CN1329352C

CN1329352C - Auto thermal cracking reactor

Info

Publication number: CN1329352C
Application number: CN 200480004544
Authority: CN
Inventors: D·A·科尔曼; M·J·A·马休曼; I·A·B·赖德; V·C·威廉斯; W·T·伍德芬
Original assignee: Innovene Europe Ltd
Current assignee: Ineos Europe AG; Ineos Commercial Services UK Ltd
Priority date: 2003-02-18
Filing date: 2004-02-06
Publication date: 2007-08-01
Anticipated expiration: 2024-02-06
Also published as: ZA200506214B; GB0303723D0; CN1751009A; UA83025C2

Abstract

The present invention provides a reactor design that enables an auto-thermal cracking process to be conducted at any suitable pressure wherein the gaseous reactants are preheated separately before mixing and then presented to the reaction zone in a uniformly distributed manner. In particular, the present<->invention-relates to apparatus <->for reacting a first and second gaseous reactant to form a gaseous product wherein the apparatus comprises at least one first supply means for the first gaseous reactant, at least one second supply means for the second gaseous reactant, a resistance zone and a reaction zone, preferably comprising a catalyst, wherein the first supply means comprises a plurality of first outlets for delivery of the first gaseous reactant, and the second supply means comprises a plurality of second outlets for delivery of the second gaseous reactant, the resistance zone is porous, the reaction zone is positioned downstream of the resistance zone with respect to the flow of the first and second gaseous reactants and wherein the first supply means and the second supply means are arranged such that the first gas and the second gas are contacted in an essentially parallel manner and mixed prior to contacting the resistance zone. The present invention also provides a process for the production of a mono-olefin utilizing said apparatus.

Description

Auto thermal cracking reactor

The present invention relates to be adapted to pass through the reactor that autothermal cracking is produced alkene.

Autothermal cracking is the currently known methods that is used to produce alkene.EP-A-0332289 has described an example of this method.In the method, hydrocarbon contacts with catalyzer with oxygen-containing gas, and this catalyzer can be supported in above the burning under the rich oil limits of inflammability situation.Hydrocarbon is partly burnt, and the heat of generation is used to drive the dehydrogenation that the hydrocarbon charging generates alkene.

In autothermal cracking process, before contact catalyst, hydrocarbon and oxygen-containing gas can be mixed and preheating equably.Yet, if wish under high pressure to carry out this method, because flammable restriction, with hydrocarbon with oxygen-containing gas mixes and preheating is problematic.So, wish to reduce from forming the hot gas reagent to the time making mixture and catalyzer contacting.

The invention provides a kind of reactor design, it can make autothermal cracking process carry out under any suitable pressure, and wherein gaseous reactant was separated the ground preheating before mixing, and delivered to reaction zone in equally distributed mode then.

Therefore, the invention provides and be used to make the reaction of first gaseous reactant and second gaseous reactant, forming the equipment of gaseous product,

Wherein, this equipment comprises at least one first feedway of using for first gaseous reactant, second feedway that at least one is used for second gaseous reactant, restriction section and reaction zone, preferably its comprise catalyzer and

Wherein, first feedway comprises many first outlets that are used to carry first gaseous reactant, and second feedway comprises many second outlets that are used to carry second gaseous reactant,

Restriction section is a porous, with regard to the flowing of first and second gaseous reactants, is positioned in the downstream of first and second feedwaies, and is communicated with the first and second feedway fluids,

With regard to the flowing of first and second gaseous reactants, reaction zone is positioned in the downstream of restriction section, and is communicated with the restriction section fluid, and

Wherein, first feedway and second feedway are configured such that first gas and second gas, before the contact resistance district, contact and mix in parallel basically mode.

Preferably, first feedway comprises that at least one is used for first gaseous reactant is supplied with first import and many outlets that is used to carry first gaseous reactant of coming out from first manifold of at least one first manifold, and second feedway comprises that at least one is used for second gaseous reactant is supplied with second import and many second outlets that is used to carry second gaseous reactant of coming out from second manifold of at least one second manifold.

For every square metre of reaction zone cross section, this equipment comprises at least 100, preferably at least 500, most preferably at least 1000 first and second outlets suitably.

First and second feedwaies are configured such that first and second gases contact in parallel basically mode." Bing Hang mode basically " is meant, first and second gases, and when making their contacts, both flow with substantially the same direction, for example axially flow, but not flow with opposite or tangent relative direction.Make the gas contact in parallel basically mode, but not for example contact, in the zone (mix and do not finish as yet, and may there be significant difference in the composition of gas) of the initial contact of gas, reduced turbulent flow herein in tangent mode.

Turbulent flow may increase the residence time of mixed gas in reactor, and this has increased the danger that produces flammability issues.In some cases, make gas contact may cause forming low flow region in orthogonal mode, perhaps even retention areas, it comprises combustible gas mixture near the zone of action.Make the gas contact according to the present invention in parallel basically mode, reduced the possibility that forms the low mixed gas zone of flowing, reduced the possibility of flammability issues.

In first embodiment of the present invention, contact/mixing is provided with by providing to get off: a feedway is positioned in another feedway, and suitable opening is provided at least a portion of the described feedway that is positioned at another feedway, makes a kind of gaseous reactant to contact by described opening and with another kind of gaseous reactant.

Preferably, first embodiment of the present invention provides equipment, wherein

First feedway comprises that at least one is used for first gaseous reactant is supplied with first import and many syringes that is used to carry first gaseous reactant that comes out from described first manifold of at least one first manifold, and second feedway comprises that at least one is used for second gaseous reactant is supplied with second import and many conduits that is used to carry second gaseous reactant that comes out from described second manifold of at least one second manifold

Wherein, with regard to the flowing of first gaseous reactant, second manifold is positioned in the downstream of first manifold,

Restriction section is a porous, with regard to the flowing of first and second gaseous reactants, is positioned in the downstream of second manifold, and is to be communicated with the catheter fluid of coming out from second manifold,

Wherein, each conduit comprises upstream extremity that comes out from second manifold and the downstream end that is communicated with the restriction section fluid, and the syringe that wherein comes out from first manifold is configured such that they extend through second manifold, and axially protrudes in the conduit upstream end.

Advantageously, the equipment of first embodiment generally includes: first cooling zone, and the downstream end of described many conduits that its contact is come out from described second manifold, this first cooling zone is configured such that the downstream end of described many conduit is cooled.This has guaranteed to prevent that gaseous reactant from reacting before they enter reaction zone.

In addition, the equipment of first embodiment is usually included in the product cooling zone in reaction zone downstream, makes gaseous product can be cooled when reaction zone comes out.

In first embodiment of the present invention, preferably, first manifold is first Room, and second manifold is second Room, and the syringe that comes out from first Room forms many microscler paths, and this microscler path extends to the upstream extremity of the many conduits that come out from second manifold by second Room.

The volume of first and second Room is not crucial especially.Yet in preferred embodiments, for safety, the volume of first and second Room is relatively little.Usually, when reactor diameter is 600 millimeters, the volume of first Room usually between 5-100 rises, preferably between 10-40 rises and more preferably between 15-25 rises, for example 22 liters.The volume of these chambers will be proportional with the cross-sectional area of reactor (be diameter square).

Usually, when reactor diameter is 600 millimeters, the volume of second Room usually between 20-200 rises, preferably between 30-100 rises, and more preferably between 40-80 rises, for example 50 liters.

The equipment of first embodiment generally includes the syringe and the conduit of equal amount, and each syringe protrudes in the corresponding conduit.Preferably, for every square metre of reaction zone cross section, this equipment comprises at least 100, preferably at least 500, at least 1000 syringes most preferably.

For syringe is protruded in the conduit, protrude into the internal diameter of the external diameter of the syringe in the conduit less than conduit.Accurate external diameter is not crucial for the present invention, but the external diameter of syringe is between 2.0 to 5.0mm usually, for example 4.0mm.The length of syringe is enough to extend through second Room (promptly usually greater than 170 millimeters).

Each not end at described many syringes away from manifold, first gaseous reactant can come out from pipe by suitable opening, and described opening is nozzle preferably, and its diameter is less than the external diameter of syringe, preferably between 0.5 to 3.0mm, for example between 1.0 to 2.0mm.Described nozzle, when existing, preferably has diameter less than the internal diameter of syringe, except that nozzle is sentenced, Gu this provides throttling, it helps to obtain even flow from all syringes, and does not need to provide when syringe inner diameter is this size by the drooping characteristic that syringe obtained than length.

Usually, the internal diameter of conduit between 1 to 10mm, preferably between 2 to 8mm, for example 7mm, and length between 50 to 500mm, preferably between 100 to 300mm, 210mm for example.Conduit can be with symmetric configuration setting, for example with trilateral or foursquare configuration setting.

The ratio of the diameter of the internal diameter of conduit and syringe opening (for example nozzle) is compatibly in 2: 1 to 10: 1 scopes, for example in 3: 1 to 5: 1 scope.

When the syringe of first feedway extended through the manifold of second feedway, each syringe can provide an outer tube around this syringe (this syringe forms the interior pipe in the described outer tube).When second gaseous reactant was in the temperature different with first gaseous reactant (it passes through) in interior pipe, outer tube provided the thermal insulation with second gaseous reactant.

In a more preferred embodiment, also provide suitable restrictor between the internal surface of the outside surface of syringe and conduit, its position is in or approaches syringe enters conduit at the upstream extremity of conduit position (promptly approaching second manifold).These restrictors can be positioned on the syringe and/or on the conduit, and by resistance is provided, they help to obtain the flow velocity that uniform second gaseous reactant enters each conduit.These restrictors should be positioned in the position away from the outlet of first syringe, make second gaseous reactant speed (when second gaseous reactant by or when the restrictor, it has top speed in conduit), when mixing, be lowered (from this top speed) with first gaseous reactant.Preferably, flow, have the similar order of magnitude (for example being respectively 1 crust and 0.5 crust) in the pressure drop of not holding of syringe by nozzle or other current regulator to first gaseous reactant through the pressure drop of these current regulators.This has guaranteed, when in the reaction zone or charging in pressure when little fluctuation is arranged, the ratio that enters the reactant of reaction zone keeps similar.In order to reach optimum yield, the tolerance of the restrictor of the nozzle diameter and second gaseous reactant should make the variation of gaseous mixture concentration be not more than 5%.

Usually, syringe axially protrudes into length in the conduit between the 5-40mm, preferably between the 10-30mm and most preferably between 15-25mm, for example 20mm.

When the equipment of first kind of embodiment comprised first cooling zone, first cooling zone preferably provided by cooling fluid is contacted with the outer surface region of the downstream end of conduit.Usually, the 10-20% of the outer surface region of conduit is contacted with cooling fluid.

In second embodiment of the present invention, contact/mixing setting provides by following: first feedway comprises that at least one is used for first gaseous reactant is supplied with first import of at least one first manifold and the first many syringe that is used to carry first gaseous reactant that comes out from described first manifold, and second feedway comprises that at least one supplies with second import of at least one second manifold and the second many syringe that is used to carry second gaseous reactant that comes out from described second manifold with second gaseous reactant, and wherein each syringe has outlet and it has 1mm at the end away from manifold ²Perhaps littler cross section opening, and wherein the outlet of first and second syringes is mix-configuration.

" mixing " used herein is meant that the outlet of described many first syringe is dispersed between the outlet of described many second syringe, and/or conversely.Therefore, for example, when existing than more first syringe of second syringe, the outlet of second syringe will be dispersed between the outlet of first syringe, and the optimum configuration of the outlet of second syringe is to make each second syringe will have the outlet of the outlet of at least one first syringe as its nearest neighbour.

Compatibly, at least 10,000 first and second syringes of every square metre of existence.Use the mixing tube of described number, provide in described pipe exit rapidly and mixed.

In order best first and second gaseous reactants to be transported to restriction section, the outlet of the syringe of second embodiment should be all with planar configuration location basically.

The outlet of first syringe can be arranged with symmetric configuration, for example arrange with trilateral, square, rectangle or hexagonal configuration, and/or the outlet of second syringe can for example be arranged with trilateral, square, rectangle or hexagonal configuration with symmetric configuration arrangement.

In this second embodiment, the cross section of outlet can be any suitable shape, for example trilateral, rectangle, square, sexangle, D-shape, ellipse or circular.

When the cross section opening of number of tubes increase and pipe outlet was lowered, the mixing of gas became rapider.

Therefore, aspect second embodiment of the present invention preferred, it is 0.5mm that each syringe has its cross section opening at the end away from manifold ²Perhaps littler outlet.More preferably, the cross section opening of outlet is 0.2mm ²Perhaps littler, 0.1mm for example ²Perhaps littler.Compatibly, the cross section opening of outlet is 0.004mm ²Or more than.

For a kind of syringe of reactant, the size and dimension of outlet can change, but preferably identical.Similarly, the outlet of second gaseous reactant can have different or identical size and dimension with the outlet of first gaseous reactant.

Most preferably, outlet is a D-shape, and for example semicircle, the cross section opening is at 0.01mm ²To 0.05mm ²Between.

The equipment of this second embodiment can comprise first and second syringes of carrying described first and second gaseous reactants that are respectively applied for of equal amount.Selectively, it can be different being used to carry the relative populations of the syringe of every kind of gaseous reactant, for example is used to carry the relative populations of the syringe of every kind of gaseous reactant can be proportional with the relative quantity of the every kind of gaseous reactant that is transferred.Yet the relation between the number of tubes is not crucial for the present invention, and the speed of first and second gaseous reactants that for example come out from corresponding syringe can be different, and preferably different.Especially, when using the syringe of fixed number,, allow described first and second gas reactants that obtain different ratios for each use different in flow rate of first and second gaseous reactants for every kind of reactant.

Preferably, one of reactant more preferably has the reactant of lowest molecular weight, to come out from one group of syringe than the higher speed of another kind of reactant of coming out from another group syringe.For example, a kind of size of syringe of reactant and number can be so that the ratio of velocity of discharge be at least 10: 1, for example a kind of velocity of discharge of reactant is 100m/s at least, and the number of the syringe of another kind of reactant and size can so that velocity of discharge less than 10m/s.The V-bar of the mixed flow that comes out from syringe can be about 3m/s.

When the cross section of outlet pipe opening reduces, so the number of first and second syringes of the reaction zone cross section of per unit area can increase.Therefore, the equipment of second embodiment can comprise every square metre reaction zone cross section at least 100000, for example at least 1000000,4000000 syringes (sums of first and second syringes) for example.

Similarly, when the cross section of outlet pipe opening reduces to increase with the number of first and second syringes, the distance between an outlet and its most contiguous outlet also will reduce.Therefore, in second embodiment, one the outlet and its most contiguous outlet between distance can be less than 2000 microns, for example less than 1000 microns with preferably in 100 to 500 micrometer ranges.Distance between the adjacent pipe preferably has and the similar size of the size of outlet own, for example for cross exit opening maximum sized half to twice.

Carry first and second gaseous reactants by being respectively applied for, obtained the rapid mixing of first and second gaseous reactants according to the mixing setting of first and second syringes with relatively little outlet opening of second embodiment of the present invention.Usually, have the cross section opening and be 0.5mm by using ²The mixing setting of first and second syringes of perhaps littler outlet has obtained enough mixing in the distance of distance syringe outlet less than 5mm, allow that gas in short distance (and therefore in short time) mixes and contacts with restriction section.

The equipment of second embodiment is usually included in the product cooling zone in reaction zone downstream, makes gaseous product can be cooled when reaction zone comes out.

Preferably, in second embodiment of the present invention, first manifold comprises first Room, and second manifold comprises second Room, and corresponding first and second gaseous fractions are from wherein coming out and entering the first and second many syringes.Having the cross section opening is 1mm ²The syringe of perhaps littler outlet preferably forms as the path in the diffusion-bonded parts.The diffusion-bonded parts that diffusion-bonded by etched structured metal layer forms are known for heat exchange applications, and usually for example are being described in the following document: " industrial micro-channel device-present situation (Industrial Microchannel Devices-Where are we Today ?) " Pua, L.M. and Rumbo ld, S.O.; International microchannel and thin passage meeting (FirstInternational Conferences on Microchannels andMinichannels) for the first time, Rochester, NY, April, 2003.

Use the diffusion-bonded technology in the present invention, allow to form many paths that respectively first and second Room are connected to the first and second many outlets, described outlet is mix-configuration, as desired for the syringe that forms second embodiment of the present invention.

As the situation of first embodiment, the volume of first and second Room is not crucial especially, but for safety, preferably the volume of first and second Room is relatively little in second embodiment.

After mixing according to the inventive method, no matter the equipment by means of first embodiment still is the equipment of second embodiment, perhaps other equipment, blended first and second gaseous reactants contact with the restriction section in the downstream that is positioned at first and second feedwaies.

Restriction section is a porous.The perviousness of porous restriction section has guaranteed the dispersion when liquid reactants passes through this district.Fluid is by laterally and axially (axially being that reactant passes through restriction section mobile general direction) motion of channel network, and leaves restriction section in equally distributed substantially mode on the restriction section cross section.

Preferably, restriction section laterally with axially have identical perviousness.More preferably, in any direction in, restriction section has substantially the same perviousness, for example the perviousness in any direction is in what its direction in office infiltrative 0.2 to 5 times.

The infiltrative method of measuring porous medium is known.The pressure gradient or the pressure that can use the inertia resistance coefficient to define the per unit length by restriction section fall, and wherein pressure gradient equals the product of inertia resistance coefficient and velocity pressure.Velocity pressure is half of product of fluid density and surface velocity, and has the unit of pressure.The inertia resistance coefficient has the unit of length inverse.The average inertia resistance coefficient that restriction section has usually (i.e. mean value on all directions) be 500-10000/ rice (/m), preferred 2000-4000/m, and advantageously between 2500-3500/m, for example 3250/m.

Restriction section can be formed by porous metal structure, but preferred porous material is nonmetal for example stupalith.The stupalith that is fit to comprises lithium aluminosilicate (LAS), aluminum oxide (zirconium white, aluminum oxide titanate, niascon and the calcium zirconyl phosphoric acid salt of α-A1203), stabilized with yttrium oxide.Preferred porous material is a gamma-alumina.

In first embodiment, distance between restriction section and the catheter tip, and in second embodiment the distance between the outlet of restriction section and pipe, for preferably less than 20 millimeters, more preferably between 1 to 10 millimeter, more preferably between 1.5 to 5 millimeters, for example 2 millimeters.

If reaction zone comprises supported catalyst, the porous material in the preferred restriction section can be identical with the porous material as support of the catalyst.Porous material can be the form of spheroid, other particle shape or ceramic foam.Reaction zone can comprise the supported catalyst of the monolith forms that continuous multi-channel structure is provided.

For the porous material in the restriction section, advantageously at least 70%, preferred at least 80% and advantageously at least 90% hole has less than 5.0mm, for example usually between the 0.1-3.0mm, preferably at the pore width between 0.5-1.5mm between the 0.2-2.0mm and most preferably.

Usually, restriction section have 10-60 hole per square inch, per square inch and most preferably 30-45 hole be per square inch in preferred 20-50 hole.

Usually, the degree of depth of restriction section is 5-100mm, but preferred 10-50mm.

Usually, the degree of depth that reaction zone has is between 10-200mm, but preferred 20-100mm, for example 60mm.Preferred this reaction zone comprises catalyzer.

(degree of depth of restriction section and reaction zone is to measure in the flow direction of reactant gas.Usually, the preferred degree of depth, because this determines duration of contact and as the situation of other size of measuring in gas flow direction, for most of actual purposes, is had nothing to do with reactor cross-section by the flow definition of reactant gas.)

When using catalyzer, compatibly catalyzer is the platinum metals of load.Preferably, this metal is platinum or palladium, perhaps its mixture.

Though can utilize solid support material widely, preferably use aluminum oxide as carrier.Solid support material can be the form of spheroid, other particle shape or ceramic foam.Preferably, carrier is the monolithic with continuous hyperchannel ceramic structure, has cellular outward appearance usually.The preferred vector of catalytically-active metals is a gamma-alumina.Load on the carrier by the mixture of the well-known usual way of those skilled in the art platinum and palladium.Before using, the mixture that obtains is heat-treated to 1200 ℃ then.Promotor also can be loaded on the carrier.The promotor that is fit to comprises copper and tin.

Catalyzer is fixed on the upholder that is fit in the reactor usually, for example catalyst basket.Preferably, between catalyzer and upholder, walk around catalyzer, with sealing material catalyst filling that is fit to and any gap between the upholder in order to prevent gas.The sealing material that is fit to comprises artificial mineral wool, and pottery hair for example can be centered around it edge of the catalyzer in the upholder.In addition, can use the material similar to apply, to help this sealing at the edge of catalyzer to the Primary Catalysts solid support material.

This equipment can be included in the product cooling zone in reaction zone downstream, makes gaseous product can be cooled when reaction zone comes out.The product cooling zone can provide by means of one or more injection nozzles, and described injection nozzle can be injected into condensation product from the product stream that reaction zone comes out.

Preferably, the housing of first and second manifolds, syringe, conduit (if existence), restriction section and reaction zone is a metal, for example steel.When pure oxygen is used as gaseous reactant, with the alloy manufacturing of anti-and oxygen reaction or apply described equipment some or might contact oxygen part may be necessary.When the speed of the temperature height of oxygen and/or oxygen is high, with the reaction of oxygen be more possible.The alloy that is fit to comprises Monel metal.

Just in the downstream of reaction zone, wherein the temperature of reaction product is high, and the preferred construction material is a Langaloy, for example English health nail (unit of length) alloy, Incaloy, Hastelloy or Paralloy.Metal can be configured as definite shape by one or more following technology: static casting, rotary casting, forging, mechanical workout and welding.

Described equipment can comprise suitable thermal sleeve, to reduce the just thermal stresses on the equipment in reaction zone downstream.No matter thermal stresses may occur when the temperature of device interior changes relatively sharp, be to raise rapidly or reduction, for example when starting or stop.The internal surface of appts wall is promptly heated or is cooled off, but the heating of outside surface or cooling are slower, therefore produces stress (for example wall is thick relatively, so that bear the pressure reduction between device interior and the outside) in wall.Use the thin material sleeve pipe, it can be similar to the material of appts wall, as the thermal sleeve of device interior, reduced the rate temperature change of the internal surface that influences wall, and therefore reduced thermal stresses.

Advantageously use described equipment with oxidizing gas raw material partly.Preferably, first kind of gaseous reactant is that oxygen-containing gas and second kind of gaseous reactant are the gaseous paraffin hydrocarbon.

The present invention also provides the method for using previously described device fabrication monoolefine.

Therefore, use the equipment of first kind of embodiment, the invention provides the method for manufacture order alkene, described method comprises

Oxygen containing gas is fed first manifold, and oxygen-containing gas is injected many conduits by many syringes,

By second manifold gaseous paraffin hydrocarbon is fed many conduits, wherein the gaseous paraffin hydrocarbon contacts with oxygen-containing gas in parallel basically mode and mixes,

Gaseous mixture is fed reaction zone by the porous restriction section, and

Preferably in the presence of the incendiary catalyzer that can be supported in beyond the rich oil limits of inflammability, combustion gas mixt partly in reaction zone is with manufacture order alkene.

Therefore, use the equipment of second embodiment, the invention provides the method for manufacture order alkene, described method comprises

From at least one first import, via at least one first manifold, oxygen-containing gas is fed the first many syringes, and from least one second import, via at least one second manifold, the gaseous paraffin hydrocarbon is fed the second many syringes, and wherein each syringe has outlet at the end away from manifold, and its cross section opening that has is 1mm ²Perhaps littler, and wherein the outlet of first and second syringes is located mutually with mix-configuration,

Gaseous mixture is fed reaction zone by the porous restriction section, and

The preferred method of manufacture order alkene has used the equipment with previously described preferred feature.Therefore, for example, for the method for the equipment that uses second embodiment, preferred equipment is to make each syringe have outlet at the end away from manifold, and its cross section opening is 0.5mm ²Perhaps littler.More preferably, the cross section opening of outlet is 0.2mm ²Perhaps littler, 0.1mm for example ²Perhaps littler.

From the method for the raw material production monoolefine that comprises the gaseous paraffin hydrocarbon, paraffinic hydrocarbon can compatibly be ethane, propane or butane.Paraffinic hydrocarbon can be pure basically or can be and other hydrocarbon and the mixture of other material randomly that described other material for example is methane, nitrogen, carbon monoxide, carbonic acid gas, water vapor or hydrogen.Can use the fraction that comprises paraffinic hydrocarbon, for example petroleum naphtha, gasoline, vacuum gasoline or its mixture.The raw material that is fit to is the mixture of gaseous paraffin hydrocarbon, mainly comprises ethane, is produced by separation of methane from Sweet natural gas.Preferred raw material is the paraffinic hydrocarbon that mainly comprises ethane, and it provides and mainly comprises the product of ethene as monoolefine.

As oxygen-containing gas, can compatibly use oxygen or air.The preferred oxygen that uses is randomly used rare gas element, for example nitrogen dilution.The ratio of gaseous paraffin hydrocarbon and oxygen-containing gas mixture normally hydrocarbon and oxygen-containing gas is carried out 5 to 20 times of stoichiometric ratio that perfect combustion generates carbonic acid gas and water.Preferably consist of 5 to 10 times of stoichiometric ratio of hydrocarbon and oxygen-containing gas.

Though described equipment can use under any pressure, for example between 0-100barg, useful especially is under high pressure to use.At the pressure of first and second ingresss preferably between the 10-50barg, most preferably between the 20-40barg and advantageously between 25-35barg, 30barg for example.

Oxygen-containing gas is charging at ambient temperature, but is preheating to 50 to 150 ℃, preferred 80-120 ℃ usually, for example 100 ℃.Oxygen-containing gas is injected in the conduit, and perhaps from the outlet injection of described many syringes, its speed should prevent to make the possibility of flame stabilization in the syringe outlet.Especially, in first embodiment of the present invention, the end of syringe can be the nozzle that is fit to, to improve velocity of discharge.Velocity of discharge usually greater than 30m/s, be preferably greater than 50m/s and advantageously greater than 70m/s.

The gaseous paraffin hydrocarbon is preheating to 100 to 400 ℃, preferred 150-350 ℃ usually, and for example 300 ℃, and be passed into described conduit or send from the described second many syringe, wherein it is mixed nearly with oxygen-containing gas.The gaseous paraffin hydrocarbon enter conduit or the speed of coming out from the described second many syringe usually above 5m/s, preferably be higher than 15m/s and advantageously be higher than 20m/s.

In first embodiment, the speed of the oxygen-containing gas that comes out from syringe and the speed that enters the gaseous paraffin hydrocarbon of conduit preferably have at least 1.5: 1, preferably at least 3: 1 and most preferably less than 6: 1,4: 1 ratio for example.This ratio has guaranteed rapid mixing.

In second embodiment, the ratio of the speed of the speed of the oxygen-containing gas that comes out from first syringe and the gaseous paraffin hydrocarbon that comes out from second syringe will depend on the ratio of the relative ratios of the quantity of first and second syringes, their relative dimension and desirable oxygen and paraffinic hydrocarbon, but preferred described ratio is at least 0.1: 1, preferably at least 1: 1 and most preferably at least 5: 1 is common, and the velocity of discharge of oxygen-containing gas is 50m/s at least, 100m/s at least especially.For example, the size of the syringe of oxygen-containing gas and number can be so that velocity of discharge be 100m/s at least, and the number of the syringe of gaseous paraffin hydrocarbon and size can be so that velocity of discharge be less than 10m/s, and the V-bar of the mixed flow that comes out from syringe can be about 3m/s.

The temperature of gaseous mixture usually between 100 to 400 ℃, preferred 100 to 300 ℃, for example 200 ℃.Except that the gaseous paraffin hydrocarbon is fed the conduit or second syringe, other gas also can be led to the described conduit or second syringe, for example hydrogen, carbon monoxide and/or carbonic acid gas.

In first embodiment, gaseous mixture can be cooled by first cooling zone, refrigerant wherein, and for example water passes through around the outer surface region of catheter downstream end.The cooling of catheter downstream end has prevented the local heating of conduit, forms at the conduit outlet place under the situation of stationary flame, and it has eliminated the tendency of any " flame creep retraction ".

The temperature of refrigerant usually between 20-200 ℃, and preferably between 80-120 ℃, for example 100 ℃.The coolant flow Be Controlled make coolant temperature raise less than 100 ℃, preferably less than 50 ℃ and most preferably less than 30 ℃.

First cooling zone makes the temperature of gaseous mixture reduce at least 10 ℃, preferably at least 20 ℃ and most preferably at least 30 ℃.

In two kinds of embodiments, gaseous mixture usually with 1.0-10.0m/s, preferred 2.0-6.0m/s and most preferably the average cross-section speed of 2.5-3.5m/s feed restriction section.

Gaseous mixture usually with 1.0-10.0m/s, preferred 2.0-6.0m/s and most preferably the speed of 2.5-3.5m/s feed reaction zone.

Pressure drop by restriction section is usually between the 0.01-0.2 crust and preferably between the 0.05-0.1 crust, for example 0.08 crust.

Temperature in the reaction zone usually above 500 ℃, for example be higher than 650 ℃, usually above 750 ℃ with preferably be higher than 800 ℃.

Upper temperature limit can compatibly be the highest 1200 ℃, for example the highest 1100 ℃, preferably the highest 1000 ℃.The temperature of the product that comes out from reaction zone is higher than 800 ℃, for example is higher than 900 ℃, and pressure is usually between the 10-50barg, most preferably between the 20-40barg and advantageously between 25-35barg, for example 30barg.

Preferred product is promptly cooled off in the product cooling zone.This has guaranteed high olefins yield, and therefore the speed of reaction because the product cooling step has slowed down in the gaseous product logistics prevents further reaction.

Advantageously, the gaseous product logistics by with in condensation product (preferably at many points) the injecting gas product logistics, make the evaporation of condensation product that gaseous product logistics cooling is cooled.

Condensation product can be gas or liquid.When condensation product was gas, it is inert gasses preferably.Preferably, condensation product is a for example water of liquid.

Inject condensation product with high pressure and high temperature and guaranteed most condensation product flash evapn under reactor pressure, therefore in the gaseous product logistics, provide very fast temperature to fall.

Therefore, condensation product, water for example injects with the pressure that is higher than the gaseous product logistics pressure usually, 100barg for example, and usually 100-400 ℃ and preferred 200-350 ℃, for example inject under 300 ℃ the temperature.

Preferably, after coming out from reaction zone, the temperature of gaseous product logistics is at 60mS, preferred 40mS and advantageously be reduced to 800 ℃, preferred 600 ℃ in the 20mS.

Illustrate the present invention by means of accompanying drawing now, wherein:

Fig. 1 represents the equipment according to first embodiment of the present invention,

Fig. 2 a diagrammatically represent to be used for second embodiment of the present invention equipment first and second syringes mix-configuration section and

Fig. 2 b diagrammatically represents the side-view of the equipment of second embodiment of the present invention.

In Fig. 1, oxygen-containing gas feeds first Room (2) via first import (1), enters many syringes (3) then.The gaseous paraffin hydrocarbon enters second Room (5) via second import (4), enters many conduits (6) then.Oxygen-containing gas injects conduit (6) via syringe (3), and gaseous paraffin hydrocarbon and oxygen-containing gas are mixed therein.

Gaseous mixture feeds restriction section (7) then, and wherein the momentum of gaseous mixture is lowered, and makes it feed reaction zone (8) in uniform mode, and described reaction zone comprises catalyzer, and this catalyzer can be supported in the burning beyond the rich oil limits of inflammability.Gaseous reactant is transformed in reaction zone (8), and the product stream that comprises alkene is provided.

Gaseous mixture is being fed restriction section (7) before, first cooling zone (9) that contacts the downstream end of described many conduit is used to reduce the temperature of gaseous mixture.

At last, the product stream that comprises alkene is passed into product cooling zone (10), to reduce the temperature of product stream before reclaiming.

In Fig. 2 a, arrange with triangle configuration by a series of first syringes (23) that open circles shows.The outlet of first syringe is dispersed between many second syringes (26), and second syringe is arranged with rectangular configuration.In overall the arrangement (this figure only shows a part), the quantity of second syringe that exists in this configuration is about twice of the first syringe quantity.

In Fig. 2 b, oxygen-containing gas is passed into first Room (22), enters many first syringes (23) then.The gaseous paraffin hydrocarbon is passed into second Room (25), enters many second syringes (26) then.Oxygen-containing gas and gaseous state paraffinic hydrocarbon come out and mixing promptly from corresponding syringe.

Gaseous mixture feeds restriction section (27) then, wherein the speed of gaseous mixture is by average (momentum of gaseous mixture is lowered), make it feed reaction zone (28) in uniform mode, described reaction zone comprises catalyzer, and this catalyzer can be supported in the burning beyond the rich oil limits of inflammability.Gaseous reactant is transformed in reaction zone (28), and the product stream that comprises alkene is provided.

At last, the product stream that comprises alkene is passed into product cooling zone (not shown), to reduce the temperature of product stream before reclaiming.

Claims

1. the method that is used for manufacture order alkene, this method forms monoolefine by oxygen-containing gas and gaseous paraffin hydrocarbon reaction, and this method is used a kind of equipment, and this equipment comprises:

First feedway, it comprises first outlet and second feedway that is used to carry oxygen-containing gas, it comprises second outlet that is used to carry the gaseous paraffin hydrocarbon, restriction section, and reaction zone, for every square metre of reaction zone cross section, this equipment comprises at least 100 first and second outlets

Wherein, restriction section is a porous, with regard to the flowing of oxygen-containing gas and gaseous state paraffinic hydrocarbon, be positioned in the downstream of first and second feedwaies, and be communicated with the first and second feedway fluids, reaction zone is positioned in the downstream of restriction section with regard to the flowing of oxygen-containing gas and gaseous state paraffinic hydrocarbon, and be communicated with the restriction section fluid, and wherein, first feedway and second feedway are configured such that first gas and second gas, before the contact resistance district, contact and mix in parallel mode, described setting provides by following:

(a) feedway is positioned in another feedway, and at least a portion of the described feedway that is positioned at another feedway, provide opening, make a kind of gaseous reactant to contact by described opening and with another kind of gaseous reactant, or

(b) first feedway comprises that at least one is used for oxygen-containing gas is supplied with first import of at least one first manifold and first syringe that is used to carry oxygen-containing gas that comes out from described first manifold, and second feedway comprises that at least one is used for the gaseous paraffin hydrocarbon is supplied with second import of at least one second manifold and second syringe that is used to carry the gaseous paraffin hydrocarbon that comes out from described second manifold

Wherein, each syringe has outlet at the end away from manifold, and its cross section opening is maximum 1mm ², and

Wherein, the outlet of first and second syringes is located mutually with mix-configuration,

This method comprises:

Oxygen-containing gas is fed described first feedway, and the gaseous paraffin hydrocarbon is fed described second feedway, make the gaseous paraffin hydrocarbon contact and mix with oxygen-containing gas,

With gaseous mixture via the porous restriction section feed reaction zone and

In the presence of the incendiary catalyzer that can be supported in beyond the rich oil limits of inflammability, combustion gas mixt partly in reaction zone is with manufacture order alkene.

2. the process of claim 1 wherein that described equipment comprises at least 1000 first and second outlets on every square metre of reaction zone cross section.

3. the method for claim 1 or claim 2, wherein said equipment is included in the product cooling zone in reaction zone downstream, wherein, by with condensation product in many some injecting gas product logistics, make the evaporation of condensation product that the gaseous product logistics is cooled off, and with gaseous product logistics cooling promptly in the product cooling zone.

4. any one method of aforementioned claim, wherein the temperature of gaseous product logistics is reduced in the back 60ms that comes out from reaction zone and is lower than 800 ℃.

5. any one method of aforementioned claim, wherein the average inertial pressure gradient factor of restriction section is between 1000-5000/m.

6. any one method of aforementioned claim, wherein the gaseous paraffin hydrocarbon is ethane, propane or butane, it is randomly with other hydrocarbon with randomly mix with other material.

7. any one method of aforementioned claim, wherein the ratio of gaseous paraffin hydrocarbon and oxygen-containing gas mixture is a hydrocarbon and oxygen-containing gas perfect combustion generates 5 to 20 times of ratio of the stoichiometry of carbonic acid gas and water.

8. any one method of aforementioned claim, wherein at the pressure of first and second ingresss between 10-50barg.

9. any one method of aforementioned claim, wherein first feedway comprises that at least one is used for oxygen-containing gas is supplied with first import of at least one first manifold and the syringe that is used to carry oxygen-containing gas that comes out from described first manifold, and second feedway comprises that at least one is used for the gaseous paraffin hydrocarbon is supplied with second import of at least one second manifold and the conduit that is used to carry the gaseous paraffin hydrocarbon that comes out from described second manifold

Wherein, with regard to the flowing of oxygen-containing gas, second manifold is positioned in the downstream of first manifold, and

Restriction section is a porous, with regard to the flowing of oxygen-containing gas and gaseous state paraffinic hydrocarbon, is positioned in the downstream of second manifold, and is to be communicated with the catheter fluid of coming out from second manifold,

And wherein, each conduit comprises upstream extremity that comes out from second manifold and the downstream end that is communicated with the restriction section fluid, and wherein the syringe that comes out from first manifold is configured such that they extend through second manifold, and axially protrudes in the conduit upstream end

This method comprises:

Oxygen-containing gas is fed first manifold, and oxygen-containing gas is injected conduit via syringe,

And by second manifold gaseous paraffin hydrocarbon is fed many conduits, wherein the gaseous paraffin hydrocarbon contacts with oxygen-containing gas and mixes.

10. the method for claim 9, wherein first manifold is that first Room and second manifold are second Room, and the syringe that comes out from first Room forms many microscler paths, they extend into the upstream extremity of the many conduits that come out from second manifold by second Room.

11. the method for claim 9 or 10, wherein the end of syringe is a nozzle, and it provides current regulator at opening part, and it has 0.5 to 3.0mm internal diameter.

12. any one method of claim 9 to 11, wherein restrictor is provided between the internal surface of the outside surface of syringe and conduit, the position that is in or approaches to enter at the upstream extremity syringe of conduit conduit.

13. any one method of claim 1 to 8, wherein first feedway comprises that at least one is used for oxygen-containing gas is supplied with first import and many syringes that is used to carry oxygen-containing gas that comes out from described first manifold of at least one first manifold, and second feedway comprises that at least one is used for the gaseous paraffin hydrocarbon is supplied with second import and many second syringes that is used to carry the gaseous paraffin hydrocarbon that comes out from described second manifold of at least one second manifold

Wherein, the outlet of first and second syringes is located mutually with mix-configuration, and

Wherein every square metre has at least 10000 first and second syringes altogether.

14. the method for claim 13, wherein every square metre has at least 100000 first and second syringes altogether.

15. the method for claim 13, wherein every square metre has at least 1000000 first and second syringes altogether.

16. any one method of claim 13 to 15, wherein the outlet of syringe is all located with the planar configuration.

17. any one method of claim 13 to 16, wherein each syringe has outlet at the end away from manifold, and its cross section opening is 0.004 to 0.5mm ²

18. any one method of claim 13 to 17, wherein syringe forms as the path in the diffusion-bonded parts.

19. an equipment, it is suitable for the reaction of first gaseous reactant and second gaseous reactant formation gaseous product, and this equipment comprises:

First feedway, it comprises first outlet that is used to carry first gaseous reactant, with second feedway, it comprises second outlet that is used to carry second gaseous reactant, restriction section, and reaction zone are for every square metre of reaction zone cross section, this equipment comprises at least 100 first and second outlets

Wherein, restriction section is a porous, with regard to the flowing of first and second gaseous reactants, be positioned in the downstream of first and second feedwaies, and be communicated with the first and second feedway fluids,

Reaction zone is positioned in the downstream of restriction section with regard to the flowing of first and second gaseous reactants, and is communicated with the restriction section fluid, and

Wherein, first feedway and second feedway are configured such that first gas and second gas, before the contact resistance district, contact and mix in parallel mode, and described setting provides by following:

A feedway is positioned in another feedway, and at least a portion of the described feedway that is positioned at another feedway, provide opening, make a kind of gaseous reactant to contact by described opening and with another kind of gaseous reactant.

20. an equipment, it is suitable for the reaction of first gaseous reactant and second gaseous reactant formation gaseous product, and this equipment comprises:

First feedway, it comprises that at least one is used for first gaseous reactant is supplied with first import of at least one first manifold and first syringe that is used to carry first gaseous reactant that comes out from described first manifold, with second feedway, it comprises that at least one is used for second gaseous reactant is supplied with second import of at least one second manifold and second conduit that is used to carry second gaseous reactant that comes out from described second manifold, restriction section, and reaction zone

Each syringe has outlet at the end away from manifold, and its cross section opening is maximum 1mm ², have at least 10000 first and second syringes for the described equipment of the cross section of every square metre reaction zone, and the outlet of first and second syringes is located mutually with mix-configuration.