CN100450603C - Device and method for heat synthesis - Google Patents

Abstract

The present invention relates to a device for thermally converting one or more reactants into a required final product, which comprises an insulated reactor chamber and a limited contracting-expanding nozzle, wherein a high-temperature heater, such as a plasma torch, is arranged at the inlet end of the insulated reactor chamber, and the limited contracting-expanding nozzle is arranged at the outlet end of the insulated reactor chamber. In a thermal converting method, reactants are injected in the front surface of the reactor chamber to cause the reactants to be thoroughly mixed with a plasma stream before the reactants enter the reactor chamber, and the reactor chamber has a reaction region, the temperature of which is kept to be basically uniform. The obtained thermal air stream passes through the nozzle to be rapidly cooled, so that one or more final products in a heating balanced reaction stage are frozen, and the thermal air stream is discharged through an outlet pipeline under the condition of no contracting-expanding nozzle; then, the required final products are separated from the air stream.

Description

The apparatus and method of thermal synthesis

Technical field

The present invention relates generally to a kind of process for thermosynthesizing.The present invention is specifically related to the reactant heat deflection in the thermodynamically stable high temperature gas flow is become required end product, as the method and apparatus of gas or ultrafine solids particle.

Background technology

In the U.S., the price of natural gas (wherein methane is main hydrocarbon) is low, and is the energy that is underutilized.A large amount of storages of known natural gas are present in new-world remote districts, but this energy can't be economical and come from these area transportations safely.In recent decades, studied natural gas is transformed into the higher hydro carbons of value, but this research obtained success on modern economy is very limited.In recent years, having carried out some studies to estimate natural gas (being to be used for direct burning now) is transformed into the technology as the acetylene of household chemicals raw material.The utilization to existing a large amount of natural gas reservoir relevant with oil field and cheap labour makes the technology that is transformed into acetylene by natural gas be used to be manufactured on this part especially attracting in the world household chemicals.

Acetylene can be used as the plastics manufacturing or the certified catalytic reaction of mat is transformed into the raw material that liquid hydrocarbon fuel is used.Acetylene is well-known and is to generally acknowledge as the versatility of initiation material.The raw material that present plastics are used is the raw material of petrochemistry base.The supply from the home and overseas oil storage of making these petrochemistry based raw materials descends, and this has just constituted pressure to the substitute of seeking the petrochemistry based raw material.Therefore, the present interest of having recovered once more the acetenyl raw material.

Methane thermal is transformed into liquid hydrocarbon comprises indirect method or direct method.Conventional methyl alcohol is made gasoline (MTG) method and Fischer-Tropsch (FT) method is two main examples of this indirect transformation method, and they are that methane reforming (reforming) is become synthesis gas, are converted into end product then.These expensive heat sink methods are operated under high temperature and high pressure.

Seek a kind of with methane direct catalysis being transformed into light olefin (C for example ₂H ₄), the method that is transformed into liquid hydrocarbon has then become the focus of present natural gas conversion techniques.Oxidative coupling, hydrogen-oxygen chlorination (oxyhydrochlorination) and partial oxidation are the examples that directly changes method.These specification requirements are operated under the condition of elevated pressures, moderate temperature and use catalyst.It is the ultimate challenge that these technology of exploitation face that exploitation is used for the special catalyst that natural gas straight switches through political reform.The conversion ratio of this method is low, compare its expense height with indirect method, and these technology is not confirmed also.

Light olefin can be by extracting hydrogen in very high temperature (＞1800 ℃) from methane, and then coupling hydrocarbon free radical makes.The methane high temperature transformation becomes acetylene can use reaction equation 2CH ₄→ C ₂H ₂+ 3H ₂Expression, this is an example.This process is known one section long time.

Methane becomes the transition process of acetylene, is to use cold liquid hydrocarbon quencher to prevent back reaction at present.Perhaps the most well-known in these processes is the Huels method, and this method was used many years in using in that Germany is commercial.By " directly " between high-temperature electric arc (15000-20000K) and methane feed contact, the arc reactor of Huels just can transfer electrical energy.Water and liquefied propane quenching product gas are in order to prevent back reaction.For the Huels method, the single track productive rate of acetylene is less than 40%.By all hydrocarbon beyond acetylene and the ethene are recycled C ₂H ₂Gross production rate can increase to 58%.

Although use commercial, the Huels method only is worthwhile reluctantly economically, because single track efficient is lower, and need isolate product gas from quench gas.The subsidy of German Government has helped still to make in this way on producing.

Use the similar approach of 9MW reactor to be set up by E.I.Du Pont Company, this method is in the operation of 1963 to nineteen sixty-eight, and the acetylene that it will make from the liquid hydrocarbon source is delivered to neoprene factory.It is reported and confirmed that also this method uses methane feed to carry out with the scale of pilot plant test.And the operation of plant layout is confined to liquefied petroleum gas or liquid hydrocarbon distillate.The scale of method for testing is not reported in this Du Pont.In Du Pont process, make the electric arc rotation with magnetic methods, and in original Huels method, electric arc is the gas " whirlpool is stable " that injects with tangential.In Du Pont process, all raw materials that dilute with hydrogen all pass through arc column.In the Huels method, be that the downstream position at electric arc injects a part of reactant.

Westinghouse uses the hydrogen plasma reactor to come cracking natural gas to make acetylene.In plasma reactor, hydrogen is sent into arc region, be heated to plasmoid.Temperature is higher than the red-hot H of 5000K ₂Plasma outlet stream and natural gas rapid mixing below the arc district, electric energy is transferred in the raw material indirectly.With the same in the Huels method, with the product gas of liquefied propane and water quenching heat, in case non-return reaction.Yet, the same with the Huels method, need from quench gas, isolate product gas.It is reported that all hydrocarbon can make gross production rate bring up to 67% beyond recirculation acetylene and the ethene.Be used for the H that natural gas changes ₂Plasma method had carried out widely test with small-sized scale already, but also need further develop and verify with pilot-scale.

A kind of reactor of being made up of two concentric, heat-resisting graphite-pipes has been developed in Norway's science and industrial research foundation (Scientific and Industrial ResearchFoundation of Norway).When temperature was 1900-2100K, the cracking reaction of methane occurred in two narrow annular space between the pipe.In operating process, the carbon that forms in annular space can cause tangible operational issue.Equally also use the liquefaction quencher to come the quenching product, in case non-return reaction.The same with above-mentioned previous two kinds of acetylene autofrettages, need from quench gas, isolate product gas.From then on the multiple tracks acetylene gross production rate that heat-resisting reactor obtains is about 80%, and this method is tested in pilot plant.

Therefore, need make improvements observed medium methane conversion efficiency, acetylene yield, selectivity and energy expenditure rate in above-mentioned those methods.

The high corrosion resistance that titanium had and the performance of intensity combine with its lower density and make titanium alloy be ideally suited for many high-tech purposes, especially in air line.The application of titanium in chemical plant and power plant also is attractive.

Unfortunately, the extensive use of titanium is subjected to serious restriction owing to its expense is high.This high cost is the direct result that is used to make the batch characteristic of the conventional Kroll of titanium and Hunter method and uses required high energy rate.

For many years, the method for large scale production that uses in titanium industry is constant comparatively speaking.They comprise following key step: the impure oxide ore of (1) chlorination, (2) purification TiCl ₄, (3) make titanium sponge with sodium or magnesium-reduced, and (4) remove titanium sponge, and (5) leaching, distillation and vacuum melt again, to remove Cl, Na and Mg impurity.The resultant effect of the intrinsic cost of these processes, relevant with the machining titanium with forging difficulty and the deficiency on titanium sponge utilizes in recent years make that all the use of titanium is less.

At present ongoing a kind of most promising for preventing that the method that the titanium alloy member high cost is developed from being the powder metallurgic method of making near last component shape.For example, for every kilogram of titanium that in aircraft, uses at present, estimate to produce 8 kilograms of waste materials.Powder metallurgic method can reduce this refuse rate greatly.Although mainly comprising, this technology makes powder then with its dense easy steps that changes into closely knit goods, but still it is being carried out quite a large amount of research at present, make this method optimization, make final product have the performance that is equal at least with forging or founding materials, and lower than the latter on expense.

A kind of possible powder metallurgic method approach of making titanium alloy member is that the metal element powder is directly mixed, then compacting.At present, use the titanium sponge particulate from the Kroll method, but a major defect is its high residual impurity content (mainly being chloride), described impurity can form hole in final material.Other alternative powder metallurgic method comprises that direct use titanium alloy powder carries out the high temperature insostatic pressing (HIP) compacting.

In making the optimized process of this titanium alloy powder, relate to several schemes at present.The result is very likely, but all schemes comprise that all use Kroll titanium is as initiation material.Use this existing powder will use the many expensive as mentioned above purifications and the step of alloying.

In nearest 30 years document, the method for making titanium under condition of plasma receives publicity successively.Report is usually directed to hydrogen reduction titanium tetrachloride or titanium dioxide, and some other document then relates to sodium or magnesium and reducing.

In electric arc furnaces, studied use hydrogen reduction titanium tetrachloride.When 2100K, only carried out partial reduction.Studied the same reaction system in plasma flame more widely, and in low titanium chloride (Deutsche Bundespatent 1,142, on January 10th, 159,1963) and titanium (Japan Patent on May 23rd, 6854,1963; 7408, October 15 nineteen fifty-five; U.S. Patent No. 3,123, on March 3rd, 464,1964) obtained patent on the preparation method.

Should be when the 2500K although early stage calculation of thermodynamics points out with hydrogen titanium tetrachloride to be reduced into Titanium, this system is not a simple system.Calculating shows that it is more favourable on thermodynamics to form low titanium chloride in this temperature range.

U.S. Patent No. 3,123,464 have disclosed to low, better are to surpass under the temperature of titanium boiling point (3535K) to heat reactant (TiCl ₄And H ₂), can successfully titanium tetrachloride be reduced into the liquid titanium.Under so high temperature, can be reduced H effectively by atomic hydrogen although disclosed titanium tetrachloride vapors ₂Take place dissolving or with the tendency of Ti reaction and not obvious, formed HCl 10% disassociation of only having an appointment, and the formation of low titanium chloride is not favourable.The titanium tetrachloride vapor product is condensed into liquid then or in the water cooled steel condenser of about 3000K, therefrom overflows to flow in the mould, perhaps with the hurried powder that is cooled to of hydrogen, it is collected in the hopper.Because the liquid titanium that condenses only has gaseous by-product or impurity, estimate that its purity (dehydrogenation impurity is outer) is high from gas.

Japan Patent 7408 has been described following reaction condition: make TiCl ₄Gas and H ₂The mixture of (50% is excessive) is with 4 * 10 ^-3m ³The flow of/min is the tungsten electrode nozzle of 5mm by internal diameter, and discharge (3720V and 533mA) is to another electrode apart from 15mm.Heat the Powdered crystal of gained in a vacuum, make 99.4% pure titanium.

The neither one patent is clearly mentioned energy consumption in above-mentioned patent.Once used self-solidifying crucible smelting furnace to attempt to develop plant-scale hydrogen reduction method, but this effort had been interrupted afterwards.Recently, the someone claims and produced a spot of titanium in hydrogen plasma, but when confirming that product is titanium carbide really, this saying has just shunk back subsequently.

In a word, attempt in hydrogen plasma, to handle TiCl ₄Historical process show that as if the mixture that has only partial reduction promptly to be reduced into titanium and its subchloride is possible, unless reach very high temperature (＞4000K).Previous researcher draws a conclusion, and need be about to the condensation of vapor phase titanium earlier, to overcome the thermodynamic phase on its system.

Therefore, need to overcome or to avoid the method and apparatus of the problems referred to above and restriction.

Summary of the invention

An object of the present invention is to provide a kind of method and apparatus that one or more reactant heat deflections in the thermodynamically stable high temperature gas flow is become required end product.

A further object of the present invention provides a kind of improved process transformation efficiency and product productive rate that one or more reactant heat deflections in the thermodynamically stable high temperature gas flow is become required end product.

It is the method and apparatus of the productive rate of acetylene from the natural gas heat deflection that a further object of the invention provides a kind of raising.

In order to reach above-mentioned these purposes, press the existing and broadly described the present invention of presents, a kind of method and apparatus that one or more reactant heat deflections in the thermodynamically stable high temperature gas flow is become the required end product of gas or ultrafine solids particle form is provided.In general, this method comprises the steps.At first, the end at an axial flow reactor adds the reaction logistics.Then, when reaction logistics axial flow is crossed injection canal that diameter reduces with turbulization with respect to axial flow reactor,, mix up hill and dale with hot gas thereby will react logistics to reaction logistics heating.Subsequently, allow the reaction logistics of thorough mixing axially by the reaction zone of axial flow reactor, this reaction zone keeps even temperature basically in its length range.Axial flow reactor has certain length and temperature, and it is operated under certain condition, and described condition is enough to the reaction logistics is heated to the selected reaction temperature that required product stream is produced on the close position of the axial flow reactor port of export.

Specifically be that method of the present invention comprises the steps.At first, comprising that at least one pair of feeds the plasma arc air-flow between the plasmatorch electrode of the electrode of close axial flow reactor chamber inlet end.This plasma arc air-flow feeds with selected flow, make electrode accept selected plasma input (plasma inputpower level) simultaneously, produce plasma in the injection canal of restricted diameter system, this injection canal extends in the reactor chamber and orientating reaction device chamber outlet end.Secondly, at least a reactant is injected injection canal, the reaction logistics of introducing is sneaked in the plasma up hill and dale, obtain to mix completely, introduce in the reactor chamber then.Reactor chamber keeps even temperature basically in whole field of flow, make reaction reach balance.The air-flow that leaves nozzle is in the port of export cooling of reactor chamber, and its way is to reduce its speed, simultaneously to be enough to prevent that the speed that its power temperature improves from removing heat.Isolate required end product in the gas that from cooling blast, keeps then.

Compare with existing conventional method, the invention provides the raising on method transformation efficiency and the acetylene yield.This improvement mainly be by with the more effective injection of reactant and and plasma gas mixing, and make thermograde in the reactor and cold boundary layer reduce to Minimal Realization.Improved mixing and thermal control also can increase following this feature, promptly reduce the acetylene productive rate of hydrocarbon in addition.The quenching speed that reaches by the heat transmission on the wall in little reactor is enough to suppress the acetylene decomposition and forms soot.The formation of other hydrocarbon is not subjected to obviously to improve the influence of quenching speed beyond the ethene.

These and other purposes, features and advantages of the present invention will more completely illustrate by describing below with appended claims, perhaps can be by grasping according to following described enforcement the present invention.

Description of drawings

For the mode that reaches above-mentioned and other advantage of the present invention and purpose is described, will make more specific description to the present invention who sketches above with reference to some particular of explanation in the accompanying drawings.What should understand is that these accompanying drawings only illustrate the typical embodiment of the present invention, therefore can not think that they are used for limiting its scope.By using accompanying drawing, will the present invention be described with additional feature and details.

Fig. 1 is the schematic cross-section of one embodiment of the invention reactor system;

Fig. 2 is the schematic cross-section of another embodiment of the invention reactor system;

Fig. 3 is the schematic cross-section of another embodiment reactor system of the present invention;

Fig. 4 is the figure that describes the theoretical maximum of the methane that can transform in reactor system of the present invention;

Fig. 5 is the figure that describes transformation efficiency and methane feed discharge relation;

Fig. 6 is the figure that the time of staying and methane inject discharge relation in the temperature of reactor describing to estimate and the reactor;

Fig. 7 is the figure that describes methane conversion efficiency and reactor pressure relation;

Fig. 8 is the figure that describes acetylene yield and methane injection discharge relation;

Fig. 9 is the figure that describes acetylene yield and methane injection discharge relation;

Figure 10 is the figure that describes hydrocarbon productive rate and methane injection discharge relation;

Figure 11 is the figure that describes hydrocarbon (no methane) productive rate and methane injection discharge relation;

Figure 12 is the figure that describes transformation efficiency and methane feed discharge relation;

Figure 13 is the figure that describes acetylene yield and methane feed discharge relation;

Figure 14 is the figure that describes productive rate efficient and methane feed discharge relation;

Figure 15 is the figure that describes hydrocarbon (no methane) productive rate and methane feed discharge relation;

Figure 16 is the figure that describes acetylene yield and pressure dependence;

Figure 17 is the figure that describes hydrocarbon productive rate and reactor pressure relation;

Figure 18 describes the acetylene that produced and the figure of energy expenditure rate and methane feed discharge relation.

The specific embodiment

The present invention relates generally to the reactant heat deflection is become the required end product such as the method and apparatus of gas or ultrafine solids particle.Device of the present invention generally includes a porous road syringe, and it is used for reactant is injected a chamber in the front of reactor, thereby reactant is mixed with plasma jet.Reactor for example uses that the carbon lining insulate, and the reactor of described insulation can make radial symmetry gradient reduce to minimum for the time of staying that provides of reaction simultaneously.The port of export at reactor can also connect a converging-diverging nozzle, and it can produce ultrasonic wave and expand, thereby greatly improves quenching speed.

Have the various reactors and the method that are used for pyroreaction, in these reactors and method, need again fast cooling to freeze product in case non-return reaction or resolve into undesired product.For example, the U.S. Patent No. 5,749,937 of Detering (below be called " the Detering ") thermal insulation of using gases and expansion of constant entropy in converging-diverging nozzle comes fast quench.This expansion can make cooling velocity surpass 1010K/s, so just only can preserve the product of balance at high temperature.

Yet still continuation needs to improve the value of transformation efficiency and productive rate.Find that thermograde and bad mixing can cause temperature uneven distribution in reactor.The composition of product stream becomes with the dynamics or the speed of reaction, and also the inhomogeneities with temperature becomes.These effects can cause the composition of product stream that obvious variation is arranged.If quench process is too slow or delay, product that then makes such as acetylene meeting thermal decomposition become the solid carbon soot or may mainly further react on hot surface again, form benzene and heavier hydrocarbon.

The present invention is just at these problems.The uneven temperature problem can have the structure of reactor of " hot wall " of insulation lining to overcome if any the reactor of carbon lining by use, and described reactor can make the heat loss of radial symmetry gradient and reactor part reduce to minimum.Mixing bad problem can be solved by the design of adopting the restricted access syringe, and described design can be sneaked into reactant in the plasma jet well.The effect of quenching speed can be by putting into device with ultrasonic wave quenching nozzle, makes it just in time be positioned at the back location of reactor part and solved.In ultrasonic nozzle, from the hot gas rapid expanding of reactor part to lower pressure.Like this, heat energy just is transformed into kinetic energy, so mixture cools off fast.This process is sometimes referred to as pneumatic quench.Can reach the quenching speed of 107 ° of-108 ℃/s, it is than big one to two order of magnitude of the quenching speed of reporting in original Huels method.Do not having under the situation of this converging-diverging nozzle, approximately having only 0.1 * 106 ℃/s by the quenching speed that heat transmission on the wall reaches.

Although the notion of this reactor is to develop from the process of natural gas formation acetylene in research at first, but the technology skilful person of this area can be appreciated that method and apparatus of the present invention can be used in other process that needs fast quench (comprising the production of titanium).

The high temperature (5,000 °-20,000 ℃) that fast quench reactor as herein described and method of operating have utilized high-temperature heating equipment such as heat plasma body device to be produced is manufactured on thermodynamically stable material under this high temperature.These materials comprise metal, alloy, intermetallic compound, composite, gas and pottery.

Fast quench reactor of the present invention and method are put up with a nonstorage calorifier and are described and illustrate that described nonstorage calorifier comprises plasmatorch and plasma arc air-flow.Yet what should understand is that nonstorage calorifier also can comprise other the nonstorage calorifier such as the flame such as the oxygen/hydrogen flame of laser instrument and suitable fuel oxidation generation.

What should understand is that the various features of describing in various embodiments can be exchanged below, and the present invention is provided other included embodiments.For example, various embodiments can comprise or not comprise converging-diverging nozzle, mixing chamber, downstream syringe or anode syringe.

Referring now to accompanying drawing,, Fig. 1 is the schematic diagram of hypervelocity chilling apparatus 10.Device 10 generally includes axial flow reactor chamber 16, converging-diverging nozzle 18 and the cooling segment 20 of torch part 12, syringe part 14, sealing.

In one embodiment of the invention, device 10 is the fast quench axial flow reactors that are used for one or more reactant heat deflections of thermodynamically stable high temperature gas flow are become the required end product of gas or ultrafine solids particle form.Device 10 comprises the device that is used for introducing at the arrival end of axial flow reactor or place, its front the reaction logistics, and described device for example is to be positioned at the porous road syringe of syringe part 14 or torch part 12 or back with the anode syringe of stating.Device 10 also comprises the heater that is used for producing in the arrival end front of axial flow reactor thermal current, and this thermal current axially flows towards the port of export of axial flow reactor.This heater can be selected from flame such as oxygen/hydrogen flame and their equivalent that the torch, laser instrument, the suitable fuel oxidation that produce plasma produces.In addition, device 10 also comprises the device that makes the injection canal turbulization that reaction logistics and thermal current reduce by diameter, mix up hill and dale with thermal current thereby will react logistics, this injection canal 23 for example is arranged in syringe part 14 or torch part 12 or its equivalent.Device 10 also comprises and is used for the radial symmetry gradient of axial flow reactor is reduced to minimum device, for example is insulating barrier or its equivalent on reactor chamber 16 inside.Axial flow reactor is enough to the reaction logistics is heated to more fortunately operates required end product under the condition near the selected reaction temperature that produces on the position of the axial flow reactor port of export.Each parts of device 10 will be described below in further detail.

Torch part 12 comprises plasmatorch, and it is used for making the air-flow plasma at gained when sending into by the inlet of reactor chamber that enters to carry out thermal decomposition.

Plasma is a kind of high temperature luminous gas, it to small part (1-100%) be ionization.Plasma is made up of gas atom, gas ion and electronics.Whole mutually in, plasma is electroneutral.Allow gas pass through the electric arc that between two electrodes (anode and negative electrode), produces, can obtain the plasma of heat.In time, electric arc is heated rapidly to very high temperature by resistance heat and radiant heat with gas in some microseconds of gas by electric arc.Plasma is generally luminous in the temperature that is higher than 9000K.

Can produce plasma with any gas in such a way.Because gas can be (hydrogen, methane, ammonia, the carbon monoxide) of neutral (argon gas, helium, neon), reproducibility or (oxygen, nitrogen, the carbon dioxide) of oxidisability, the chemical reaction generation better controlled in so just can the article on plasma body.The gaseous mixture of oxygen or oxygen/argon can be used for making the pottery and the composite of metal oxide.Other nitride, boride and gases such as carbide ceramics material require such as nitrogen, ammonia, hydrogen, methane or carbon monoxide are to obtain to be used for the synthetic required appropriate chemical environment of these materials.

The details that produces the torch of plasma is well-known, concerning the technology skilful person of this area, is appreciated that the content that this paper is disclosed, this is not needed further detailed explanation.

Represent the plasma air-flow that enters with arrow 31.Plasma gas also can be reactant or inertia.Normally with one or more reactant flows (arrow 30) dividually in the injected plasma, described plasma flows towards the outlet of reactor chamber 16.Axially the air-flow by reactor chamber 16 comprises and injects plasma arc or at the reactant of carrier gas.

Syringe part 14 comprises the injection canal 23 of injection orifice 22 and restricted diameter, and reactant and plasma are mixed, and reaction mass enters reactor chamber 16 then.Owing to allow reactant and plasma mix before entering reactor 16, thermal loss is just less, and the efficient of system just can improve.

Gas and liquid are the better forms of injecting reactant.Can inject solid, but it evaporates usually too slowly, so that in the plasma that flows fast, be difficult to take place chemical reaction before the gas cooled.If as reactant, then being heated usually, the use solid becomes gaseous state or liquid state before injected plasma.

In free-pouring plasma, the order of magnitude of the typical time of staying of material is a millisecond.Mix in order to make reactant and plasma gas reach maximum, (10-100 atmospheric pressure) injects reactant (liquid or gas) by aperture under pressure, is enough to penetrate the speed that plasma also mixes with it to reach.Better be the reactant that no matter when all uses gaseous state or evaporation, because just need in plasma, not carry out phase transformation like this, thus the dynamic performance of improvement reactor.In addition, the reaction logistics of injection better is and the at right angles direction injection at (90 ° of angles) of plasma gases flow.Yet in some cases, the plus or minus deviation that is up to 30 ° of 90 ° of angles may be best therewith.

The high temperature of plasma makes the liquid material rapid evaporation of injection, and makes its gaseous molecular material split into its atomic component.Various metals (titanium, vanadium, antimony, silicon, aluminium, uranium, tungsten), metal alloy (titanium/vanadium, titanium/aluminium, titanium/aluminium/vanadium), intermetallic compound (nickel aluminide (nickel aluminide), titanium aluminide) and pottery (metal oxide, nitride, boride and carbide), it is synthetic can be that metal halide (chloride, bromide, iodide and fluoride) with liquid state or gaseous form injects from anode arc connecting portion back in the torch outlet or along the plasma of the suitable gas of reactor chamber length.

The axial flow reactor chamber 16 of sealing links to each other with syringe part 14 at an arrival end, and links to each other with nozzle 18 at a port of export.The reactor chamber 16 of one embodiment of the invention has an insulation lining 34 on the surface within it.The reactor of insulation can make radial symmetry gradient reduce to minimum for the time of staying that provides of reaction simultaneously.The general cooling water jecket (not shown) that is provided with in the outside of reactor chamber 16.

Reactor chamber 16 is exactly the place that chemical reaction takes place.Reactor chamber 16 starts from the inlet of plasma arc back, ends at nozzle throat 26 places.Reactor chamber 16 comprises the key reaction device zone that forms product and the convergence portion 24 of nozzle 18 parts.

Temperature requirement in the reactor chamber and its physical dimension depend on for the desired temperature of the poised state that reaches each required end product content.

Because reative cell is red-hot and zone that chemism is high, so the material of the reactor chamber of making and temperature and chemism are adapted, make and reduce to minimum, and make because minimum is reduced in fusing degraded and ablation that the strong plasma resonance of gained causes from the chemical attack of reactant.Reactor chamber is made with stainless steel, nickel, titanium or other suitable material of water-cooled usually.Reactor chamber also can be made with ceramic material, to resist strong chemical environment and thermal environment.

As mentioned above, add lining for the wall of reactor chamber, to keep stationary temperature gradient in the reactor chamber 16 with insulator such as carbon.The purpose of insulator provides the barrier layer of conducting heat, with the thermal loss that reduces process in the cooling jacket of reactor chamber outside.Various insulating materials can use, if selected material not with reactor chamber in reactant reaction and have the enough low coefficient of expansion, in case the outer wall swelling and the explosion of reactor chamber.Like this, such as carbon is the good insulation performance body than good material, and they are chemically inert to the process reaction thing, have the low coefficient of expansion, and stands the high temperature of for example about 2000 ° of-3000 ° of K.Other suitable material for example comprises boron nitride, zirconia, carborundum etc.Yet any heat that can reduce can adopt from the insulating materials that reactor chamber 16 is transmitted on the outer wall, as long as meet above-mentioned standard.

Combine by radiation, convection current and conduction, the wall of reative cell is heated internally.The wall of reative cell cooled off to prevent to take place in its surface unnecessary fusing and/or corrosion.The system that is used to control this cooling should remain on wall the high temperature that the wall material selected for use can allow, and described wall material must be an inertia the reactant of wall temperature in reactor chamber 16 of expection.This is concerning only equally also being suitable for by convection current and the nozzle wall that heats of conduction.

Size to reactor chamber 16 will be selected, and makes the recirculation of plasma and reactant gas reduce to minimum, enters the nozzle throat to keep enough heats (enthalpy), prevents degraded (unwanted back reaction or side reaction).

Must at first use the elongation pipe that can allow the user reach the goal response threshold temperature, determine the length of reactor chamber 16 with the method for experiment.Can allow reactor chamber 16 be designed to enough length then, make reactant under high reaction temperature, have enough time of staying and reach poised state, and be completed into required end product.This reaction temperature can be from minimum about 1700 ℃ to 4000 ℃.

Determine the internal diameter of reactor chamber 16 by the fluid property of plasma and mobile air-flow.The internal diameter of reactor 16 must be enough greatly, can allow required air communication mistake, but should be too not big, cause unnecessary whirlpool or the stagnant wake of backflowing on the wall of reactor, to form.This harmful type of flow is refrigerating gas prematurely, and undesired product such as subchloride or carbon are precipitated.Usually, the internal diameter of reactor chamber 16 should be in the scope of about 100-150% of the plasma diameter at reactor chamber 16 arrival end places.

Converging-diverging nozzle 18 is positioned at the back of reactor chamber 16 coaxially.The effect of converging-diverging nozzle is that the power temperature in the air flow is descended fast.This can " freeze " or stop all chemical reactions effectively.When gas cools off fast, can collect required end product effectively and need not to reach equilibrium condition.Because the transformation mutually (gas-solid) that produces or be cooled to the stabilisation of lower poised state (gas-gas), just can collect after the reason produce in the plasma at high temperature but be the end product that thermodynamic instability maybe can't obtain at a lower temperature.

The convergence portion of nozzle 18 is that upstream portion is limiting passing through of gas, and is controlling the time of staying of thermal current in reactor chamber 16, makes the inclusion of reactor reach thermodynamical equilibrium.When passing through the convergence portion of nozzle 18, the contraction that occurs on the air-flow cross sectional dimensions changes the motion (comprise rotatablely move and oscillating movement) of gas molecule on random direction into the rectilinear motion parallel with the reactor chamber axle.The size of reactor chamber 16 and the gas flow rate of introducing are selected, can in limited nozzle throat, be reached velocity of sound.

When the expansion that enters nozzle 18 when limited air-flow is the downstream part,, its pressure hypervelocity ground is descended owing to increase gradually along the volume of jet expansion cone-shaped wall.The pressure that is produced changes the temperature that has reduced air-flow at once and reaches new equilibrium condition.

By suitably selecting the size of nozzle, reactor chamber 16 can under atmospheric pressure or under pressurized conditions be operated, and the effect of the cooling segment 20 that is in nozzle 18 back by pump remains under the vacuum pressure.The unexpected variation of pressure can make air-flow be under the lower equilibrium condition at once when air communication is crossed nozzle 18, and the undesired back reaction that may take place under the cooling condition that prevents to spin out in the time.

The convergence portion 24 of nozzle 18 its objective is the hot gas Fast Compression is entered in the limited nozzle throat 26, makes the heat loss minimum by wall, keeps laminar flow and minimum turbulent flow simultaneously.This requires the length-width ratio of nozzle diameter to change greatly, with held stationary carry out the transition to first steep angle (＞45 °), and then carry out the transition to less angle (＜45 °), enter the nozzle throat.

The purpose of nozzle throat 26 is Compressed Gas, reaches velocity of sound in the thermal current that flows.This process is transformed into translational energy (speed) on the air-flow axial direction with the random energy of hot gas.So just can reduce the power temperature of gas and the carrying out of almost further limiting chemical reaction at once effectively.Pressure differential between expansion 28 downstreams of reactor chamber 16 and nozzle 18 is being controlled the speed that reaches in nozzle throat and the nozzle downstream expansion.Can apply negative pressure in the downstream for this purpose or apply malleation in the upstream.

The purpose of the expansion 28 of nozzle 18 is to expand reposefully and the gas that quickens to leave nozzle reaches supersonic speed from velocity of sound, and this can further reduce the power temperature of gas.

Term " steadily quicken " requires to use and comes expanding gas less than 35 ° the less angle of flare in practice, and can not produce and assemble harmful result that wall separates and bring out turbulent flow.The branch defection of expanding gas and expansion wall makes at wall and the gas that leaves some part between the gas jet of nozzle throat and backflows.This hot again and bad degradation reaction in part of backflowing and can cause expanding gas, thus the productive rate of required end product is reduced.

Comprise that in device observed hypervelocity quenching phenomenon reaches through following process in the embodiment of the present invention of converging-diverging nozzle,, make the heat energy of gas be quickly converted to kinetic energy by the improved thermal insulation of converging-diverging nozzle and the expansion of constant entropy.Detailed description about the nozzle physical action can be referring to the patent of Detering.

Another kind of reactant under the environment temperature such as hydrogen can tangentially inject the expansion of nozzle 18, to finish reaction or the back reaction when preventing gas cooled.

Cooling segment 20 is positioned at the back of nozzle 18 coaxially, and it is used for further cooling blast and quencher is carried out in reaction.The wall of reactor chamber 16, nozzle 18 and coaxial cooling segment 20 all cools off with cooling water flow.

The end product of reaction can be collected in cyclone separator (not shown).The liquid trap in downstream such as liquid nitrogen trap can be used for condensation and collect product such as hydrogen chloride and superfines in the air-flow before air-flow enters vavuum pump.

Try Fig. 2 now, the device 50 of another embodiment of the invention generally has torch/injection portion 52, syringe part 54, insulated reactor chamber 56 and cooling segment 58.What should understand is, most of parts are as top device 10 is described.

Concerning the good effect that obtains this embodiment of the present invention, find that it is unnecessary that various improvement recited above makes nozzle 18.Therefore, do not had nozzle assembly, replacement be the cooling straight-tube portion that has same inner diameter with the back pipeline.Although not shown in the figures, in the time of need avoiding solid material to block, the present invention also can use with the similar convergent portion of the convergence portion 24 of converging-diverging nozzle 18 and assign to replace nozzle assembly 18.If there is not this requirement, then 58 unexpected transition still is suitable from reactor chamber 56 to cooling segment.

The feature that this embodiment of the present invention also has is that the part of individual anode syringe 64 as torch/injection portion 52 arranged.Anode syringe 64 is placed on comparatively place near plasma arc, just can reduce heat loss, thereby mixing efficiency is just higher.Yet this embodiment has also illustrated also can have one or more syringe bore 60 in torch/injection portion back, and the reactant injection orifice that separates that links to each other with injection canal 62 is provided.

The reactor chamber 56 of this embodiment of the present invention has insulation lining 66 within it on the surface.

Try Fig. 3 now, the device 100 of another embodiment of the invention generally comprises torch/injection portion 102, insulated reactor chamber 104 and cooling segment 106.This embodiment has specifically been cancelled the syringe part of using in the above-mentioned embodiment.What should understand is, most of assembly is still as device 10 is described.

Device 100 comprises anode syringe 110, but does not have the syringe of its back.Like this, anode syringe 110 is just near plasma arc, and it has the space that thorough mixing can be provided before entering reative cell, and it is also comparatively near reative cell, in order to avoid undue cooling.Yet torch part 102 still comprises the injection canal 112 that diameter reduces as can be seen, thereby guarantees that with turbulization reactant thoroughly mixes with plasma before entering reactor chamber 104.

Just because of on reactor chamber 104 inwalls, insulating barrier 108 being arranged, injection canal 112 is arranged and validly anode syringe 110 is placed on comparatively place near plasma arc, device 100 just can reach required reaction with high efficient, even without converging-diverging nozzle.

Although the disclosed content of this paper mainly concentrates on from methane and makes acetylene, the technology skilful person of this area should be understood that and also can adopt method and apparatus of the present invention to prepare other material.These materials comprise (only as an example) titanium, vanadium, aluminium and titanium/vanadium alloy.

Provide some following embodiment the present invention is described, but they do not limit the scope of the invention.

Embodiment

In process of the test, except gas chromatography (GC), all appts that uses among the following embodiment all is directly connected on the data acquistion system of recording occurring continuously system parameter.In case after reaching process power, pressure and the gas flow of appointment, adopt gas chromatography continuously air-flow to be taken a sample 7 minutes time, so that guarantee to obtain representational sample, gas chromatographic analysis is carried out in formal then sampling.Be to clean three times of sample pipe required time fully this sample time of 7 minutes haply.Pressure with oil-sealed rotary pump and flow control valve control quenching nozzle back.Test pressure can be adjusted to atmospheric pressure between about 100 torrs independently, looks experimental condition and different.Spent 1 minute or the shorter time, test reaches stable status.Determine the arrival of steady state operation with the residual gas analyser (RGA) of continuous-reading.To all cooling water flows and entrance and exit temperature monitoring record in addition, so that calculate the energy balance of whole system.

Used plasma gas is Ar and H ₂Mixture; Methane or natural gas are injected in back at the transverse injection syringe of restricted access.Used DC plasmatorch is if use pure hydrogen, just can't long-time operation and do not produce serious anodic attack, so use the plasma gas that contains certain tittle Ar at least to obtain all test datas.Use the Ar of the not participation process chemical reaction of inertia, its advantage is that it can provide system interior object of reference, is used for confirming the mass balance of whole process.By forming the tungsten cathode heavy corrosion that volatility carbonization tungsten takes place, just avoided the direct processing of methane in discharge process.Two most critical aspects of test are the chemical analysis and the whole mass balances of product stream.

Carried out two groups of embodiment experimental series, the main distinction between these two groups is with maybe contracting-expand the quenching nozzle.When the quenching nozzle was installed, downstream valve was opened, and the capacity of vavuum pump has been determined downstream pressure.The downstream pressure of this type test is generally the 100-200 torr.In this structure, the position that is flowing in the converging-diverging nozzle throat is restricted, and the pressure of reactor is decided by the mass flow of nozzle throat diameter, temperature of reactor and plasma gas and reactant gas.Under these conditions, when the pressure ratio in upstream and downstream was 4-6, reactor pressure was generally the 600-800 torr.Corresponding Mach 2 ship 1.6-1.8.The assumed response actuator temperature is 2000 ℃, and pneumatic quench can be reduced to 1100-1300 ℃ fast with temperature.Look the kind and the flow situation of admixture of gas, the thermal efficiency of the plasmatorch that records is 80-90%.The power of article on plasma torch is regulated, and reaches to enter 60kW constant in the plasma gas.Because plasmatorch voltage mainly by the ratio decision of argon gas with hydrogen, so just can regulate power by regulating electric current, enters the required 60kW of plasma with acquisition.The energy balance of syringe ring, reactor part and nozzle assembly shows that the power of the about 14.6kW of loss is given cooling water in these parts.The distribution of these energy losses is listed in the table below in 1:

Table 1

The position	Torch	Syringe	Reactor	Nozzle
					Energy loss:	+ 60kW enters plasma	-7.3kW enters cooling water	-3.9kW enters cooling water	-3.4kW enters cooling water

The result is that the power of nearly 45kW can be used for the transformation of natural gas to acetylene.To the system careful design of row again, be included in the length optimization (shortening) of placing the parts of syringe function in the torch body and making reactor, these losses may reduce 70% or more.Fig. 4 is a figure in the theoretical maximum of the methane that can be transformed into acetylene under the nominal operation condition in present structure.The nominal operation conditional definition is: for plasmatorch gas is 160 standard liter/min (slm) Ar, 100slm H ₂, the power that enters plasma is 60kW.The target temperature of reactor is 2000 ℃.Under this nominal condition, the theoretical maximum amount that can be transformed into the methane of acetylene is about 145slm.

During the pure methane injection, transformation efficiency is defined as:

$|\mathrm{CE}=1-\frac{\left[{\mathrm{CH}}_4\right]{\stackrel{\&CenterDot;}{Q}}_{\mathrm{STP}}}{{\stackrel{\&CenterDot;}{Q}}_{{\mathrm{<figure-callout\; id="4"\; label="CH"\; filenames="C0214693600432.png"\; state="\{\{state\}\}">CH</figure-callout>}}_4}}=1-{\mathrm{<figure-callout\; id="4"\; label="y\; CH"\; filenames="C0214693600432.png"\; state="\{\{state\}\}">y</figure-callout>}}_{{\mathrm{CH}}_{}}$

[CH wherein ₄] be the molar fraction of methane in flowing by the product that GC obtains, Q _CH4It is the injection flow of methane.

The productive rate of acetylene (for pure methane injection) is defined as:

$y_{C_2{\mathrm{<figure-callout\; id="2"\; label="H"\; filenames="C0214693600341.png,C0214693600432.png"\; state="\{\{state\}\}">H</figure-callout>}}_2}=\frac{2\left[C_2{H}_2\right]{\stackrel{\&CenterDot;}{Q}}_{\mathrm{STP}}}{{\stackrel{\&CenterDot;}{Q}}_{{\mathrm{<figure-callout\; id="4"\; label="CH"\; filenames="C0214693600432.png"\; state="\{\{state\}\}">CH</figure-callout>}}_4}}$

[C wherein ₂H ₂] be the molar fraction of acetylene in the product stream that records of GC, the actual gas flow that records that converts standard conditions (1 atmospheric pressure and 0 ℃) to is Q _STP

Embodiment 1

That provide in this embodiment, is the result who tests in the presence of converging-diverging nozzle.Transformation efficiency is shown among Fig. 5 with the situation of methane injection changes in flow rate.In the process that obtains these group data, the power that enters in the plasma remains constant 60kW, and the constant flow of plasma gas is the Ar of 160slm and the H of 100slm ₂The reactor pressure that records is comparatively constant, looks the injection flow situation of methane, and this pressure changes between about 670-730 torr.The transformation of methane is complete basically, and promptly at the feed rate of methane during up to about 100slm, transformation efficiency is 100%.When feed rate was higher than 100slm, transformation efficiency began to descend, and when feed rate was about 120slm, transformation efficiency was brought down below about 95%.Overall gas temperature in the reactor of estimation and in reactor the corresponding time of staying be plotted among Fig. 6.This estimation is to account from the maximum system energy that records, the flow of plasma gas and methane, and the supposition acetylene yield is to obtain under 100% situation.The target temperature that is reached when methane flow is about 145slm is about 2000 ℃.For the injection flow of the methane situation less than 145slm, the temperature of reactor of estimation is higher than 2000 ℃.If the non-uniform temperature of reactor (true really not so), and, estimate then that in temperature transformation efficiency will begin decline during than 2000 ℃ much lower (the methane feed flow is greater than about 145slm) if process is undertaken by the balance chart among the figure shown in Figure 4.

The another kind of this situation is shown among Fig. 4, wherein the possible in theory maximum to methane conversion is depicted as the relation with utilisable energy (power).Deduct the loss in syringe, reactor and nozzle assembly about 15kW for the 60kW that enters plasma gas, clean amount is about the nominal operation condition of 45kW, and the maximum of the methane that can transform is about 145slm.Surpass 145slm for the injection flow, available energy shortage is so that the methane decomposition of injecting and be transformed into acetylene with 100% efficient, and it is 2000 ℃ that the result makes the temperature of product stream.In injection ring and reactor, there is inevitable cold boundary layer, the gas of certain tittle is not decomposed by reactor.When lower flow and corresponding higher temperature, methane almost completely changes, and transformation efficiency reaches 100%.When 120slm (this value is a little less than the desired value of 145slm), observes transformation efficiency and descend.This may be owing to there is a cold boundary layer flow, or since time of staying when decomposing cause inadequately.Observe the time of staying curve among Fig. 6, the time of staying in the visible reactor is comparatively constant, and irrelevant with methane injection flow.The increase that the speed of mass flow and expection increases with methane injection flow since also along with methane injection flow improve the admixture of gas that takes place cool off offset.

The constant straight tube of section of diameter that is complementary with the internal diameter with downstream line replaces converging-diverging nozzle, estimates the time of staying influence possible to transformation efficiency.Remove converging-diverging nozzle, can control the pressure of reactor, and irrelevant with flow.And when converging-diverging nozzle had been installed, flowing in the nozzle throat was restricted (reaching velocity of sound).Under this condition, reactor pressure and downstream pressure are irrelevant, and it is only determined by mass flow and temperature.When having removed converging-diverging nozzle, reactor pressure is by the Position Control of downstream valve.Reducing reactor pressure has just improved the speed in the reactor and has shortened the time of staying.For the test of this series, pressure changes between the 300-700 torr, and the time of staying in the reactor shortens to 1/2.3rd, promptly shortens to 1.4ms from about 3.25ms.As shown in Figure 7, under lower pressure, observing transformation efficiency has slightly reduction, reduces about 2 percentage points.Although this shows there is slight dependence the time of staying, this is not enough to the decline of the transformation efficiency seen in the key diagram 5.This existence that shows cold boundary layer is in fact to the transformation efficiency of the being seen significant feature that descended.The time of staying in reactor should be enough to make methane decomposition, and as mentioned below, also should be enough to form acetylene.

The productive rate of acetylene is shown among Fig. 8 with the situation of methane injection changes in flow rate.The variation tendency of the variation tendency of observed productive rate data and transformation efficiency shown in Figure 5 is similar.When methane was injected flow less than about 100slm, acetylene yield was about 95%.Methane injection flow further raising can cause productive rate to descend.When the injection flow was 145slm (can so that the theoretical maximum feed flow that transformation efficiency and productive rate are handled near 100% time), the actual productive rate that records reduced to 75%.In Fig. 9, the productive rate that records is carried out the decline of the transformation efficiency that normalization explanation records.

This normalization is simple.

This normalized productive rate is the optionally tolerance that is transformed into acetylene.As shown in Figure 9, this normalization has illustrated the major part of the acetylene yield decline that is observed.Improving transformation efficiency can make the productive rate curve obviously flatten.This explanation make cold boundary layer reduce to the thinnest meeting to cause improvement on the system overall performance by improving thermal design, and the intrinsic productive rate of acetylene all improves in very wide reactant flow (temperature of reactor) scope.

The productive rate that records descends and can not be used for illustrating the reduction of transformation efficiency, and this is owing to formed the material of other carbon containing.These materials comprise other hydrocarbon and soot.Among Figure 10 and 11 figure that the carbon back productive rate of other hydrocarbon of being observed changes with methane injection flow.The productive rate that provides is expressed as introducing with methane the percentage of the carbon of system.Different and do not exist the methane except Figure 11 coordinate yardstick, these two figure are the same.In Figure 10, in the process that methane production improves, see that significantly transformation efficiency descends with the raising of methane injection flow.Figure 11 is the same data of describing with the yardstick that amplifies.It is because the productive rate of other carbonaceous material improves that the normalization productive rate of being seen descends.The material of representing on this figure only is that those gas-chromatographies can observed material.Enough what is interesting is, at alkene+C ₆Heavier (C ₅₌/ C ₆₊) after the productive rate of hydro carbons began to improve, relative quantity slightly descended when methane injection flow is higher.Adopt GCMS to analyze these heavier hydro carbons subsequently, determine that it almost is benzene all.Other carbonaceous material of being seen is that ethene, allene and t-2-butylene stably increase with the raising of methane injection flow.With Ar and H ₂Ratio reduce 1/2nd after, the productive rate that detects conversion ratio, productive rate and other hydro carbons is to Ar and H ₂The dependence of ratio relative quantity.The result is to the transformation efficiency or the not significantly influence of composition of product stream.Because the feature of product stream always is rich in H ₂So as if the Ar that exists seldom or not influence dynamics, and can not change the balance of product stream.

Except use methane is tested as reactant gas, also used pipe natural gas to carry out limited test.The productive rate of the transformation efficiency that is observed, acetylene yield and other hydrocarbon and previous coming to the same thing when using pure methane as raw material.Analysis result to natural gas and product stream is listed in the table 2.

Except having is the N of inertia basically ₂And CO ₂Be transformed into outside the CO, the result in fact with pure methane test in identical.In being rich in the system of carbon, about 1000 ℃ during than moderate temperature, CO-CO ₂Balance trend towards CO.

Embodiment 2

What provide in this embodiment is result of the test when not using converging-diverging nozzle.As if productive rate transformation efficiency of the method that is drawn (～100% pair 70%) and selectivity (95% pair 51%) are better than original Huels method slightly.This may be because mix better, temperature evenly or quenching cause faster.The analysis and laboratory scale the results are summarized in the table 2 of Huels product stream.

In order to estimate the effect of fast pneumatic quenching, carried out 1 described identical a series of tests, but do not used converging-diverging nozzle with embodiment.In these trials, system pressure remains on the 700-900 torr, and is identical haply with reactor pressure in embodiment 1 campaign.The results are summarized among Figure 12-14 of transformation efficiency, productive rate and normalization productive rate.The productive rate of other hydrocarbon is summarized among Figure 15.

In the productive rate and the transformation efficiency result that do not have to obtain under the pneumatic quenching situation of converging-diverging nozzle and ultrasonic wave, what in fact obtain when having nozzle before came to the same thing.When having nozzle, when higher methane injection flow, as if some less improvement is arranged on productive rate, but deviation is in can not deterministic estimated range, and error range is obviously overlapping.As shown in figure 15, the testing result to other hydrocarbon productive rate shows that between without nozzle and the result with nozzle (Figure 11) gained, there is tangible difference on the statistics in the productive rate of ethene.Obviously, the high quenching speed that is provided by nozzle has the effect that ethene suppressing forms, and the productive rate of ethene is cut down about 30%.The accurate mechanism that ethene forms is still unclear so far; Yet, CH ₂The dynamics of free radical and number may play an important role.

Under the situation without converging-diverging nozzle, reactor pressure can independently be controlled with valve.This structure can be studied the influence of pressure to productive rate.As shown in Figure 7, only there are slight influence the before verified pressure and the time of staying to transformation efficiency.The acetylene yield that records is depicted among Figure 16 with the situation that reactor pressure changes.The power invariability that enters gas is at 60kW, and flow remains on the Ar of 160slm, the H of 100slm ₂CH with 98.5slm ₄As if acetylene yield improve slightly with pressure and descend, but this effect and little.As shown in figure 17, when acetylene yield descended, the productive rate of benzene also slightly descended, and the productive rate of ethene improves.Usually, the pressure in 300-700 torr scope changes the influence that does not have very greatly.

Embodiment 3

In following table 3-5, provide comprehensive data of a test.This test is carried out under the situation of converging-diverging nozzle not having.Table 3 has been listed the summary situation of the pressure of flow, power, the torch thermal efficiency, nozzle geometry and the reactor that record and outlet.

Table 3

Test SEPT13A-4P
		Ar(slm)	160.4
H 2(slm)	100.1
		CH 4(slm)	75.9
Net power (kW)	60.2
		Efficient (%)	85
Geometry	Straight
		Outlet pressure (torr)	409
Reactor pressure (torr)	550

Table 4 has been listed productive rate, volume flow, the energy expenditure rate (SER) and relative productive rate of acetylene and hydrogen in this test.The title of file and line has been enough to illustrate included data usually.Specifically, be designated as the file of productive rate %: Qt meas. provides acetylene and the productive rate of hydrogen and the transformation efficiency that records that derives from methane feed.Acetylene yield is the percentage that generates carbon in the methane feed of acetylene, and hydrogen yield is the percentage of hydrogen in the methane feed of generting element hydrogen.The Qt representative is based on the measurement result of downstream turbine flowmeter.Be designated as the file of productive rate %: Qt At std. provides acetylene and the productive rate of hydrogen and the transformation efficiency that records that derives from methane feed.Q Ar std representative is based on the measurement result of argon gas input flow rate and data from gas chromatography.

The file that is designated as volume flow (slm) provides from the acetylene of methane feed generation and the volume flow of hydrogen.The Qt representative is based on the measurement result of downstream turbine flowmeter.Q Ar std representative is based on the measurement result of argon gas input flow rate and data from gas chromatography.

Ensuing four files provide energy expenditure rate.The Qt representative is based on the measurement result of downstream turbine flowmeter.Q Ar std representative is based on the measurement result of argon gas input flow rate and data from gas chromatography.

The file that is designated as the R productive rate provides relative productive rate.This productive rate numeral has been carried out normalization to transformation efficiency.

Table 4

Table 5 has been listed the flow and the mass balance data of various materials in this test.Concerning those skilled in the art, the title of file and ranks be enough to usually to illustrate comprising data.Specifically, the file that is designated as [conc%] provides the concentration of representing with mole percent with gas chromatography determination.Table 5 divides two parts to list owing to its length is very big.

Table 5. part A

Table 5. part B

Material	mdot C in	mdot C out	Productive rate Qt	Q Ar std	mt Ar std	mdot H Ar	mdot C Ar std	Productive rate Ar std
									H 2(hydrogen)	0.00	0.00	0.0	369.13	15.10	15.10	0.00	0.0
C5＝/C6+ (C 6H 6)	0.00	2.63	6.5	369.13	2.79	0.21	2.58	6.34
									C 3H 8(propane)	0.00	0.00	0.0	369.13	0.00	0.00	0.00	0.00
C 2H 2(acetylene)	0.00	39.93	98.2	369.13	42.35	3.26	39.09	96.14
									C 3H 6(propylene)	0.00	0.00	0.0	369.13	0.00	0.00	0.00	0.00
C 1H 10(iso-butane)	0.00	0.00	0.0	369.13	0.00	0.00	0.00	0.00
									C 3H 4(allene)	0.00	0.00	0.0	369.13	0.00	0.00	0.00	0.00
C 1H 10(normal butane)	0.00	0.00	0.0	369.13	0.00	0.00	0.00	0.00
									C 1H 8(1-butylene)	0.00	0.00	0.0	369.13	0.00	0.00	0.00	0.00
C 4H 8(iso-butane/isobutene)	0.00	0.00	0.0	369.13	0.00	0.00	0.00	0.00
									C 4H 8(t-2-butylene)	0.00	0.07	0.2	369.13	0.08	0.01	0.07	0.16
C 1H 8(c-2-butylene)	0.00	0.00	0.0	369.13	0.00	0.00	0.00	0.00
									C 1H 6(1,3-butadiene)	0.00	0.00	0.0	369.13	0.00	0.00	0.00	0.00

C 5H 12(isopentane)	0.00	0.00	0.0	369.13	0.00	0.00	0.00	0.00
									C 5H 12(pentane)	0.00	0.00	0.0	369.13	0.00	0.00	0.00	0.00
CO 2(carbon dioxide)	0.00	0.00	0.0	369.13	0.00	0.00	0.00	0.00
									C 2H 4(ethene)	0.00	1.85	4.6	369.13	2.12	0.30	1.82	4.47
C 2H 6(ethane)	0.00	0.00	0.0	369.13	0.00	0.00	0.00	0.00
									Ar (argon gas)	0.00	0.00	0.0	369.13	286.43	0.00	0.00	0.00
N 2(nitrogen)	0.00	0.00	0.0	369.13	0.00	0.00	0.00	0.00
									CH 4(methane)	40.66	0.29	0.7	369.13	0.38	0.10	0.29	0.70
CO (carbon monoxide)	0.00	0.00	0.0	369.13	0.00	0.00	0.00	0.00
Amount to g/min	40.66	44.78	110.1		349.25	18.98	43.84	107.8
									%'s is poor		-10.14			0.09	15.59	-7.81
Soot % based on the Carbon balance generation		-10.14					-7.81

It is better slightly that transformation efficiency that records in the laboratory reaction body described in this embodiment 1 and 2 system and acetylene yield are reported in usually than document; Confirm transformation efficiency (CE) near 100%, productive rate is in the scope of 90-95%, and the soot that is produced is 2-4%.As if this than Huels method (CE=70.5%, C ₂H ₂Productive rate=51.4%, carbon soot 2.7%) and the DuPont method (CE-does not report, C ₂H ₂Productive rate=70%) some improvement.As if acetylene also had slightly better selectivity in this reported method.In the improvement on transformation efficiency, productive rate and the selectivity mainly is because the improvement in injector designed and the mixing (" stirring-type " reactor preferably) and make thermograde and minimum cause is reduced in cold boundary layer.As if be enough to quencher product stream by the cooling velocity due to heat is transmitted on the wall, prevent that acetylene from further resolving into soot or preventing that further reaction generates heavier hydrocarbon products.Obviously improving quenching speed by converging-diverging nozzle rapid expanding product stream, only improve to some extent reluctantly on the composition of product stream, mainly is the productive rate that has reduced ethene.

The energy that acetylene consumed (kW-hr) final decision that Board Lot (kg) produces the economic benefit of this method.It is reported that the Huels method has consumed the C that 12.1kW-hr/kg produces ₂H ₂Although do not measure, the energy expenditure rate of estimating the DuPont method is the C that 8.8kW-hr/kg produces ₂H ₂Back one numeric ratio is 100% and the about 7.9kW-hr/kg-C of theoretical minimum value of the product stream that makes when not having electric loss or heat loss at 2000 ℃ temperature, transformation efficiency and productive rate ₂H ₂Better.The energy expenditure rate that will record in the laboratory scale method of this research is depicted among Figure 18.The minimal energy consumption rate that records is about the C that 16kW-hr/kg produces ₂H ₂Estimation can be improved to this numerical value about 13kW-hr/kg-C by improving thermal design ₂H ₂This improvement comprises injection moved in the torch body, just can avoid the heat loss in the syringe ring and reduce the heat loss of reactor in partly.The recovery of process heat can further reduce energy expenditure rate about 20% again, reaches about 10kW-hr/kg-C ₂H ₂Scope.The energy expenditure rate of these numeric ratios Huels and DuPont method report is better, and while transformation efficiency and productive rate are also higher.

Under the situation that does not depart from its marrow or principal character, the present invention can show in other concrete mode.Will be understood that described embodiment only is illustrative aspect all, and nonrestrictive.Therefore, scope of the present invention is by appending claims but not the description of front is specified.The institute of making in the implication of claims equivalents and scope changes and all is included in its scope.

Claims (50)

1. one or more reactants are transformed into the method for at least a required product, it comprises:

The reaction logistics is introduced in the injection canal of axial flow reactor one end;

With the injection canal that the introducing of hot gas stream is used for and the reaction logistics mixes;

In injection canal, will react logistics and mix the reaction logistics of the thorough mixing of generation one before it enters reactor chamber with hot gas stream up hill and dale; With

Allow the reaction logistics that mixes axially enter reactor chamber from injection canal;

When the reactant stream that mixes passes through reactor chamber, make the volume that limits by reactor chamber keep even temperature basically at its length range; With

On the close position of the axial flow reactor port of export, produce at least a required end product.

2. the method for claim 1 is wherein reacted logistics and is comprised methane, and at least a required end product comprises acetylene.

3. the method for claim 1 is wherein reacted logistics and is comprised methane or carbon monoxide, and at least a required end product comprises hydrogen.

4. the method for claim 1 is wherein reacted logistics and is comprised titanium compound, and at least a required end product comprises titanium or titanium dioxide.

5. the method for claim 1, wherein the temperature of reaction zone remains on 1500-4000 ℃.

6. method as claimed in claim 5, wherein the temperature of reaction zone remains on 1700-2000 ℃.

7. the method for claim 1 is wherein introduced hot gas stream also to be included in the injection canal feeding the plasma arc air-flow between the plasmatorch electrode, produces a plasma and also this plasma is introduced in injection canal.

8. method as claimed in claim 7, it comprises that also the reaction logistics of the mixing that makes in the reactor chamber reaches poised state.

9. the method for claim 1, it also comprises:

Leave in the logistics that comprises at least a required end product behind the port of export of axial flow reactor its cooling, its way is to reduce the speed of this hybrid reaction logistics, simultaneously to be enough to prevent that the speed that its power temperature raises from removing heat energy;

At least a required end product is separated with gas in staying cool stream.

10. method as claimed in claim 9, wherein when axial flow reactor is left in logistics, the residual gas of required end product and logistics cooled off and reduce its speed and comprise quench gas is added in this logistics, the formation that it adds should be able to condensation at least a required end product of inbound traffics and suppress other equilibrium products when reactor is left in logistics.

11. the method for claim 1, it also comprises allows the hybrid reaction logistics that comprises at least a required end product cool off fast, and this comprises allows this mixed reactant stream by being positioned at a coaxial converging-diverging nozzle near the axial flow reactor port of export.

12. method as claimed in claim 11, it also comprises the size of selecting the limited opening throat in the nozzle, is controlled at the time of staying and the reaction pressure of the reaction logistics that mixes in the axial flow reactor.

13. method as claimed in claim 11, it also comprises descends the pressure of the hybrid reaction logistics that comprises at least a required product ultrafastly, its way is to make this hybrid reaction logistics quicken reposefully and expand along the expansion of nozzle, thereby further reduces its power temperature and prevent unwanted side reaction or back reaction is carried out.

14. the method for claim 1, wherein will react logistics and introduce injection canal and this reactant stream is selected before also being included in reaction logistics reaction or thermal decomposition, and make it comprise at least a reactant that is selected from titanium tetrachloride, vanadium tetrachloride, alchlor, methane and the natural gas.

15. the method for claim 1, wherein:

Hot gas stream comprises plasma, and described plasma produces from the gas that comprises inert gas, hydrogen or its mixture;

The reaction logistics comprises the gaseous state or the volatile compound of selected metal:

The operation axial flow reactor, comprise and form an equilibrium mixture, described mixture comprises the required product of at least a selected metal or its oxide or alloy form, and this selected metal, metal oxide or metal alloy are thermodynamically stable under selected reaction temperature; Described method also comprises:

When the port of export of axial flow reactor is left in the logistics that comprises at least a required product it is cooled off, its way is to reduce the speed of this logistics, simultaneously to be enough to prevent that the speed that its power temperature raises from removing heat energy;

At least a required product is separated with gas in staying cool stream.

16. method as claimed in claim 15, the gaseous state of wherein said selected metal or volatile compound are gaseous state and volatilizable halide.

17. method as claimed in claim 15, wherein said selected metal is titanium, vanadium or aluminium.

18. method as claimed in claim 15, the compound of wherein said selected metal are titanium tetrachloride, vanadium tetrachloride or alchlor.

19. method as claimed in claim 15, wherein said reaction logistics also comprise the another kind of at least material that can react the equilibrium mixture that forms the oxide comprise selected metal or alloy under reaction temperature.

20. method as claimed in claim 19, wherein this method forms the alloy of titanium and second kind of metal, and described reaction logistics comprises the gaseous state or the volatilizable compound of titanium chloride and this second kind of metal.

21. method as claimed in claim 20, wherein second kind of metal is vanadium.

22. method as claimed in claim 19, wherein this method forms the metal oxide of selected metal, and described reaction logistics also comprises oxygen.

23. method as claimed in claim 22, wherein this method forms titanium oxide, and described reaction logistics comprises titanium tetrachloride and oxygen.

24. the method for claim 1, wherein:

Hot gas stream comprises plasma, and described plasma produces from the gas that comprises inert gas, hydrogen or its mixture;

Described reaction logistics comprises the hydrocarbon of gaseous state or volatilization: described method also comprises:

Formation comprises the equilibrium mixture of at least a required product, and described required product is thermodynamically stable under reaction temperature;

When the equilibrium mixture that comprises at least a required product leaves the port of export of reactor it is cooled off, its way is to reduce the speed of this equilibrium mixture, simultaneously to be enough to prevent that the speed that its power temperature raises from removing heat energy;

At least a required end product is separated with gas in staying the cooling equilibrium mixture.

25. method as claimed in claim 24 is wherein reacted logistics and is comprised natural gas or methane.

26. method as claimed in claim 24, wherein at least a required product comprises acetylene.

27. a device that is used for one or more reactant heat deflections are become at least a required product, this device comprises:

Axial flow reactor, it comprises arrival end, the port of export and extend the also surface that the insulation lining is arranged in part defined reaction district between the arrival end and the port of export, wherein the operating condition of axial flow reactor is enough to the reaction logistics is heated to selected reaction temperature, and the logistics that comprises at least a required product is being produced near on the position of the axial flow reactor port of export at least;

The torch part is constructed to be permeable to it to produce hot gas in the upstream of axial flow reactor;

The syringe part, it comprises hot gas inlet, reactant entrance and outlet, the inlet of syringe part is positioned at the exit near the torch part, the outlet of syringe part is positioned at the porch near axial flow reactor, on the transverse direction of longitudinal extension by the axle of the reaction zone of syringe part and axial flow reactor, the cross-sectional area of the outlet of described syringe part is littler than the cross-sectional area of the inlet of described axial flow reactor.

28. device as claimed in claim 27, it also comprises converging-diverging nozzle, this nozzle links to each other with the port of export of axial flow reactor, and being constructed to be permeable to the logistics that fast cooling comprises at least a required product, its way is to produce adiabatic when the logistics axial flow is crossed nozzle and constant entropy expansion is transformed into kinetic energy with heat energy.

29. device as claimed in claim 28, wherein converging-diverging nozzle has convergence portion and expansion, leads to respectively and forms limited opening throat, and this expansion has vertically that the axle of reactor is the tepee structure at center.

30. device as claimed in claim 29, wherein the angle of the tepee structure of nozzle expansion is less than 35 °.

31. device as claimed in claim 28, wherein converging-diverging nozzle has the convergence portion that carries out the transition to throat, and described nozzle has first angle greater than 45 °, enters throat with second angle less than 45 ° then.

32. device as claimed in claim 28, it also comprises the cooling segment of deriving from converging-diverging nozzle.

33. device as claimed in claim 32, wherein cooling segment is constructed to be permeable to reduce the speed of the logistics that comprises at least a required product, removes heat energy with the speed that is enough to prevent its power temperature rising and keep at least a required product therein simultaneously.

34. device as claimed in claim 27, it also comprises the cooling segment that links to each other with the port of export of axial flow reactor.

35. device as claimed in claim 34, wherein cooling segment is constructed to be permeable to reduce the speed of the logistics that comprises at least a required product, removes heat energy with the speed that is enough to prevent its power temperature rising and keep required product therein simultaneously.

36. device as claimed in claim 34, it also comprises the convergence portion that is inserted between the axial flow reactor port of export and the cooling segment.

37. device as claimed in claim 27, wherein the reactant entrance of injection portion comprises the porous road.

38. device as claimed in claim 27, wherein torch partly comprises the anode syringe.

39. device as claimed in claim 38, wherein the anode syringe comprises porous road syringe.

40. device as claimed in claim 27, wherein torch partly comprises plasmatorch, and this plasma torch has introduces plasmatorch to produce the plasma arc inlet of plasma with the plasma arc air-flow.

41. device as claimed in claim 40, wherein plasmatorch comprises that at least one pair of is positioned at the electrode of reaction zone arrival end upstream.

42. device as claimed in claim 41, wherein the plasma arc inlet applies selected plasma input power to electrode simultaneously in the upstream that is used for the plasma arc air-flow is introduced the electrode between the electrode with selected plasma gas flow rate.

43. device as claimed in claim 42, wherein reactant entrance comprises the porous road syringe near the plasmatorch in the torch part.

44. device as claimed in claim 27, wherein torch partly comprises one or more laser instruments or is used for from the structure of the oxidation generation flame of suitable fuel.

45. device as claimed in claim 27, wherein syringe partly comprises the injection canal that diameter is littler than reaction zone diameter, injection canal fully in torch part, part partly neutralizes part between the arrival end of torch part and axial flow reactor or between the arrival end of torch part and axial flow reactor at torch.

46. device as claimed in claim 27, it also comprises the insulating barrier around the reaction zone that is enclosed in axial flow reactor.

47. device as claimed in claim 46, wherein insulating barrier comprises the material that is selected from carbon, boron nitride, zirconia, carborundum and its combination.

48. device as claimed in claim 46, it also comprises the cooling layer that is enclosed in around the insulating barrier.

49. device as claimed in claim 48, wherein cooling layer comprises a water layer.

50. device as claimed in claim 28, wherein converging-diverging nozzle is constructed to be permeable to make reaction zone to operate under atmospheric pressure or higher pressure, and cooling segment keeps vacuum state simultaneously.

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