrogen peroxide by injecting minute bubbles of hydrogen and oxygen into a liquid stream of an aqueous solution of water and an inorganic acid and a Group VIII metal catalyst in which the liquid stream flows at high velocity.
  • the primary conventional industrial method for production of hydrogen peroxide uses a chemical agent first for the reduction or hydrogenation.
  • alkylanthraquinone such as ethyl or tertiary butyl anthraquinone
  • This working solution contains organic solvents such as di- isobutylcarbinol and methyl naphthalene. Oxidation of the intermediate product of the reduction reaction produces hydrogen peroxide and the original alkylanthraquinone. The anthraquinone is recycled back through the process.
  • U.S. Patent 4,996,039 describes first absorbing hydrogen into the aqueous reaction mixture with a catalyst; dropping the pressure to remove all the hydrogen in the gas phase; and then introducing the oxygen in order to produce hydrogen peroxide. This technique minimizes the presence of hydrogen in the gaseous phase. This process is expensive to repressure the reactor with oxygen and doesn't lend itself to continuous processing.
  • U.S. Patent No. 4,279,883 describes a process for preparing hydrogen peroxide in an aqueous medium.
  • the aqueous medium contains dissolved hydrogen and a platinum-group catalyst having absorbed thereto hydrogen.
  • Inert nitrogen and argon are blown into the aqueous medium so that no dissolved oxygen is present in the aqueous medium during the hydrogen absorbing treatment.
  • Oxygen gas is injected into the medium after the absorption of the hydrogen on the catalyst and the_ gaseous zone and liquid zones are stirred.
  • This patent has the shortcoming of requiring an injection of an inert gas into the reactor during the hydrogen absorption phase to prevent an explosion between the hydrogen and oxygen gases.
  • U.S. Patent No. 5,194,242 ( , 242 patent) describes a process for preparing hydrogen peroxide in which an acidic aqueous solution fills an elongated reaction zone in a tubular reactor. A catalyst is provided to the reaction zone. Oxygen together with recycled gas and then hydrogen are dispersed into the solution in proportions that are above the lower flammability limit for hydrogen and oxygen and are maintained at a temperature and pressure until the reaction mixture has decreased to below the lower flammability limit for the hydrogen and oxygen mixture. The partial pressure of hydrogen and oxygen is super- atmospheric in the range of about 20 to about 400 psi. The aqueous solution flows through the reactor at liquid velocity at rate from about 4 to about 8 ft/sec.
  • the ratio of the flow of the aqueous medium to the aggregate flow of the hydrogen and oxygen is such that a gas phase regime of large elongated bubbles may be produced, which, if reacted violently would not be surrounded by sufficient liquid volume to cool the gas mixture, resulting in elevated temperature and pressure which can result in an explosion of the gas mixture.
  • Patentees provide no teaching of the importance of operating in a regime in which small discrete individual bubbles exist which can be quenched by the surrounding medium. It is desirable to provide a safe direct combination process for producing hydrogen peroxide which has low manufacturing costs.
  • the invention comprises a method and apparatus for producing hydrogen peroxide in which hydrogen and oxygen are separately injected into a liquid filled reactor to form a plurality of discrete individual bubbles in a continuous rapidly flowing liquid stream.
  • Each bubble is surrounded by a continuous liquid phase such that if the hydrogen and oxygen gas reacted, there is sufficient liquid available to quench/cool down the reaction in order to prevent an explosion propagating throughout the reactor. It has been found that it is critical to maintain the ratio of the volume of flow of aqueous medium to the aggregate volume of flow of hydrogen and oxygen, at a high value so as to avoid uncontrolled reaction of hydrogen and oxygen bubbles to form water.
  • a pipeline reactor is used having a plurality of passes within the reactor.
  • the pipeline reactor can be formed of a plurality of tubes arranged vertically or horizontally and connected with curved (elbow) tubes.
  • the liquid stream can be formed of water, a dilute acid and a Group VIII metal catalyst.
  • the Group VIII metal catalyst can be platinum or palladium or a mixture of the two on an inert support such as alumina, silica or carbon.
  • the liquid stream fills the reactor. Fine dispersed hydrogen gas bubbles can be dissolved into the flowing liquid stream. After the hydrogen is dissolved, finely dispersed oxygen gas bubbles are injected into the liquid stream for reacting with hydrogen to form hydrogen peroxide. After this first reaction is complete, multiple injections of first hydrogen and then oxygen can be used to raise the concentration of hydrogen peroxide produced to a predetermined level. The number of injections of hydrogen and oxygen bubbles can be varied for producing the desired concentration of the hydrogen peroxide.
  • the present invention has the advantage of avoiding a continuous gas phase between the hydrogen and oxygen and having full utilization of the entire volume of the reactor.
  • the production of hydrogen peroxide occurs in the liquid phase between the dissolved hydrogen gas and oxygen in the presence of a catalyst.
  • the method prevents an explosive reaction from expanding, thereby allowing the concentration of unreacted hydrogen and oxygen to be within the explosive range.
  • Fig. 1 is a schematic diagram of an apparatus for continuously producing hydrogen peroxide from hydrogen and oxygen according to an environment of the invention.
  • Fig. 2 is a schematic diagram of an apparatus for producing hydrogen peroxide in a semicontinuous batch process according to another embodiment of the invention.
  • DETAILED DESCRIPTION OF THE INVENTION Fig. 1 illustrates a schematic view of the apparatus 10 for producing hydrogen peroxide from hydrogen and oxygen.
  • Water 12 and catalyst 14 are added to tank 16.
  • Catalyst 14 is preferably a supported Group VIII metal catalyst.
  • catalyst 14 is palladium or platinum or mixtures thereof. Examples of a support useful for supporting the catalyst in a dispersed fashion are carbon, silica and alumina. It will be appreciated that other catalysts known in the art of hydrogen peroxide production can be used in the present invention.
  • Stabilizer 15 can be an acidic solution having a Ph in the range of about 2 to 7. Examples of acids useful for the present invention are hydrochloric, phosphoric, and other commercially available inorganic acids. Typically, the amount of stabilizer 15 added to water is less than about 1% of the reaction medium.
  • Solution 17 within tank 16 can be stirred with an automatic or manual agitation means 18.
  • Solution stream 20 is circulated with recirculating pump 22 as input stream 24. Liquid stream 24 is received at pipeline reactor 26 and fills pipes 27 of pipeline reactor 26. Liquid stream 24 has a flow velocity of greater than 10 feet pef second for avoiding the presence of a continuous gas phase or elongate ⁇ bubbles within reactor 26.
  • the flow velocity of liquid stream 24 is in the range of more than 10 feet per second to about 50 feet per second. Most preferably, the flow velocity of liquid stream 24 is in the range of about 11 to about 20 feet per second.
  • Pipeline reactor 26 is preferably formed of a plurality of pipes 27 joined with a 180° bend. Joined pipes 27 can be arranged either vertically or horizontally. The length and diameter 27 of pipes are predetermined for providing the desired flow velocity. Preferably, pipes 27 are formed of a commercially available heavy wall pipe such as a U.S. schedule 160 which has a wall thickness form 0.44 to 1.31 inches over the size range of 3 to 12 inches. Pipes 27 useful for practice of the present invention can have diameter in the range of 2 inches to at least 12 inches.
  • the preferred length of pipeline reactor 26 can vary widely depending on the number of joined pipes 27 used in the reactor. Typically, joined pipes 27 have a total length in the range of about 50 to about 60,000 feet. Preferably, joined pipes 27 have a length of about 2,000 to about 45,000 feet. It will be appreciated that the number of pipes
  • the 27 used in pipeline reactor 26 can be varied to change the number of injection points or passes in the pipeline reactor 26.
  • the number of passes of pipeline reactor 26 is between about six and about 48 passes.
  • the pipeline reactor 26 operates at a pressure in the range of about between 30 to about 300 atm.
  • the reaction temperature normally is in the range of 0°C to 60°C. The lower the temperature of the aqueous medium the higher the solubility of hydrogen is in solution. Similarly, the higher the pressure, the greater the solubility of hydrogen is in solution.
  • the reaction temperature can be maintained by providing jacketing on each pipe 27 or by installing the entire pipeline reactor 26 within a vessel in which a refrigerant is being evaporated or cold liquid solution is circulated.
  • the ratio of the volumetric flows of the aqueous reaction medium and the aggregate flows of the gaseous hydrogen and oxygen at of broadly from 300 to 30, preferably from 200 to 40 and most desirably from 150 to 50. If the flow ratios are maintained within these ranges and the velocity of the flowing liquid is maintained at above 10 feet per second, as described above, a regime of tiny bubbles surrounded by adequate aqueous medium is created and the risk of runaway explosion by reaction of bubbles is substantially obviated.
  • the local increase of the temperature due to the reaction of hydrogen and oxygen bubbles to form water is desirably less than 3°C This is achieved with the volumetric flow rates and velocities of the invention.
  • the volumetric ratio of oxygen to hydrogen may be in the range of 1:1 to 50:1.
  • the art has recognized that higher ratios of oxygen to hydrogen may be desirable to force the reaction to completion. It is recognized that oxygen is by far the cheaper of the reactants and accordingly, excess oxygen can be vented from the system without excessive economic penalty.
  • the reaction takes place in the flammable range, the volume ratio of oxygen to hydrogen being from 1:1 to 20:1.
  • the foregoing ratios of the flows of aqueous medium to the aggregate volumetric flows of hydrogen and oxygen in turn set the ratios of the volume of aqueous medium to each of the volumes of hydrogen and oxygen, respectively, at the several hydrogen and oxygen gas inlets.
  • the ratio of the volumetric flow of aqueous medium to the volumetric flow of hydrogen at each hydrogen gas inlet is broadly from 15,000 to 60.
  • the ratio of the volumetric flow of aqueous medium to the volumetric flow of oxygen is from about 15,000 to 60.
  • a gaseous stream of hydrogen 28 is injected by valve 30 into a flowing liquid stream 24 at point 31. Liquid stream 24 flows between points 31 and 33 of pipe 27. Hydrogen is dissolved in a liquid stream 24.
  • a gaseous stream of oxygen 34 is injected by valve 32 into liquid stream 24 at point 33. Within pipeline reactor 26, the dissolved hydrogen 28 reacts with the gaseous oxygen 34 to form hydrogen peroxide in solution.
  • gaseous hydrogen 28 and gaseous oxygen 34 are sparged into liquid stream 24 by a small diameter nozzle for producing a plurality of minute bubbles.
  • the nozzle has a diameter in the range of about 0.001 inches to about 0.25 inches to produce fine minute bubbles which are surrounded by rapidly flowing liquid stream 24.
  • the minute bubbles of hydrogen and oxygen are of a size which is small enough to be surrounded by flowing liquid stream 24.
  • the volume of liquid stream is sufficiently large and continuous so that in the event of any explosion of a single bubble the surrounding liquid can expeditiously quench the explosion within the bubble to prevent the propagation of the explosion throughout the entire regime of the reactor.
  • the flow rate of liquid stream 24 and the injection of minute bubbles provide a dispersed bubbly regime in liquid stream 24.
  • Additional gaseous hydrogen 28 can be injected at a plurality of passes through pipeline reactor 26 with respective valves 35, 46, 50, 55 and 59 at points 36, 47, 51, 56 and 60 for dissolution into liquid stream 24.
  • Additional gaseous oxygen 34 can be injected downstream of hydrogen injection points 36, 47, 51, 56 and 60 with respective valves 40, 48, 53, 57 and 61 at respective points 41, 49, 54, 58 and 62 for reacting with the dissolved hydrogen.
  • the point of oxygen introduction is sufficiently distanced from that of hydrogen injection to permit the hydrogen to have become distributed throughout the aqueous medium as tiny dispersed bubbles and to dissolve in the aqueous medium.
  • the second volume of hydrogen and subsequent volumes of hydrogen introduced along the elongated reaction zone are introduced after about 50% of the previously introduced hydrogen has been reacted with oxygen and preferably after at least 75% of the previously introduced hydrogen has been reacted.
  • stream 64 flows from pipeline reactor 26.
  • a diluent gas 66 can be added to stream 64.
  • An example of a diluent gas useful for practice of the invention is nitrogen.
  • a pressure letdown valve 68 can be used before gas-liquid separator 70 for reducing the pressure of the inlet mixture 69 to gas-liquid separator 70.
  • Gas liquid separator 70 separates liquid 72 from gas 74.
  • Gas 74 containing unreacted oxygen, nitrogen and some unreacted hydrogen from separator 70 can be recycled with recycled gas compressor 78 and can be injected at point 75 into liquid stream 24.
  • separated gas 74 can be purged with valve 76. It will be appreciated that a gas liquid separator useful for practice of the present invention is known in the art.
  • Stream 64 can be received at additional pipeline reactors 26 for connecting the reactors in series before gas liquid separator 70.
  • Separated liquid 72 containing the hydrogen peroxide product in the aqueous solution of catalyst and acid is passed to filter 80 for recovering the catalyst as a filter cake 82.
  • Filter cake 82 can be-added to tank 16 for recycling the catalyst.
  • Filtrate 84 includes the hydrogen peroxide product and the aqueous acid water solution. Filtrate 84 is received at ion exchange, apparatus 86 for removing the acid from the filtrate.
  • Hydrogen peroxide product 88 from ion exchange apparatus 86 can be directly used as a hydrogen peroxide product.
  • hydrogen peroxide product 88 can be received at column 90 for concentrating the hydrogen peroxide product 88 in order to produce a concentrated hydrogen peroxide product 94.
  • Column 90 can be an evaporation or distillation column. Water 92 removed from column 90 can be recycled into water stream 12 as make-up water.
  • the concentration of hydrogen peroxide product 82 produced by pipeline reactor 26 depends on the number of injections of hydrogen and oxygen in the passes of pipeline reactor 26.
  • hydrogen peroxide product 82 has a concentration in the range of about 2% to about 30% of hydrogen peroxide in solution.
  • hydrogen peroxide product 94 has up to 70% concentration.
  • the present invention has the advantage of providing an economical and safe process for producing hydrogen peroxide.
  • the process does not specifically inject an inert gas or chemical agent within the reactor, thereby reducing costs.
  • the entire regime of the pipeline reactor comprises a dispersed bubbly regime in a rapidly flowing liquid stream for preventing the formation of an explosive gas phase with the reactor.
  • the entire pipeline is utilized for the production of the hydrogen peroxide.
  • the high surface to volume relationship of the reactor provides inexpensive removal of heat from the reactor.
  • a circulating aqueous stream of a suspended group VIII metal catalyst deposited on an inert carrier with an acid stabilizer is delivered at a pressure of 200 atmospheres (3000 psi) to the first of two tubular reactors operated in series at a flow rate of 195,000 pounds per hour per reactor in the reactor shown in Fig. 1.
  • the reactor consists of 4" schedule 160 pipes 100 feet long, each connected together by 180° U bends.
  • the liquid flow rate has a liquid velocity of 13 feet/second.
  • the liquid stream is introduced into the reactor at 15°C.
  • At the reactor inlet 27.2 pounds per hour of hydrogen gas is injected through a nozzle to form fine individual bubbles in the liquid stream flowing at 13 feet/second.
  • Recycled gas from the gas-liquid separator can be injected into the process fluid. This is followed by the injection of 432 lbs/hr. of oxygen as finely dispersed bubbles which reacts with the hydrogen to form hydrogen peroxide. This is followed by repeated injections for each reactor of first hydrogen and the oxygen to form hydrogen peroxide of increasing concentration. The heat of reaction is removed by the circulation of cooled water (or refrigerant) outside the reactor pipes.
  • the effluent After passing through the second reactor, the effluent flows through a pressure letdown valve before a gas-liquid separator. Nitrogen or other diluent gas is added to the reactor effluent as needed to assure the exit gas from the separator is outside the explosive/flammable limits of hydrogen and oxygen. This gas can be either recycled to the first reactor or vented to atmosphere.
  • the liquid phase is filtered to remove the suspended catalyst slurry so that it can be resuspended in the aqueous medium. This is done in a mix tank where the concentration of each ingredient is checked and adjusted as needed. This includes the acid used as a stabilizer for hydrogen peroxide.
  • the filtrate from the filter that contains the desired hydrogen peroxide product passes over an ion exchange or equal agent to remove residual acid values from the hydrogen peroxide product.
  • This product can then be used directly or can be concentrated in an evaporator or distillation column to concentrated in an evaporator or distillation column to concentrations up to 70% following conventional practice. A total production of 100,000,000 pounds per year of hydrogen peroxide can be produced from these two reactors.
  • FIG. 2 illustrates an alternate method of operating the process of the invention in a batch, semicontinuous fashion.
  • a fresh batch of reaction medium consisting of a group VIII metal catalyst on an inert support in an acidic aqueous solution, is charged through valve 1 to separator 2.
  • the solution is charged to the reactor via valve 3 and recirculating pump 4. Once the system is filled, flow of fresh solution is stopped by closing valve 1. The pressure in the system is increased by closing valve 5.
  • the velocity of the medium is maintained at 10 feet per second or more.
  • Hydrogen is injected at injection system 6. The amount of hydrogen introduced is at or less than the solubility limit in the flowing medium. Oxygen is introduced at point 8, at a sufficient distance downstream (pipe length 7) to ensure the absorption of hydrogen. At full capacity, hydrogen flow is about 15 pounds per hour and oxygen flow is approximately 250 pounds per hour. Sufficient pipe length 9 is provided downstream of the oxygen injection to permit the maximum conversion to hydrogen peroxide.
  • the pipeline is cooled by a coolant on the outside of the pipe to maintain an operating temperature between 5 and 30°C.
  • the reactor effluent passes to separator 2 to disengage the gas 10 from the liquid.
  • the exit gas is outside the flammable range so it can be recycled back to the reactor by recycle compressor 11.
  • fresh oxygen 12 is added to the recycle stream before it is injected at point 8.
  • nitrogen 13 is injected into the effluent stream.
  • Effluent gas 14 is then vented from the system.
  • Pump 4 recirculates the liquid medium until the hydrogen peroxide reaches its desired concentration, desirably between 4-15% by weight, preferably 5-8%. Gas injection will continue for from one to three hours.
  • the reactor system, including the separator, pump and piping is then drained.
  • the system is then refilled with a fresh reactor charge following the procedure outlined above. This batch semicontinuous procedure produces from 1,000,000-1,500,000 pounds per year of hydrogen peroxide product. With smaller or larger diameter pipe of the same length, lower or higher quantities, respectively, of hydrogen peroxide are produced.
  • EXAMPLE III EXAMPLE III
  • the batch semicontinuous process described in Example II can be carried out in a modified way to reduce both the capital costs and operating costs of the reaction system.
  • the basic flow diagram of Fig. 2 is used with the exception that a second reaction medium charge pump is provided in parallel with recirculating pump 4 in order to fill the system and the pressure let down valve 5, rather than being at the effluent of the reactor pipeline upstream of the separator, is downstream of the separator in the gas effluent line.
  • the operating pressure in the separator remains high (1,000-4,000 psi) throughout the course of the reaction. Pressure is maintained by "head" gas above the separator liquid.
  • the gas to be recycled enters recycle compressor upstream of the pressure letdown valve.
  • the exit gas in line 10 passes through a pressure letdown valve.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Installation et procédé permettant de produire en toute sécurité du peroxyde d'hydrogène par injection de bulles minuscules dispersées d'hydrogène (28) et d'oxygène (34) dans un milieu liquide (24) en écoulement rapide. Les bulles minuscules sont enrobées par le milieu liquide en un volume suffisant pour interdire toute réaction explosive entre l'hydrogène et l'oxygène. Le milieu liquide est constitué d'une solution acide aqueuse et d'un catalyseur métallique du groupe VIII (14). L'hydrogène (28) est projeté dans le milieu en écoulement (24) afin d'y être dissous. Les bulles d'oxygène (34) réagissent avec l'hydrogène dissous pour former le peroxyde d'hydrogène (72). Selon le mode de réalisation préféré, le milieu liquide s'écoule à une vitesse d'au moins 10 pieds par seconde pour produire un régime d'écoulement bouillonnant dans le réacteur. De l'eau (12) et le catalyseur (14) sont introduits dans la cuve (16). De préférence, une certaine quantité de stabiliseur de peroxyde d'hydrogène est déversée dans la cuve (16). Cette méthode et cette installation permettent d'obtenir du peroxyde d'hydrogène dans des conditions de sécurité et à un faible coût.
EP95929511A 1994-08-16 1995-08-10 Installation et procede de production de peroxyde d'hydrogene a partir de l'hydrogene et de l'oxygene Withdrawn EP0776316A4 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US29143794A 1994-08-16 1994-08-16
US291437 1994-08-16
US509841 1995-08-01
US08/509,841 US5641467A (en) 1994-08-16 1995-08-01 Method for producing hydrogen peroxide from hydrogen and oxygen
PCT/US1995/010304 WO1996005138A1 (fr) 1994-08-16 1995-08-10 Installation et procede de production de peroxyde d'hydrogene a partir de l'hydrogene et de l'oxygene

Publications (2)

Publication Number Publication Date
EP0776316A1 EP0776316A1 (fr) 1997-06-04
EP0776316A4 true EP0776316A4 (fr) 1998-05-13

Family

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Family Applications (1)

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EP95929511A Withdrawn EP0776316A4 (fr) 1994-08-16 1995-08-10 Installation et procede de production de peroxyde d'hydrogene a partir de l'hydrogene et de l'oxygene

Country Status (5)

Country Link
EP (1) EP0776316A4 (fr)
JP (1) JPH10504008A (fr)
AU (1) AU710994B2 (fr)
CA (1) CA2197655A1 (fr)
WO (1) WO1996005138A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6042804A (en) * 1994-08-16 2000-03-28 Advanced Peroxide Technology, Inc. Method for producing hydrogen peroxide from hydrogen and oxygen
DE19642770A1 (de) 1996-10-16 1998-04-23 Basf Ag Verfahren zur Herstellung von Wasserstoffperoxid
FR2774674B1 (fr) * 1998-02-10 2000-03-24 Atochem Elf Sa Procede de preparation d'une solution aqueuse de peroxyde d'hydrogene directement a partir d'hydrogene et d'oxygene et dispositif permettant sa mise en oeuvre
FR2806399B1 (fr) * 2000-03-17 2002-09-13 Atofina Procede d'obtention directe du peroxyde d'hydrogene
IT1318679B1 (it) * 2000-08-11 2003-08-27 Enichem Spa Processo per la produzione di acqua ossigenata.
JP2005330159A (ja) * 2004-05-21 2005-12-02 Mitsubishi Gas Chem Co Inc 食塩から化学パルプの無塩素漂白用薬品の製造方法
FR2930772B1 (fr) * 2008-04-30 2010-04-30 Arkema France Synthese directe d'eau oxygenee sur le site d'une papeterie
TWI628146B (zh) * 2016-11-28 2018-07-01 東聯化學股份有限公司 Preparation method and application of titanium-containing cerium oxide material with high thermal stability
CN110342469B (zh) * 2019-06-17 2021-04-16 浙江大学 一种高氢氧比条件下氢氧直接合成过氧化氢的方法

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CA2197655A1 (fr) 1996-02-22
AU3324495A (en) 1996-03-07
EP0776316A1 (fr) 1997-06-04
AU710994B2 (en) 1999-10-07
WO1996005138A1 (fr) 1996-02-22
JPH10504008A (ja) 1998-04-14

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