CN106458584A - Method for producing hydrogen peroxide - Google Patents

Method for producing hydrogen peroxide Download PDF

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Publication number
CN106458584A
CN106458584A CN201580024705.XA CN201580024705A CN106458584A CN 106458584 A CN106458584 A CN 106458584A CN 201580024705 A CN201580024705 A CN 201580024705A CN 106458584 A CN106458584 A CN 106458584A
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fixed bed
catalyst
described fixed
reactor
hydrogen
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T·哈斯
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Evonik Operations GmbH
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Evonik Degussa GmbH
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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
    • 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
    • B01J8/0242—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 the fluid flow within the bed being predominantly vertical
    • 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
    • B01J8/0242—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 the fluid flow within the bed being predominantly vertical
    • B01J8/025—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 the fluid flow within the bed being predominantly vertical in a cylindrical shaped bed
    • 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
    • B01J8/0278—Feeding reactive fluids
    • 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
    • B01J8/0285—Heating or cooling 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
    • 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
    • B01J8/0292—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 with stationary packing material in the bed, e.g. bricks, wire rings, baffles
    • 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
    • B01J8/04—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 the fluid passing successively through two or more beds
    • B01J8/0446—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 the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
    • B01J8/0449—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 the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
    • B01J8/0453—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 the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds the beds being superimposed one above the other
    • 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
    • B01J8/04—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 the fluid passing successively through two or more beds
    • B01J8/0492—Feeding reactive fluids
    • 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
    • B01J8/04—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 the fluid passing successively through two or more beds
    • B01J8/0496—Heating or cooling 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
    • 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
    • B01J8/06—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 in tube reactors; the solid particles being arranged in tubes
    • B01J8/067—Heating or cooling the reactor
    • 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
    • B01J2208/00115—Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
    • B01J2208/0015—Plates; 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
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00884—Means for supporting the bed of particles, e.g. grids, bars, perforated plates
    • 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
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00938—Flow distribution elements
    • 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
    • B01J2219/00761—Details of the reactor

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a method for producing hydrogen peroxide by converting hydrogen and oxygen in the presence of a liquid reaction medium and a particulate noble metal support catalyst in a fixed-bed reactor, wherein the liquid reaction medium and a gas phase containing hydrogen and oxygen flow against the fixed bed from below. The fixed bed is arranged in the reactor such that the volume of the fixed bed expands by 1 to 10% in the operating state relative to a rest state without a flow against the fixed bed. As a result of the fixed bed expansion according to the invention, the fixed bed can be prevented from clogging due to abrasions on the catalyst.

Description

The method preparing hydrogen peroxide
Technical field
The present invention relates to a kind of by by hydrogen and oxygen in the presence of loaded noble metal catalyst in fixed bed reaction The method that in device, hydrogen peroxide is prepared in reaction.
Background technology
It is known that using the admixture of gas comprising hydrogen and oxygen be directly synthesized by by this admixture of gas in On noble metal catalyst, in the presence of aqueous solution, water-organic or organic reaction medium, hydrogen peroxide is prepared in reaction.From direct The available hydrogenperoxide steam generator of synthetic method is interesting as partners for oxidant for the catalysis oxidation of organic compound.It is directly synthesized Method can be used noble metal catalyst as suspended catalyst or as loaded noble metal catalyst in fixed bed.
The advantage of the reaction in fixed bed is not need to separate product from catalyst.This reaction can be as bubble Carry out in the reactor of cover tower, wherein comprise the fixed bed experience liquid reactions of loaded noble metal catalyst under operation Medium and comprise hydrogen and oxygen gas phase upper up-flow.Such as EP 0 049 806 and WO 2004/096701 disclose accordingly Reaction.In addition, WO 2005/108285 discloses having under suitable design conditions under this method of operation in reactor Reactor material can be avoided to corrode.
As disclosed in EP 1 308 416, by using being at least liquid of 0.3m/h by fixed bed high cross-section flow velocity The yield of the reaction carrying out on fixed bde catalyst and selectivity can be made to be improved.But, such as by WO 98/16463 Know, high flow rate may result in undesirable catalyst abrasion.
The inventor have discovered that when comprise described loaded noble metal catalyst fixed bed experience liquid reaction medium and During the upper up-flow of the gas phase comprising hydrogen and oxygen, aggravated by the problem that catalyst abrasion causes.By asking that this present invention solves Entitled find a kind of upper up-flow fixed-bed process form wherein avoiding catalyst abrasion.
Now, surprisingly have been found that by arranging fixed bed in the reactor so that not having compared to fixed bed There is the non-operating state of experience stream, fixed bed expansion 1 volume % solves this difficult problem to 10 volumes % under operation.
Content of the invention
Invention accordingly provides a kind of method preparing hydrogen peroxide, it is situated between in liquid reactions including making hydrogen and oxygen React in fixed bed reactors in the presence of matter and microgranular, loaded noble metal catalyst, wherein exist under operation The fixed bed comprising loaded noble metal catalyst in reactor experiences described liquid reaction medium and comprises hydrogen and oxygen The upper up-flow of gas phase, methods described is characterised by arranging fixed bed in the reactor so that not experiencing stream compared to fixed bed Non-operating state, under operation fixed bed expand 1 volume % to 10 volumes %.
Include making hydrogen and oxygen deposit in liquid reaction medium and loaded noble metal catalyst according to the method for the present invention In lower reaction.Described reaction preferably uses the admixture of gas comprising hydrogen and oxygen and implements, and wherein hydrogen and oxygen is formed Selection make this admixture of gas not have explosivity.Even if preferably using the solvent partial pressure considering to increase also in explosion limit It is outward reliable admixture of gas.Described admixture of gas advantageously also includes one or more noble gas, except hydrogen and Preferred nitrogen outside oxygen.The hydrogen content of this admixture of gas is preferably more than 6 volumes % for this purpose, more preferably no more than 5 volumes %.Described hydrogen content is more particularly in the range of 3 volume %-5 volumes %.The oxygen of described admixture of gas contains Amount is preferably stoichiometric or hyperstoichiometry, and more preferably in the range of 10 volume %-50 volumes %, more particularly 15 volumes % are to 45 volumes %.Hydrogen and oxygen are preferably respectively supplied to reactor.Described oxygen can in a pure form or There is provided in the form of air or oxygen-enriched air.When this reaction is continuously run, partly or entirely obtain in reactor outlet Residual gas capable of circulation enter reactor to be reduced to reclaim the effort that unconverted hydrogen does.
The liquid reaction medium using can be aqueous solution, water-organic or organic reaction medium.Described liquid reaction medium Preferably substantially it is made up of the mixture of alcohol or alcohol and water, preferably the mixture of methanol or first alcohol and water.
Described liquid reaction medium preferably further comprises with to peroxide on suppression noble metal catalyst in being directly synthesized Change the halogenide decomposing effectively amount dissolving of hydrogen.Preferably halogenide is bromide and/or iodide, particularly preferred bromide. Concentration in liquid reaction medium for the halogenide is preferably from 10-6Mol/l to 10-2In the range of mol/l, more preferably from 10-5Mol/l to 10-3In the range of mol/l, and more particularly from 10-5Mol/l to 5 × 10-4In the range of mol/l.It is higher than The halide concentration of described preferred scope can weaken the stability of prepared hydrogenperoxide steam generator, and is less than described preferred scope Halide concentration normally result in the selectivity of hydrogen peroxide and descend below tolerable limit.In view of further using being obtained Hydrogenperoxide steam generator, preferably relatively low halide concentration.Described halogenide can be with the shape of alkali metal or alkali salt Formula is added in reaction medium, preferably NaBr or NaI.This halogenide can also be added in the form of halogen acids, such as HBr or HI.
Described liquid reaction medium optionally comprises strong acid further.In the context of the invention, art mentioned above Language strong acid can be regarded as any thering is pKaAcid less than 3, and preferred pKaLess than 2.Especially, useful strong acid is mineral acid, such as Sulphuric acid, phosphoric acid and nitric acid.Equally available for can dissolve sulfonic acid in media as well and phosphonic acids.Acid concentration is preferably in 0.0001mol/ In the range of l to 0.5mol/l, more preferably in the range of 0.001mol/l to 0.1mol/l.Acid concentration higher than preferred scope Liquid phase can be led to cause undesirable corrosivity, and the acid concentration being less than preferred scope can lead to subtracting of hydrogen peroxide selectivity Few.In view of further using the acid concentration that the hydrogenperoxide steam generator being obtained is preferably relatively low.
In the method for the invention, reaction is carried out in the presence of microgranular, loaded noble metal catalyst.At this In bright context, term " microgranular, loaded noble metal catalyst " can be regarded as by a pure form or alloy form comprises The catalyst of the discrete particle composition of the carrier material of one or more noble metal.Preferably noble metal is platinum group metal, especially Platinum and gold.Element in the group being made up of Rh, Ru, Ir, Cu and Ag can also exist.Particularly a preferred catalyst comprises as urging Change the palladium with alloy or at least 80 mass % of unalloyed form of active metal and the platinum of 0 mass %-20 mass % and 0 matter The amount gold of % to 20 mass % and/or the silver of 0 mass %-5 mass %.Most preferably comprise the catalyst of palladium and platinum.
Described carrier material be microparticle material, for example powder, extrudate, bead or other derive from pulverulent material shaping Thing.Preferably use oxide, silicate or nitride carrier material, especially aluminium oxide, silicon dioxide, titanium dioxide, dioxy Change zirconium and zeolite.Selectively, carbon-based supports material, such as absorbent charcoal carrier, it is possible to use.
Described loaded noble metal catalyst can be by by with the catalytic active component of very discrete form and powder carrier Material mixing, by mixture plasticizing and shaping, and makes the mode of mold solidification prepare by the way of calcining.Selectively, in advance Carrier processed can obtain, by the suspended substance infiltration comprising very scattered catalytic active component, the catalyst being referred to as coating.? Can enter in the presence of known binders to be about to described catalytically-active materials to be applied on carrier material and/or interior, described adhesive Such as waterglass, the compositionss of calcium oxalate, boric acid and other formation glass.Generally catalytically-active materials are deposited to carrier material On follow the calcining step being followed by from 300 DEG C to 600 DEG C closely.The catalyst of the activity load of described catalysis can be by soaking carrier Moisten and subsequently carry out hydrogenating in the solution comprising catalytically-active metals compound, calcine and washing step finally obtains.
The size of carried noble metal catalysed particulate in extensive limit, and preferably in the range of from 0.1mm to 10mm. Low particle size leads to relatively high pressure drop, and too big particle size can reduce catalytically active surface and amass.Particularly preferably Using by median dp50Scope is the loaded catalyst of the spheroidal particle composition of 0.5mm to 5mm.
The method according to the invention is used and is configured at the carried noble metal in fixed bed reactors with fixed bed form Catalyst.In the context of the present invention, term fixed bed can be regarded as any filling of loaded noble metal catalyst granule Thing.This implant optionally comprises extra catalytic inert particle further.
In the method according to the invention, fixed bed experiences liquid reaction medium under operation and comprises hydrogen and oxygen The upper up-flow of the gas phase of gas, that is, liquid reaction medium and gas phase enter fixed bed from below, flow through fixed bed in the same direction and from fixation The top of bed is discharged.Fixed bed is preferably provided with the reactor on the pallet of gas and fluid permeable, by this pallet liquid Precursor reactant medium and gas phase can enter fixed bed and pass through whole fixed bed cross section.Fixed bed is preferably subjected to table under operation Face gas flow rate is 50m/h to 500m/h, the more preferably gas phase stream of 50m/h to 200m/h.Fixed bed is preferably subjected to surface velocity For 5m/h to 50m/h liquid reaction medium stream.This surface velocity is defined as volume flow m by fixed bed3/ h and fixed bed Cross-sectional area m2Business.
The basic feature of the method according to the invention is the setting of fixed bed in the reactor so that not having compared to fixed bed There is the non-operating state of experience stream, fixed bed expands 1 volume % to 10 volumes % under operation.
The lid (cover) that this feature preferably passes through setting gas and fluid permeable on a fixed bed limits fixed bed Expand, therefore prevent fixed bed from expanding into more than the degree according to volume fraction of the present invention.This lid can be for example with fixation The fabric of setting or the form of grid or screen tray.
Particularly preferably work as gas or the lid of fluid permeable includes sieving (screen), net, fabric or adhesive-bonded fabric, its setting On a fixed bed, and by described lid limit the movement of fixed bed.In such an implementation, described setting is on a fixed bed Sieve, net, fabric or adhesive-bonded fabric relative response container are moveable, but are arranged by way of fixing with relative response container Lid part limit its movement.This embodiment prevents catalyst granules in the vortex on fixed bed top.
Described fixed bed reactors preferably include at least one and are configured such that in fixed bed loaded catalyst and cold But the distance between apparatus surface is less than the chiller of 30mm.This can be achieved on.For example, when fixed bed reactors are pipe Bundle reactor, the pipe being wherein filled with loaded noble metal catalyst uses common cooling jacket cooling.Selectively, this is fixed Bed reactor be alternatively plate bundle reactor (plate bundle reactor), wherein by fixed bed between respective parallel-plate with layer Form setting, cooling medium flows through between parallel-plate.
Described fixed bed reactors advantageously can also include multiple fixed beds arranging top of each other in the reactor, each The setting of fixed bed make under operation its compared to non-operating state expand 1 volume % to 10 volumes %.This setting is permitted Permitted the extra injection between fixed bed of hydrogen and/or oxygen, and it is relatively equal to be ensured through reactor cross-section between permission fixed bed The installation of the vapor distributor of even Gas distribution.
Fixed bed is arranged in the reactor according to the present invention and prevents fixing caused by the abrasion of catalyst in the reaction Blocking in bed and the increase passing through the pressure drop of fixed bed therewith.
Following examples are used for illustrating the invention without limitation of the present invention.
Embodiment
Embodiment 1 (non-invention)
Reaction is carried out in bubble-column reactor, and this reactor has the internal diameter of 16mm and the length of 200cm and comprises cold But sleeve pipe.Catalyst fixed bed being arranged in reactor with about 400ml bed volume makes its not expansion between two sieves.Make Catalyst is load type palladium catalyst, and it comprises spherical form, and having median diameter is 2mm 0.1 matter on alumina Amount % palladium.
Below reactor, the speed with 2l/h provides it liquid reaction medium, and it is by the methanol of 98 weight portions and 2 weights The water composition of amount part, comprises the sodium bromide of 0.0001mol/l and the sulphuric acid of 0.01mol/l in wherein said water.1Nm simultaneously3/h Admixture of gas adds from reactor bottom, and this admixture of gas is by the hydrogen of 3 volumes %, the oxygen of 20 volumes % and 77 bodies The nitrogen composition of long-pending %.In course of reaction, reactor holding pressure is 5MPa (50bar) and reaction temperature is 30 DEG C.Liquid reactions Medium and admixture of gas flow through catalyst fixed bed in the same direction from bottom to top.F liquid cross section flow velocity is about 10m/h, and gas Body cross section flow velocity is about 100m/h, and this is to be determined by the flow velocity of liquids and gases and cross-sectional reactor area.
Reactor run 24h after hydrogen conversion be 24% and take out hydrogenperoxide steam generator in have content to be 1.9 weights The hydrogen peroxide of amount %.Based on the hydrogen of reaction, in reaction, the selectivity of hydrogen peroxide is 71%.Through catalyst fixed bed Pressure drop is 1.2bar.Pressure drop after reactor runs 37h increases as more than 10bar within a few minutes, and reactor has to close.
Embodiment 2 (non-invention)
Repeat embodiment 1, except sieve between space catalyst be only filled with 80% capacity rather than be filled up completely with.It is urged Agent is provided based on its static volume 20% at reaction conditions for the additional volume expanding.
Reactor run 24h after hydrogen conversion be 20% and take out hydrogenperoxide steam generator in have content to be 1.6 weights The hydrogen peroxide of amount %.Based on the hydrogen of reaction, in reaction, the selectivity of hydrogen peroxide is 73%.Through catalyst fixed bed Pressure drop is 210mbar.After running 127h, pressure drop increases as more than 10bar within a few minutes, and reactor has to close.
Embodiment 3 (present invention)
Repeat embodiment 2, except substituting top sieve, one layer is coated with 20ml Raschig ring filling thing and (is purchased from Gebr ü 3 × 3mm glass AR Raschig ring of der Rettberg GmbH) the layer of about 12ml PTFE floss (Semadeni PTFE is close Envelope floss) it is deposited on catalyst fixed bed.Described Raschig ring forms immovable rigid reaction-filling at reaction conditions Thing, and therefore catalyst fixed bed during the course of the reaction by compress PTFE floss expand only about the 3% of its volume.
Reactor run 24h after hydrogen conversion be 22% and take out hydrogenperoxide steam generator in have content to be 1.8 weights The hydrogen peroxide of amount %.Based on the hydrogen of reaction, in reaction, the selectivity of hydrogen peroxide is 72%.Through catalyst fixed bed Pressure drop is 215mbar.Pressure drop after running 3000h is kept stable at 215mbar.Hydrogen conversion is 21% and the peroxidating taken out There is the hydrogen peroxide that content is 1.7 weight % in hydrogen solution.Based on the hydrogen of reaction, in reaction, the selectivity of hydrogen peroxide keeps 72%.
Described embodiment shows that the method according to the invention reactor allows continuous service 3000h not need to fixed bed Flow resistance makes any change.On the contrary, can not expand under operation or can be inflatable under operation when catalyst fixed bed 20%, the blocking of the fixed bed that the abrasion that catalyst suffers from is led to and the increase of flow resistance can be so that reaction can not continue.

Claims (9)

1. a kind of method preparing hydrogen peroxide, it includes making hydrogen and oxygen expensive in liquid reaction medium and particulate supported type React in fixed bed reactors in the presence of metallic catalyst, wherein under operation, in described reactor, make to comprise The fixed bed of described loaded noble metal catalyst experiences described liquid reaction medium and comprises the upper of the gas phase of hydrogen and oxygen Up-flow it is characterised in that
Described fixed bed is arranged in described reactor so that do not experience the inoperative shape of stream compared to described fixed bed State, described fixed bed expansion 1 volume % is to 10 volumes % under operation.
2. the method described in claim 1 it is characterised in that
Described fixed bed experience surface velocity is 50m/h to 500m/h, the gas phase of preferred 50m/h to 200m/h under operation Stream.
3. the method described in claim 1 or 2 it is characterised in that
Described fixed bed experiences the liquid reaction medium stream that surface velocity is 5m/h to 50m/h under operation.
4. aforementioned any one of claim method it is characterised in that
Limit the expansion of described fixed bed by the lid of setting gas and fluid permeable above described fixed bed.
5. the method described in claim 4 it is characterised in that
The lid of described gas or fluid permeable includes sieve, grid, fabric or adhesive-bonded fabric, and it is arranged in described fixed bed Side, and the movement of described fixed bed is limited by described lid.
6. aforementioned any one of claim method it is characterised in that
Loaded noble metal catalyst is deposited on oxide, silicate or nitride carrier material.
7. claim 6 methods described it is characterised in that
Loaded catalyst is by median dp50Spheroidal particle composition in the range of 0.5mm to 5mm.
8. aforementioned any one of claim method it is characterised in that
Described fixed bed reactors include at least one chiller, wherein in described fixed bed, loaded catalyst and institute The distance stated between chiller surface is less than 30mm.
9. aforementioned any one of claim method it is characterised in that
Described liquid reaction medium is substantially made up of the mixture of alcohol or alcohol and water, and preferably methanol or first alcohol and water is mixed Compound.
CN201580024705.XA 2014-05-14 2015-04-29 Method for producing hydrogen peroxide Pending CN106458584A (en)

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CN111107929A (en) * 2017-07-31 2020-05-05 沙特基础工业全球技术公司 System and method for dehydrogenating isobutane to isobutylene

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CN111107929A (en) * 2017-07-31 2020-05-05 沙特基础工业全球技术公司 System and method for dehydrogenating isobutane to isobutylene
CN111107929B (en) * 2017-07-31 2023-02-17 沙特基础工业全球技术公司 System and method for dehydrogenating isobutane to isobutylene

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