CN205435704U - Reactor - Google Patents

Abstract

The utility model relates to a reactor, it includes: reactor wall portion, that reactor wall portion encloses into axially extended cylindricality or the reactor inner chamber of diameter (d) the cylindricality, that have axial design size (h) and perpendicular axial's design size measurement basically, wherein the reactor inner chamber has at least one entry that is used for the reactant and have the export on the reactor bottom, have stirring component that at least one axial transported, axially extended (mixing) shaft, the (mixing) shaft passes during reactor wall portion introduces the reactor inner chamber in reactor's upper end department, a serial communication port, be provided with in the reactor inner chamber axial extension cylindricality or cylindricality basically, the external diameter (d') that has axial design size (h') and perpendicular axial's design size measurement, inject the guiding tube of guiding tube inner chamber, it constitutes the chamber to make between reactor wall portion and guiding tube, guiding tube and reactor bottom and spaced apart with the upper end of reactor inner chamber wherein, wherein to what the ratio of the axial design size of guiding tube (h') and the axial design size (h) of reactor inner chamber was suitable for be: (H' h), <= 0.9, to what the ratio of the external diameter of guiding tube (d') and the diameter (d) of reactor inner chamber was suitable for be: (D' d), <= 0.9, the (mixing) shaft that wherein has at least one stirring component extends in the guiding tube inner chamber to it can be by the heat exchanger of reaction mixture percolation to be provided with within this chamber.

Description

Reactor

Technical field

The present invention relates to reactor, described reactor can be used particularly for polymerization, especially ring-opening polymerisation lactide.Reactor is configured to rabble furnace reactor and has agitating element at this, and described agitating element is arranged in guiding tube.The invention still further relates to a kind of method for polymerization, the method being particularly useful for ring-opening polymerisation lactide, described method is so that the ways and means of the reactant mixture viscosity set between 1 and 500Pa s control.

Background technology

Polymerization or bunching equipment be usually designed so that its can between the 60% of nominal production capacity and 100%, be the most also 110% operation.Production capacity less than the 50% of nominal production capacity is the most infeasible.Bigger motility is with product quality or safety in operation as cost.Such as bulk product in reactor can not be less than the minima determined in structure, and time needed for not making the time of staying of product be longer than for technique.In the case of time of staying length, it is undesirable to by-product formation rise (product such as thermally decomposed), can not remove and be harmful to its quality from product described byproduct fraction.Result is to obtain being unsatisfactory for the fusing point decline of the product of specification, i.e. polymer, dyeing etc..Equipment at production capacity lower limit runs the interference easily causing operation, as the freezing of polymer, due to pump that converter is the most thermally-induced lost efficacy, the carrying out of the polyreaction of heat release.This interference can cause the stopping production of many days by the loss of product that causes due to the damage of part of appliance and the emergent evacuation of reactor.

US5,484,882 (DaiNippon) proposes the ROP of the two-stage of the possible lactide before utilizing rabble furnace or recirculation reactor to engage to have the tubular reactor of stable hybrid element.The prepolymerized feature that will be used for discharging the gear pump of prepolymer and anchor agitator is enumerated as in rabble furnace.

WO2010/012770A1 (Purac) relates to the method with the two-stage of the continuous print mixing reactor in the first order, and described mixing reactor can be configured to recirculation reactor or be configured to rabble furnace." degree of polymerization " (reaction expressed possibility) that reach in the first stage is between 5 and 90%.Feature about agitation and filtration variations does not has other explanation.

For the preparation method of PLA described in the EP2188047 (UIF), described method performs the ROP of lactide in two steps.First step is in rabble furnace or recirculation reactor in the prepolymerization of lactide, and second step is the polymerization in tubular reactor.Prepolymerization causes between 5 and 70mol% in the first step, preferred Interesterification between 30 and 60mol%.Polymerization is continued to control to following chemical equilibrium by tubular reactor, and described chemical equilibrium is according in temperature reaction between 95 to 97%.Other feature prepolymerized in rabble furnace is not mentioned.

There is series of problems in the actual realization of the ring-opening polymerisation (ROP) in rabble furnace, does not provide solution for these problem prior aries.

In lactide " with entity " ring-opening polymerisation, i.e. in the lactide melt do not have solvent during ring-opening polymerisation, the viscosity of polymer melts improves consumingly along with Interesterification.When being consecutively carried out ROP in rabble furnace, the viscosity of the product of the polymerization in reactor is not to be exceeded the scope allowed.Especially in commercial scale, the disposable agitator structure existed is only capable of the optimal mixing guaranteeing reactor content in the range of viscosities limited up and down.Too high viscosity causes agitator static due to the response of safety device, and described safety device prevents driver or the overload driving motor or the deformation of agitator.This resting state causes the continuation of the temperature in stove and viscosity to improve, and thus causes longer the interrupting and be unsatisfactory for the product of regulation until the emergent evacuation of reactor interrupts and loss of product with producing that emission problem, stable equipment run.

Too low viscosity causes the problem of the tubular reactor being connected to downstream to close with too strong back-mixing, too low reaction and too low molal weight.In rabble furnace itself, it causes: is designed for the agitator in higher year and no longer brings default mixing and transport performance.Such as, forming race way and static eddy current in the reactor, its infringement exchanges with the material of remaining reactor content and then stops the uniform of whole reactor content to mix.Too low viscosity can be paralysed immixture and transporting power in extreme circumstances.Observing limited range of viscosities during polymerization in rabble furnace is operation method and the premise of whole equipment economically.

The ROP reaction of lactide is heat release, and the lactide of i.e. every molar reactive forms the heat of about 23.3kJ.In addition there is the stirrer-driven power being only converted into heat in product in the reactor.Therefore, when static, it is necessary to the derivation heat in the melt of reaction from stove.In theory this is sufficient that: the temperature of the monomer (lactide) carried keeps below product temperatur certain numerical value in the reactor and then product cools down along with input.This required temperature difference is drawn from simple thermal balance and is located substantially between 10 and 50 DEG C according to the vision purity of reaction and lactide between product and the lactide of conveying in reactor.But it practice, the temperature of the product in stove is adjusted being inadequate by the temperature by the lactide carried.Mixed process in reactor postpones the effect of the change for regulation of delivery temperature.This dead time is along with product amount and then along with equipment capacity increases present in reactor.The time-invariant product quality of holding equipment becomes difficulty.

When running temperature strong variations (temperature of the lactide such as carried and through-current capacity fluctuation in the case of), but especially in the unpredictalbe running status such as caused due to the interference being connected in the unit in downstream, discharge inefficacy such as current failure or the product from reactor and expand following danger: i.e. polymerization " departs from along towards higher or lower product temperatur and controls ".Here, reaction, mole and melt viscosity raise until agitator lost efficacy along with product temperature continuously.On the other hand, in the case of temperature regulates the slowest and reaction height, the fusing point of product raises and stove inclusions is freezed.In this case, the melt in stove must extract rapidly or carry heat, in order to prevent from the equipment that can be at most day static and produce losing efficacy.The loss of product associated with the emergent evacuation of stove also harmful economy produced.

As in whole chemical devices, equipment capacity is the biggest, produces the most economical.Big equipment capacity is equal to bulk product big in reactor.Along with the raising of equipment capacity, in rabble furnace reactor, thermal transfer surface declines in identical mean residence time with the ratio of bulk product.When lactide is with pilot scale ROP, the heat conveying that i.e. carries out via boiler casing in the stove with substantially 100kg inclusions or when drawing or be enough, this is in plant-scale reactor, i.e. have more than being infeasible in the stove of 1000kg inclusions.Therefore, big production capacity needs the special architectural feature of ROP rabble furnace, in order to when popularization, the ratio of thermal transfer surface and reactor volume is kept constant.

Therefore, although the reaction in regulation temperature and then regulation reactor also has scale to amplify, in addition it is also necessary to face is heated or cooled in the inside of reactor.

But, the heating in reactor conflicts with the desired motility in equipment capacity mutually with the setting of cooling surface: the product level in polymer reactor preferably must be held on loaded heat exchanger.If declining deeper, then the face that is heated or cooled partially or even wholly keeps not washed away by product.Adhere to the molten film on face do not exchanged and be polymerized the layer carried out lentamente to forming high viscous.In the case of continuing polymerization, the fusing point of the product of adhesion even improves the product temperatur exceeding in reactor so that it causes the polymeric layer forming solid-state.This viscous or the layer of solid-state prevents heat transfer, through decomposes, partly fall from emaciated face when level improves further, and then pollution products.Therefore, the heat exchanger loaded reduces the move place of the liquid level in reactor and then reduces the motility of production capacity.

Therefore, conveying thing (lactide) and catalyst, initiator and other additives required if desired of liquid must mix as quickly as possible and as fully as possible with the bulk product being all present in reactor.Otherwise, it is used for regulating and reacts strong fluctuation that is excessive with the dead time of product viscosity and that cause described parameter.Described requirement is more difficult to meet also with the increase of bulk product in reactor.Drive power and the driving torque of agitator improve with 55 percent power of stirrer diameter.Because stirrer diameter and reactor volume are the most associated with each other, so the expansion of reactor production capacity touches the load-bearing capacity of material and the limit of economy rapidly.

Summary of the invention

Based on EP2188047 (UIF), it is an object of the invention to: provide method and apparatus for the prepolymerization in the rabble furnace run continuously.

Big advantage during PLA generates is: the production capacity of existing polymerization unit can be matched with market demands (demand of fluctuation, the coupling to the demand slowly improved) neatly.Therefore should run neatly in the production capacity between the 25% of nominal production capacity and 100% for preparing the equipment of PLA, wherein product quality keeps identical.For this method of operation, need a kind of method and be suitable for the equipment with this.

Therefore, the present invention relates to a kind of reactor according to claim 1, and it is particularly suitable for the ring-opening polymerisation of lactide.Additionally, the method that the present invention relates to the polymerization of lactide, especially ring-opening polymerisation according to claim 14.Here, claim relevant respectively is for being advantageously improved form.

Present invention is accordingly directed to a kind of reactor, it includes

Reactor wall portion, described reactor wall portion surround axially extended cylindricality or substantially cylindrical, there is axial design size (h) and be perpendicular to the reactor inner chamber of the diameter (d) that axial design size is measured, wherein reactor inner chamber has at least one and for the entrance of reactant and has outlet on reactor bottom；

Having at least one agitating element axially transported, axially extended shaft, described shaft is incorporated in reactor inner chamber, wherein through reactor wall portion in the upper end of reactor

Reactor inner chamber is provided with axially extending cylindricality or substantially cylindrical, have axial design size (h ') and be perpendicular to external diameter that axial design size measures (d '), the guiding tube that limits guiding tube inner chamber, make to constitute chamber between reactor wall portion and guiding tube, wherein guiding tube and reactor bottom and spaced apart with the upper end of reactor inner chamber

Wherein the ratio for the axial design size (h) of axial design size (h ') and the reactor inner chamber of guiding tube is suitable for: (h '/h)≤0.9,

The external diameter (d ') of guiding tube is suitable for the ratio of the diameter (d) of reactor inner chamber: (d '/d)≤0.9,

The shaft wherein with at least one agitating element extends up in guiding tube inner chamber,

And being provided with within chamber can be by the heat exchanger of reactant mixture percolation.

Have now surprisingly found that: the reactant mixture that will enter in reactor by arranging one or more agitating element in the reactor fully mixes and with by heat exchanger, reactor content can be overturn combination forcibly, and wherein at least one in these agitating elements is arranged in guiding tube.Described agitator axially overturns total reactor inclusions in whole material position between a minimum value and a maximum value so that lactide melt, catalyst and the initiator of the thin liquid shape carried and inhibitor if desired mix at short notice and fully with reactor content.The composition in the district with velocity component radially of circulation itself is avoided in axial mixing, and described district lingeringly mixes with remaining reaction contents only strongly.

Quickly being heated or cooled and then supporting reactions and the regulation of product temperatur of reactor content is realized by the compulsory upset of heat exchanger.Force in upset arbitrary material position between a minimum value and a maximum value the available face that is heated or cooled in fully utilize structure and guarantee: heating required for offer and cooling capacity and can exist in terms of control and " lose " reaction along the direction towards high or low product temperatur.Additionally, avoid the big temperature difference in product.

Have now surprisingly found that: the agitator being arranged in guiding tube can not only meet the purpose of axial backmixing and also be able to meet the purpose forcing upset of reactor content by arranging heat exchanger in the reactor.

According to one preferred embodiment, guiding tube separates spacing (a) with its bottom with reactor wall portion, make when the shaft with at least one agitating element axially transported runs, reactant mixture as reactant mixture in the exit coming from guiding tube and the pressure loss measured to the pressure difference of porch in the chamber between guiding tube and reactor wall be reactant mixture when through heat exchanger as at reactant mixture in the maximum 10% of the pressure loss entering heat exchanger and the measurement of pressure difference when leaving heat exchanger, and/or the spacing (a) measured in the projection on reactor bottom is relative to axial design a size of 0.001≤a/h≤0.25 of reactor inner chamber (h), it is preferably 0.01≤a/h≤0.2, especially preferably 0.05≤a/h≤0.15.

Ratio for the axial design size (h) of axial design size (h ') and the reactor inner chamber of guiding tube is suitable for: 0.05≤(h '/h)≤0.5, preferably 0.075≤(h '/h)≤0.4, particularly preferred 0.1≤(h '/h)≤0.25.

Alternatively or additionally it is also preferred that: the external diameter (d ') of guiding tube is suitable for the ratio of the diameter (d) of reactor inner chamber: 0.2≤(d '/d)≤0.6, preferably 0.3≤(d '/d)≤0.5.

Another preferred embodiment proposes: guiding tube inner chamber has the internal diameter (x) being perpendicular to axial design size measurement and has the rotating diameter (y) being perpendicular to axial design size measurement with at least one at least one agitating element, wherein ratio y/x is suitable for: 0.9≤(y/x)≤0.99, preferably 0.95≤(y/x)≤0.98.

It is also preferable that: big or the most same big as the design size of the axial design size of heat exchanger and the axle phase of guiding tube (h ').

Also advantageously: guiding tube and reactor inner chamber are concentrically disposed with so that chamber is constituted circlewise or the most circlewise.

Reactor bottom can conically constitute at this and export and is arranged at the tip of cone, and wherein the subtended angle of cone is preferred > 50 °, be also preferably 55 ° to 120 °, especially preferably 60 ° to 100 °.

It is also possible that shaft has thermal protection portion through the portion of connecting in reactor wall portion, described thermal protection portion be preferably able to by means of liquid or the heat carrier of steam-like run.

It is also preferred that shaft region between the upper seamed edge of guiding tube and the upper end of reactor inner chamber in the axial direction has at least one other agitating element axially transported.

Here, following variations is feasible and is preferred respectively.

At this, at least one other agitating element can be constituted in two style so that the agitating element transported with this at least one other axis in the operation of shaft corresponds to the flowing that in the region of guiding tube inner chamber, generation is the most contrary compared with the region corresponding to chamber in projection in axial direction in projection in axial direction.

Same it is also feasible that: only in region corresponding to guiding tube inner chamber in the projection of axial direction, constitute this at least one other agitating element.

Alternative in this it is also possible that only constitute this at least one other agitating element corresponding to being formed in the region in the chamber between reactor wall portion and guiding tube in projection in axial direction.

According to the embodiment that another is favourable, at least one other agitating element axially transported has the design size (z) being perpendicular to axial direction extension, wherein the ratio for design size (z) with the diameter (d) of reactor inner chamber is suitable for: 0.7≤(z/d)≤0.99, preferably 0.8≤(z/d)≤0.98, particularly preferred 0.9≤(z/d)≤0.98.

In addition it is possible that: shaft is constituted coaxially so that at least one agitating element and at least one other agitating element can operate independently of one another.This shaft such as has two shafts arranged coaxially to each other, can operate this two groups of agitating elements independently of one another by means of described shaft, the agitating element being i.e. arranged in guiding tube and be arranged on the agitating element on guiding tube.

Also advantageously: agitating element is selected from: triumphant Pulan agitator, oblique leaf agitator, crutcher, propeller agitator, intersection leaf agitator and/or the agitator that at least one is other are selected from: tiltedly leaf agitator, intersect leaf agitator, there is the agitator that spirals spiraled of continuous print or interruption, ribbon agitator and there is the anchor agitator of the arm tilted relative to rotational plane.

In addition following feasibility is obtained: the region that guiding tube is spaced apart with the upper end of reactor inner chamber wherein exists at least one other guiding tube.

It is also possible that guiding tube has in axial direction at the upwardly extending protuberance in side of the upper end towards reactor inner chamber, described protuberance has perforation and/or is configured to orifice plate.

The axial design size of guiding tube determines in this case in the case of not considering protuberance.

According to an especially preferred embodiment, guiding tube positions in the axial direction in reactor inner chamber, the mean residence time of 2 hours is there is in the minimum loading making reactant mixture in the case of 50% less than the loading in the nominal production capacity of reactor, described minimum loading causes the minimum packed height of reactant mixture, and wherein the upper seamed edge of guiding tube sinks in reactant mixture.

Another favourable embodiment proposes: reactor wall portion can be carried out homoiothermic, preferably it is divided into the district of multiple individually energy homoiothermic in axial direction arranged, particularly preferably there is the district (I of three single energy homoiothermic, II, III), wherein the district (I) of the first energy homoiothermic constitutes the upper end to guiding tube at axial direction from reactor bottom, the district (II) of the second energy homoiothermic is constituted in the axial direction on the upper end of guiding tube, and the district (III) of the 3rd energy homoiothermic constitutes and includes the upper end (reactor cap) in reactor wall portion on the secondth district (II).

Also advantageously: guiding tube and/or the guiding tube that at least one is other are configured to be double-walled and can be by under environmental condition around and/or the heat carrier homoiothermic of liquid under service condition.

Especially it is possible that: shaft be arranged on doubly through reactor wall portion connect in portion or before with on reactor bottom.

Here, heat exchanger is especially configured to pipe heat exchanger.

At this it is possible that: heat exchanger includes by being perpendicular to the bundle that constitutes of coil pipe that axial direction stretches, and under environmental condition and/or service condition, the heat carrier flow influencing meridian of liquid crosses described coil pipe, wherein reactant mixture washing-round pipe or coil pipe around.

It is also possible that heat exchanger includes the body closed, described body has the pipe being directed through body stretched in the axial direction, wherein product stream influencing meridian crosses described pipe, described pipe in the body closed by environmental condition around and/or service condition under the heat carrier washing-round of liquid.

Heat exchanger is also included on axial direction pipe or the coil pipe stretched, and under environmental condition and/or service condition, the heat carrier flow influencing meridian of liquid crosses described pipe or coil pipe, wherein reactant mixture washing-round pipe or coil pipe around.

In addition, the present invention relates to a kind of method for being polymerized lactide, it is polymerized particular by the above-mentioned reactor according to the present invention, wherein by the reaction temperature of regulation reactant mixture, the viscosity that lactide converts with reactant mixture is set on 1 to 100Pa s, preferably 5 to 50Pa s and keeps constant." constant " is interpreted as in sense of the invention: the deviation of the disposable viscosity set is less than 20%, preferably smaller than 10%.This conversion passing through used lactide keeps constant or substantially constant to carry out.

Regulation such as can be carried out in the following way: in the case of constant is constant, (i.e. in the case of production capacity is constant), lactide transfer rate is preset regularly together with the inhibitor concentration in the catalyst concn in reactant mixture, the initiator concentration in reactant mixture and/or reactant mixture and the temperature of reactant mixture being adjusted so that, the viscosity converting and then being obtained by conversion keeps constant in the scope of the waving interval proposed before.

When changing, especially reducing reactor production capacity, guarantee by regulation conversion ratio: viscosity keeps constant in the scope of the waving interval proposed before.This most such as can be carried out in the following way: lactide convert so that viscosity in the reactor between 25% and 100% that production capacity is nominal production capacity in the case of keep constant by changing the material position of the catalyst concn in temperature and/or reactant mixture and/or initiator concentration and/or inhibitor concentration and/or reactor.

Can determine surprisingly: convert, particularly by selecting product temperatur, catalyst concn, initiator concentration and/or inhibitor concentration the viscosity of the product in reactor are maintained on about 1 to 100Pa s, preferably 5 to 50Pa s during ring-opening polymerisation and can keep constant by setting and/or regulate monomer.In this range of viscosities, it is capable of the optimal mixing of reactor content according to the agitating element of the reactor of the present invention.

Here, the temperature at this reactant mixture in reactor has main impact to conversion ratio and then the direct viscosity on reactant mixture.Especially, the method according to the invention is therefore, it is possible to affect by the temperature of regulation reactant mixture.

The regulation of product temperatur enables in particular to enter temperature by regulation and goes out combination realize and then obtain desired viscosity with the modulated heated conveying by loading that the heat exchanger in reactor carries out and thermal conductance, and wherein said heat exchanger can heat and cool down reactor content.For this purpose, heat exchanger runs preferably by the heat carrier of liquid, the heat exchanger that described heat carrier is set to outside stove on desired temperature and desired flow and flows in stove.

Similarly, thermal transfer surface and the ratio of reaction volume can be kept in the case of scale is amplified by the heat exchanger comprised in the reactor.Such as, in the reactor in the small-scale with 108kg reaction mass, the 1m provided by dual overcoat²Heating and cooling surface be enough (example 1 seen below).In reactor in commercial scale, i.e. there is 1000kg and higher reaction mass, i.e. corresponding in the commercial scale of the nominal production capacity of 500kg/h, dual circumferential surface is not enough to bring required heating and cooling capacity.It is preferably provided with the heat exchanger according to the present invention in the reactor and such as 11m is provided²/m³Thermal transfer surface and the required ratio of reaction volume.

By the measure that uses by the method according to the invention it is surprisingly found that convert identical in the case of realize production capacity being dropped on the 25% of the nominal production capacity of reactor.This realizes particularly by the following measure also separately still being able to combination with one another application:

In the case of the 100% of the nominal production capacity of reactor, set between 5% and 80%, preferably desired lactide between 30 and 60% and convert by properly selecting product temperatur, catalyst and initiator dosage in stove and keep constant.If with the 25% of nominal production capacity with < yield of the reduction between 100% runs boiler, so keep converting constant by reducing the melt level in stove, wherein the catalyst concn in the time of staying, product temperatur, product is kept identical with initiator concentration.If reaching the small powder position (illustrating in following paragraph) that structure is determined at this, then by reducing product temperatur, conversion is kept constant.If product temperatur does not reoffer the room for maneuver, then by reducing the catalyst concn in product or by determine dosage keep conversion for initiator, the lactic acid that preferably concentrates.It is surprisingly found that the rabble furnace reactor run continuously can run in like fashion to specified generative capacity 25% minimum production ability, wherein lactide converts identical and then product quality is identical.

This cascade of measure allows: the melt level in stove keeps up to making heat exchanger also always be covered by melt in the case of the minimum production ability of 25%.It is possible to fully be used for regulating product temperatur by the face of heat exchanger.Heat exchanger rinses constantly with melt.Therefore polymeric layer is avoided to be deposited in thermal transfer surface.

Preferred embodiment the temperature of reactant mixture is set between 120 and 200 DEG C according to one of the method according to the invention, between preferably 130 and 170 DEG C, and keeps constant there.

Independently or in combinationlyly, it is possible to be set between 5 and 100ppm by the catalyst concn in reactant mixture, preferably between 15 and 60ppm, wherein catalyst is preferably selected from: the organic compound of stannum, zinc, titanium and zirconium.In the case of above-mentioned metal-organic example, preferred concentration range described above designs the concentration of the metallic atom in reactant mixture at this, for when the example of organic metal-free catalyst, preferred concentration range described above herein relates to the concentration of catalyst atoms.

Same it is also feasible that: especially as single measure or with before or method set forth below feasibility in combination, being set as between 0 and 30mmol/kg by initiator concentration in reactant mixture, wherein initiator is preferably selected from: monovalence, bivalence, trivalent and the alcohol of more high price.

Same it is also feasible that: initiator is added to reactant mixture.It is preferred here that: initiator is selected from: carboxylic acid, preferred lactic acid, particularly preferably have the aqueous lactic acid of 80% to 100% concentration, and the initiator concentration in reactant mixture is set so that the reactant mixture formed when polymerization have between 5 and 15mmol/kg, preferred carboxylic group concentration between 5 and 10mmol/kg.

Another limited embodiment proposes: the temperature of reactant mixture regulates via the temperature of the lactide carried and/or amount and/or by means of heat exchanger and/or via the temperature of heat carrier and/or amount flowing to heat exchanger.

Especially, in guiding tube, the stagnation pressure of at least 100mbar is built by means of at least one agitating element.

Additionally, according to the method according to the invention preferably: reactant mixture speed with more than 10 times and preferably greater than 30 times reaction yields in the axial direction is rolled.

Need according to the method according to the invention: heat exchanger and/or guiding tube are fully covered by reactant mixture.

Especially, in the case of production capacity is corresponding to the 10% to 100% of specified generative capacity of reactor, preferably 15 to 100%, especially preferably 20 to 100%, the method is controlled.The most also realize according in the concrete design of the reactor that can use in the method according to the invention of the present invention: the economical operation of method is feasible in the case of not damaging product quality in the case of production capacity is less than the 100% of specified generative capacity, such as < the 80% or < 60% or < 40% of specified generative capacity.Therefore, the method according to the invention realizes: especially realize relating to method embodiment this production capacity, particularly flexible in the case of using according to the reactor of the present invention.At this most surprisingly: convert can be maintained in the case of reactor generative capacity is different with viscosity identical numerically.

In the case of there is protuberance for guiding tube, the preferred embodiment proposed before for it keeps filling in terms of nominal production capacity, wherein guiding tube fully sink in reactant mixture and the protuberance that only bores a hole when the lowest filling for stretch out from reactant mixture if desired.

For have another guiding tube of agitator be positioned at above heat exchanger in the case of, the only guiding tube of bottom and heat exchanger keeps being covered by melt.

It is preferred for setting conversion between 5 and 80% of lactide, between particularly preferred 30 and 60%.

It is also preferred that: the mean residence time of the reactant mixture in reactor is set to maximum 4 hours, preferably at most 2 hours.The average time of staying draws from the reaction volume about the volume flow realized of reactant mixture.The volume of the reactant mixture that reaction volume is present in reactor.

Another of the method according to the invention preferred embodiment proposes: be set in the temperature of reactant mixture in the firstth district of the temp. controllable of reactor shell, between preferably 120 and 200 DEG C, between preferably 130 and 170 DEG C, and the 3rd district of the temp. controllable of reactor shell is set to lactide fusing point and less than temp. controllable the firstth district temperature temperature between temperature on.The temperature in the secondth district selects according to the material position of reactor.For material position is selected as the upper seamed edge of guiding tube high in the case of for preferably: the heatable Part II for reactor wall portion selects and its identical temperature in the presence of Part III.For the higher situation in material position in reactor preferably: select in the secondth district of temp. controllable and temperature identical in firstth district in reactor wall portion.

The method especially introduced is run continuously at this, and i.e. it is continuously by reactant or not yet cause the reactant mixture of reaction export in reactor and extract product continuously.The material position of reactor can change at run duration, but also keeps constant.

Accompanying drawing explanation

The present invention elaborates according to figure below and embodiment, and done embodiment is the most only exemplary in nature and can not be interpreted as being limited to subject of the present invention.

Apply at this and be defined below:

Viscosity:

The most always represent dynamic viscosity.

ROP:

Ring-opening polymerisation

Nominal production capacity:

Yield in units of kg/h, it designs for reactor or polymerization unit.

Production capacity:

Yield in units of kg/h, wherein reactor or polymerization unit actually run.

Mw:

The mean molecule quantity (weighted mean) of polymer

The average time of staying:

The product quality in units of bulk product in units of Product yields kg in units of every kg/h or in the reactor of every bulk product stream

Convert:

Convert the U (representing with %) lactide concentration x from the measurement of sample and lactide concentration x when entering reactor₀In calculated as below:

U=[1 (x/x₀)] 100%；

X and x₀It it is mass percent.

Shown in the drawings:

Fig. 1 illustrates the first embodiment of the reactor according to the present invention.

Fig. 2 illustrates the second embodiment of the reactor according to the present invention.

Fig. 3 illustrates another embodiment of the reactor according to the present invention.

Fig. 4 illustrates another embodiment of the reactor according to the present invention.

Fig. 5 illustrates another embodiment of the reactor according to the present invention.

Detailed description of the invention

According to the first embodiment of the invention Fig. 1 illustrates the reactor 1 according to the present invention.For such operation method as described above, reduce especially for the mixing realized required for product, temperature regulation and production capacity, need suitable equipment.Rabble furnace reactor 1 according to the present invention includes the parts of cylindricality, in the bottom of the parts positioned beneath taper of described cylindricality.Cone tip is led in the outlet 4 of product.Disposing gear pump in outlet, described gear pump is for according to dosage extracting melt from reactor 1.The outlet of taper simplifies discharges in stable operation from reactor 1.In the case of running interference, such as in the case of the planless raising of viscosity, it makes the emptying transfiguration of the outflow of product, the filling of emptying pump and stove easy.The subtended angle of cone is preferably greater than 60 °.Less angle does not reoffer advantage when product extracts and empties, but causes district and the structure height of multiplying arrangement of the mixing degree difference in cone tip.Here, reactor 1 has reactor wall portion 2, described reactor wall portion is configured to be double-walled.The reactor wall portion 2 of double-walled is divided into three single districts I, II, III at this, and described district I, II, III are able at this through-flow by the heat-carrying agent medium of liquid and then can heat individually.Reactor wall portion 2 surrounds reactor inner chamber 3.Reactor 1 has for the entrance (not shown) of reactant and is arranged on the outlet 4 of bottom side.Reactor 1 in axial direction extends at this, and described axis illustrates the most vertically.Connecting leading axle 6 from lid (upper end of reactor), described leading axle in axial direction stretches.Here, reactor inner chamber 3 has height h, described height determines from the upper end of outlet 4 to reactor inner chamber 3.Here, reactor inner chamber 3 has diameter d.There is guiding tube 7 in the lower area of reactor 1, described guiding tube has internal diameter x and outside diameter d '.Guiding tube has design size h of axially composition at this '.Accessing heat exchanger component 10 in chamber 9 between built-in wall portion and the guiding tube being formed in reactor, described heat exchanger component is the tube bank of annular extension in the case of the example of Fig. 1.Being joined on shaft 6 by agitating element 5 in the inner chamber 8 of guiding tube 7, described agitating element can produce the axial flowing of existing reactant mixture in guiding tube 7.In current situations, agitating element 5 is crutcher.At this, comprise reactant mixture in reactor 1 to transport downwards in guiding tube when operating shaft 6 with induction element 5, make reactant mixture deflect by reactor wall portion and enter into after discharging from guiding tube 7 in the chamber 9 of the annular between guiding tube 7 and reactor outside wall portions, and upwards transported by heat exchanger 10 the most forcibly.Reactor can use reference V in FIG at this_minThe minimum fill level illustrated and Fig. 1 use V_maxRun between the Fructus Anisi Stellati position illustrated.Additionally, shaft 6 exists other agitating element 5 ' and 5 ", described agitating element is arranged on guiding tube.As shown in Figure 1, this additional agitating element is formed at this in Liang Ge district of reactor, the agitating element 5 being set directly on shaft 6 " transport downwards in the rotation direction drawn of shaft (upwards transporting in the case of rotation direction is contrary), and outside be arranged on the agitating element 5 ' at the wall portion 2 of reactor 1 stirring mixture is upwards transported (dynamic in opposite direction in the case of transport downwards).

Figure 2 illustrates another deformation of reactor 1, for general view, the reference for identical ingredient application is the most not shown the most in FIG.Difference from the reactor shown in Fig. 1 is: the reactor 1 shown in Fig. 2 has the different agitator 5 in guiding tube 7.Additionally, reactor shown in Fig. 21 and the difference of the reactor 1 shown in Fig. 1 be on shaft, be arranged on the other agitating element 5 ' on guiding tube 7,5 ".As seen in Figure 2, shaft is constituted coaxially at this, i.e. shaft arranged coaxially to each other by two, the shaft that can be operated alone.Can run, by internal shaft, the agitating element 5 being arranged in guiding tube 7, by outside shaft can run other agitating element 5 ', 5 ".

Fig. 3 illustrates the another type of reactor 1 according to the present invention, also cancels, for general view, the reference applied for identical ingredient in accompanying drawing before at this.Difference with the reactor 1 according to Fig. 1 and 2 is: this reactor for whole agitating elements 5 ', 5 " be respectively provided with identical type and identical carriage direction.In shown example, agitating element transports downwards in the middle section near shaft.Thus the outer peripheral areas near stirring wall forms downward flowing.Additionally, replace the pipe bundle heat exchanger 10 of Fig. 1 and 2 is provided with heat exchanger 10, described heat exchanger is made up of vertically disposed pipe, during wherein heat exchanger is directed to pipe and melt for can guide around pipe.As an alternative, following heat exchanger 10 is also feasible: between described heat exchanger is arranged on bottom two pipes according to Robert evaporator type, bottom described pipe lower section and up guiding tube with central authorities flush.

Fig. 4 illustrates reactor as shown in Figure 3, certainly the agitating element 5 in the top " height on there is another guiding tube 7 ', the most axially mixing in another the guiding tube described reactant mixture in reactor 1 region between top level and heat exchanger 10.

Fig. 5 illustrates another alternative of the type of reactor shown in Fig. 4.Have protuberance 7 here, connect on guiding tube 7 ", described protuberance for melt permeable constitute, be such as configured to orifice plate.

Embodiments below is universally applied to whole accompanying drawing, and the details of special each accompanying drawing belonging illustrates as this embodiment.

The lid of reactor 1 can at random shape.Preferably bottom end socket or elliptic arch, bottom described end socket or elliptic arch in middle ground be provided with and connect portion for shaft 6.In connecting portion, there is thermal protection portion, described thermal protection portion by liquid or steam-like heat carrier run.It prevents from being gone out by the hot-fluid of axle 6 from reactor 1 by heated and stirred axle 6.Therefore prevent: by heat is not enough, the polymer of solid-state is frozen on agitator 6 under specific running status.

The outer wall of reactor 1 maybe can cool down as the heat exchanger in lid and loading reactor can heat preferably by means of the heat carrier of liquid in ambient temperature around and running temperature equally.Following liquid is preferably used as heat carrier, and the boiling point of described liquid and burning-point are positioned on 220 DEG C and its freezing point is positioned under-10 DEG C and be nontoxic.High burning-point reduces quick-fried according to the consuming in protection.Avirulence neither causes the harm to operator and environment the most not cause the pollution of product in the case of leaking down in a device.

The external heat of reactor 1 is divided into multiple region I, II, III, and described district can run with different temperature.Advantageously: the height of the material position in reactor cover until in reactor 1 is set to the temperature identical with the product in reactor 1.This simplify the regulation of product temperatur and avoid freezing or overheated of polymeric film on the inwall of reactor 1.The most advantageously: to reactor cover material position on, especially on maximum horizontal and in container cover with lower temperature heat, between described temperature product temperatur in lactide fusing point and reactor 1.Thus it is possible that: avoiding the lactide resublime of solid-state to inwall and produce the lactide film of liquid, described cutin membrane is back in product under gravity.Because polymer is solvable in monomer, this prevents the growth of polymeric layer to be naturally back on wall and then prevents from polluting reactor 1 and product with the polymer decomposed.

In the lower area of reactor 1, the agitator 5 axially transported works in guiding tube 7.Crutcher, triumphant Pulan agitator, oblique leaf agitator, intersection leaf agitator or propeller agitator are suitable as type of stirrer.Described agitator produces compulsory flowing down along discharge direction.This flowing is in the annular chamber 9 that conical lower portion deflects and is directed between guiding tube and reactor wall 2.It is provided with heat exchanger 10 in this chamber 9.In order to realize the compulsory percolation by melt, the vertically extension of described melt is limited on the height of guiding tube 7.Therefore the upper seamed edge of guiding tube 7 overlaps with the upper seamed edge of heat exchanger 10.Minimum level in this horizontal line defined reaction device.Inflow during the most only thermal transfer surface can be covered by melt and be kept from outside to guiding tube simultaneously in the case of minimum level.

Chamber 9 around the annular of guiding tube 7 is filled by Tube Sheet of Heat Exchanger 10 in horizontal extension equably so that flow resistance is constant on fluoran stream surface, to managing circulation and be formed without dead zone or preferred passage equably.Heat exchanger 10 and guiding tube 7 form functional unit, and described functional unit is arranged in reactor 1 as far as possible, and therefore minimum level allows the motility of the top started for the production capacity to reduce.But, the 10% of the pressure loss that the pressure loss that the melt that the lower seamed edge with heat exchanger 10 of guiding tube 7 is only deep to flow out from guiding tube 7 so that entering heat exchanger 10 to neutralize flows is up in heat exchanger.Otherwise, it becomes possible to consider the circulation of the difference of the thermal transfer surface near reactor wall and consider the corresponding heat transfer reduced.

The tube regulator of heat exchanger 10 can be made up of the horizontally disposed bundle constituted with coil pipe, and wherein melt moves around pipe flow, and heat carrier flows through pipe.Actuator also is able to be made up of horizontally disposed pipe, during wherein heat carrier is incorporated into pipe and melt around pipe guide.

As other feasibility, can by vertical, between the pipe of internal product percolation is arranged on bottom two pipes according to the type of Robert evaporator, bottom described pipe, the guiding tube up with in lower section with central authorities terminates (shown in Fig. 3 to 5) with flushing.Then, heat carrier is flowing in the space of pipe.The specific embodiment of this variations is: parallel Guan Qi end crimping becomes hexagon, and the most hexagonal end is the most seamless unoccupied place is adjacent to each other and is welded to one another so that save bottom pipe.The advantage of this layout is: melt flowing is contrary with the minima on the blocking face of flow direction so that pressure loss is little and the stagnation with dead band can not occurs.

Guiding tube agitator 5 can build the pressure of at least 100mbar, in order to the melt volume formed in reactor 1 is carried through the heat exchanger of loading with high upset speed.Upset speed is at least 10 times of reactor rated output, preferably at least 30 times.

In the case of rotating speed is identical, the ratio of guide tube diameter and stove diameter is the biggest, and gradient and the area of agitator are the biggest, and the narrower gap between guiding tube and agitator, and function of transportation and the pressure build of the agitator 5 in guiding tube 7 are the best.When the ratio of stirrer diameter and the internal diameter of guiding tube 7 is 0.95 to 0.98, it is achieved the good function of transportation of the agitator 5 in guiding tube 7.Heat exchanger is arranged around guiding tube 7 and heat exchanger 10 condition under level in reactor 1 must limit thermal transfer surface feasible in structure under whole running statuses.In order to required thermal transfer surface be installed in described chamber, guide tube diameter and the ratio of reactor diameter d '/d are 0.2 to 0.6, preferably 0.3 to 0.5 to be attested.

If the lower seamed edge of bootstrap pipe in the case of minima of the level in reactor 1 rises measures the height being positioned at the internal diameter d corresponding roughly to reactor 1, then the agitator 5 being arranged in guiding tube 7 be enough to set axially flowing.If being positioned horizontally on it, then need one or more other agitator 5 ', described agitator is arranged on guiding tube 7.The stirring action of guiding tube agitator 5 itself is not up to above melt, because its flow resistance realizing overcoming heat exchanger.

The agitator 5 ' being disposed thereon has the effect different from guiding tube agitator: its promotion near reactor wall is axially flowed and promotes the axial flowing in the middle section around reactor axle simultaneously in opposite direction.This be preferably able to be the interruption according to Fig. 1 spiral (Agitator) or continuous print spiral, it is respectively provided with the narrow spacing away from reactor wall.This also is able to the ribbon agitator being have the big tiltedly blade common at wall in portion, and the length in described oblique portion covers ring week (PARAVISC agitator, this figure 2 illustrates) of half.Other the type of stirrer on guiding tube that is suitable for use in is‐,Alpha and Sigma's agitator, it the most axially carries out transporting, be common in wall portion and have contrary function of transportation near wall or axle.The ratio (z/d) of the rotating diameter z of this additional mixer elements 5 ' and the internal diameter d of reactor 1 is between 0.7 and 0.98 in all cases.

The spiral of continuous print spiral or interruption, blade inclination angle is chosen so as to be implemented around function of transportation upwards at wall.Near container axis or shaft 6, stream is downwardly oriented.For this purpose, install near stirrer shaft on axle or on stirring arm axially downwardly transport element, such as dihedral vane (pusher element, viscoprop element, interprop element).The stream being downwardly oriented near stirrer shaft prevents the race way of material exchange (pulling effect) with reduction around the axle rotated.When the stream that the element enough axial exclusion effects of applying of transporting near wall make central authorities be downwardly oriented draws individually from the conservation of mass, it is also possible to abandon the transport element near axle.Additionally, guiding tube agitator 5 the flowing downward by its swabbing action support central authorities transported downwards.

When heating, the natural convection in heat exchanger supports the effect upwardly-directed near wall of agitator 5 ' due to density contrast.The direction of stream can also be able to exchange by the rotation direction of reversion agitator 5 and 5 ', i.e. in guiding tube 7 and near reactor axle upwards, exchange downwards near reactor wall 2 and in heat exchanger, thus in the way of auxiliary, natural convection is acted on when cooling down melt.Here, the stream in reactor 1 only changes direction, and do not significantly change stream and formed.Due to the little temperature in melt and density contrast, and because the most not seething with excitement and then the rising of bubble not occurring, so not producing shortcoming when the rotation direction of agitator 5 and 5 ' keeps identical in heating with when cooling down.

Certainly, common at wall agitator allows in current range of viscosities until the low ring circular velocity of about 3m/s, in order to driver torque and stirrer-driven device power are maintained in the limit.The type of stirrer 5 worked in guiding tube typically requires higher ring circular velocity, i.e. 5-15m/s, in order to the function of transportation required for realization.Therefore, 8/min's and 100-200/min's for guiding tube agitator the big speed discrepancy (example Paravisc, Fig. 2) for agitator common at wall is obtained.The co-axial shafts with corresponding stirring tool driver realizes the different velocity of rotation of the agitator 5 and agitator 5 ' being disposed thereon being arranged in guiding tube 7 so that its axial action can be coordinated with each other.Therefore, it is possible to prevent from axially flowing by adjustment of rotational speed simply, the deviation of the especially recirculation zone in reactor 1.Recirculation zone forms danger, because it is in and the exchange of the reduction of remaining liquid volume in reactor 1 and then hinder optimal mixing.When in the most different productivity ratio and then running reactor 1 in the case of product viscosity extremely difference, coaxial revolvers is especially advantageous.

When for guiding tube agitator 5 and the agitator 5 ' common at wall that is disposed thereon it can be found that during the range of speeds of superposition, it is possible to abandon the coaxial stirrer of consuming.When in guiding tube 7, in the case of rotating speed is low, application has the agitator 5 of high function of transportation, this tends to realize in higher range of viscosities.Having Kaplan agitator or the crutcher of large area blade, both of which has big gradient and strong function of transportation, it is possible to run with the rotating speed identical with the agitator 5 ' common at wall being disposed thereon.Such as, the suitable range of speeds is on by the crutcher in guiding tube and guiding tubeIt is 10 to 25/min for the combination of agitator.This is applicable to the viscosity stove with the design size with Fig. 1 of 50Pas.In the case of rotating speed is identical, the function of transportation of helical can with the size of gradient and its coordinate in the function of transportation of the agitator 5 ' common at wall being disposed thereon with the size in the gap between guiding tube 7.The rotating speed of agitator 5 ' common at wall can adjust by transporting the inclination of element, its area and its resistance.

Not having coaxial revolvers to be with regard to other enough solution, two or more agitator, described agitator are arranged on the common axle in a guiding tube 7 or multiple guiding tube 7,7 ' or are arranged on protuberance 7 " in (Fig. 3,4,5).Here, arrange the deepest agitator to undertake the task of forcing to transport reactor content by the heat exchanger of loading.Melt is transported downwards in the middle section of reactor 1 by the agitator 5 ' being disposed thereon.Cancel the agitating element near wall, the most also cancel melt transport in this region.

This solution causes low cost of investment, low driver torque and actuator power.But immixture is limited.

Figure 3 illustrates a variations.On the guiding tube agitator 5 that bottom is arranged, two other agitators 5 ' of same design size are fixed on identical axle in the case of not having guiding tube.In the case of not having guiding tube, melt not only axially down and is radially outward transported by described agitator.The result in two or three districts that the recirculation on heat exchanger is made by reactor, described district is in the material exchange of reduction each other and is in the material exchange of reduction with whole reactor content.

In another variations of this arrangement, it is that intrinsic guiding tube 7 ' (Fig. 4) applied by two agitators being arranged on axle.When liquid level is under guiding tube 7 ' above, the spacing between guiding tube 7 and 7 ' allows becoming a mandarin in the guiding tube 7 from outside to bottom.When in this stove when being positioned horizontally on guiding tube 7 ', the guiding tube agitator 5 ' on top is only active.The axial orientation of stream is improved relative to Fig. 3 and then immixture is improved.But the intermediate cavity between the two guiding tube 7 and 7 ' always there is also flow component radially and then recirculation.

In the latter variations of this solution, three agitators being arranged on identical axle 5 and 5 ' work in the guiding tube 7 of common prolongation, and described guiding tube has protuberance 7 ".Guiding tube 7 is at protuberance 7 " on heat exchanger extend region in be configured to orifice plate, be made up of (Fig. 5) integral plate under it.Thus, any level in stove is until guaranteeing in minimum level to be flowed into guiding tube 7 melt from outside.Meanwhile, heat exchanger 10 fully covers with melt.Flowing radially reduces relative to Fig. 4, improves immixture further.

When lactide ROP in rabble furnace reactor 1, according to the present invention, limit production rate so that during the viscosity of the product in reactor is positioned in the range of about 1-100Pas, preferred 5-50Pas.In this range of viscosities, produce the mixing of the reaction contents of viscosity and the optimal of main axially stream guiding according to the guiding tube agitator of the present invention.It causes the stream picture in the anchor ring of rotation, the reaction contents of described stream picture detection wholly liquid state.Avoid producing the agitator of flow component radially, because it causes according to the recirculation zone with limited material exchange.

According to the present invention, in order to set the preferred range of viscosities in rabble furnace reactor 1, it is considered to the concentration of catalyst, initiator and inhibitor and type, reaction temperature.The reactor production capacity that described parameter is simultaneously used in the scope between 25% and 100% of nominal production capacity according to the present invention.

The response speed of the ROP in rabble furnace reactor 1 is the most relevant to temperature and catalyst concn.In order to keep described range of viscosities, increasingly, in order to the viscosity in this scope is kept constant, limit lactide and convert and keep constant.This is carried out in the following way: reaction temperature preferably remains in the scope of 130 DEG C to 170 DEG C.The inert temperature regulation of tending to become a mandarin in the product caused by temperature and lactide is out supplemented by carrying out heated conveying and thermal conductance fast and effectively by means of internal heat exchanger.The modulated variable that is mutually coupled with in terms of optimal regulation enters temperature and enters the combination with product temperatur of through-current capacity and heat carrier temperature and heat carrier through-current capacity as regulated variable.

Here, all for catalyst known to PLA of the prior art, the organic compound of such as stannum, preferential oxidation level+2, be suitable as catalyst such as ethyl hexanoate stannum.Other example is the organic compound of stannum, titanium and zirconium.If applying organic tin compound, then catalyst concn is between 10ppmSn and 100ppm, preferred 20ppm to 60ppm.Here, catalyst concn relates to the metal share of corresponding catalyst.The type of catalyst also is able to affect response speed.When the organic compound of the stannum of bivalence obtains the highest response speed, the compound by zirconium and the compound of titanium with by the stannum of tetravalence obtains significantly reduced speed.

Just for the mole reached in following tubular reactor at the end of being limited in polymerization, need to determine dosage for initiator.At this whole initiators well known in the prior art, the most high boiling alcohol, such as hexanol, capryl alcohol, dodecanol and glycol, such as ethylene glycol, propylene glycol, butanediol.When realizing the long chain branches of end product, such as, adding the melt viscosity in man-hour to improve, glycerol is applicable.Concentration relevant to the viscosity of end product and desired mole and between 0 and 30mmol/kg in the range of in.All initiator accelerates the ROP reaction with the lactide improving concentration.

The response speed of ROP is additionally relevant to the concentration of the carboxylic group in lactide.Wherein detect whole linear oligomer of PLA, be currently lactide lactyl lactate (linear dimer).Lactyl lactate by the open loop of the lactide under water mark effect during preparing lactide, if desired also by lactide storage and transport during atmospheric moisture effect formed.High carboxylic group concentration slows down reaction so that need the longer time of staying during ROP in rabble furnace, in order to realize the conversion preset.In the tubular reactor not allowing to change the time of staying being connected on reactor 1, convert and mole can fall after the numerical value of regulation.In order to set up the PLA that can also be used with in engineering, should the concentration of carboxylic group more than 30mmol/kg.Have the PLA of the high mole of 150000g/mol needs < the carboxylic group concentration of 15mmol/kg.The scope of mole important in engineering is between 120000 and 250000g/molMw.

In industry park plan, the agitator reactor 1 of the carboxylic group concentration with the fluctuation in lactide must be able to be competent at.Carboxylic group from substantially 15mmol/kg needs the length terminated relative to polymerization to the time of staying (described polymerization terminate in rabble furnace reactor outside realize) making to be no longer able to set up the whole spectrum of mole important in engineering.According to the present invention, therefore, in the ROP in rabble furnace reactor 1, but residence time limitation is in maximum 4h preferably 2h, enabling obtains and has to the important product spectrum of the engineering of 15mmol/kg, the carboxylic group concentration of preferred 10mmol/kg.

But, the design of the reactor 1 with this time of staying comes into question in having the lactide of the lowest carboxylic group concentration of substantially 0 to 3mmol/kg.It causes the highest response speed.The time of staying of 2h itself is too high for described lactide so that convert and then product viscosity can not be maintained in preferred scope.According to the present invention, adding inhibitor in this case, described inhibitor reduces response speed.Generally, carboxylic acid is suitable for and this.Water is similarly suitable, because its extremely fast speed in technological temperature is reacted with lactyl lactate, described lactyl lactate act as inhibitor for it.Preferably, application has between 80 and 100% lactic acid of concentration as inhibitor.Carry out determining dosage make the hydroxyl group concentration of lactide in terms of calculating between 5 and 15mmol/kg, preferably between 5 and 10mmol/kg.

Analysis method:

Determine that the lactide in PLA prepolymer converts:

Must comprise and dissolve in chloroform and by gel permeation chromatography analysis more than the sample of 10% lactide.Application has the chloroform PVD post as mobile phase.The material that UV-VIS detector detection separates on post.The lactide content of sample calculates from peak area by means of outside caliberating device, and described peak area is associated with lactide.

Determine the carboxylic group in lactide:

Lactide dissolves in methanol.Solution titrates with the KOH solution of 0.1n benzaldehyde.End product detects in the way of potentiometric analysis.Result is explanation in units of mmol/kg.

Determine the carboxylic group in reactant mixture:

The sample dissolution of reactant mixture titrates relative to the Tetrabromophenol Blue as indicator in dichloromethane and using the KOH solution of 0.1n benzaldehyde.Result is explanation in units of mmol/kg.

The measurement of the dynamic viscosity of the melt in rabble furnace reactor

Melt viscosity in reactor is relevant to temperature and conversion.It is measured by process viscometer again, and the sensor of described process viscometer is arranged in rabble furnace reactor or afterwards in position.Premise is: the mixing in reactor is sufficient so that occur without measured value and the time of staying in reactor and the dependency of position.

Process viscometer directly detects the viscosity of the melt in rabble furnace.Eliminate sample extract and will measure in sample transport to laboratory and in lab viscosity meter.This measurement is coarse, because the component (conversion) for the sample of reaction by cooling and reheats and especially changes in laboratory measurement.Additionally, there is significant time delay in measured value so that the regulation of reactor can not be built thereon.

The commercial decay measuring resonance sensor and energy loss and the equipment that is converted into dynamic viscosity be suitable as process viscometer.It provides the signal of telecommunication, the described signal of telecommunication to be the tolerance of dynamic viscosity for procedure regulation.The example of applicable equipment is the ViscoScopeVA300 of ViscoMelt5000 or the Marimex company of Hydromotion company.

Example

Method:

Example 1: the ROP method in the small-scale of the reaction generative capacity with change

Being heated or cooled from the outside through by dual outer housing by the rabble furnace with the diameter of 0.70m and the container capacity of 220kg lactide, described rabble furnace does not comprise the heat exchanger of loading.Therminol66 is used as heat carrier, its be around ambient temperature to the synthetic product that exists of the ground of liquid in the wide temperature range between on running temperature.The temperature of heat carrier sets by the heating/cooling equipment of the electricity being arranged on outside stove.Stove is equipped with the Paravisc agitator with 2 blades, and described blade about tilts 50 ° relative to rotational plane and wall product in the vicinity upwards transports.The ratio of the internal diameter of stirrer diameter and stove is 0.95.In the middle section of stirrer shaft, there is 0.3m diameter and 45 ° of intersection leaf agitators tilted support that melt transports downwards.Rotating speed keeps constant in the case of 24/min.

For rabble furnace conveying 54kg/h lactide (the 100% of nominal production capacity).Lactide comprises the carboxylic group of 5mmol/kg.Level set in stove is so that the average time of staying of the product in stove is 2 hours, the most therefore there is 108kg reaction mass or 95l reaction volume.By about 1m²The heating surface contacted by product obtain being heated or cooled the 11m of area and reaction volume²/m³Ratio.Inlet stream and the temperature of lactide keep constant by adjusting means.Entering temperature is 120 DEG C.Product temperatur is set to 150 DEG C by means of the input temp of the heat carrier of through-flow and dual outer housing via stove.Temperature-adjusting device keeps described product temperatur constant when +/-1 DEG C stable.Fall catalyst stannum (II) ethyl hexyl acid cut dosage is the Theil indices so that there is 25ppm in product.Initiator lauryl alcohol is set in the concentration of 10mmol/kg in lactide.Product is extracted out by gear pump at furnace bottom so that level keeps constant.Here, the amount of discharge is 54kg/h.It is 50% in time average that lactide in the product of discharge converts.The dynamic viscosity of 15Pas is averagely shown at the process viscometer ViscoMelt5000 of the Hydromotion company flowed out in pipeline being arranged on product.

When converting that deviation is not more than +/-5% time average, just it is referred to as being constant by this conversion.Stable state and the determination of time average need 12h, and wherein every 2h extracts Product samples and measures conversion.

Under the steady statue of stove, drop to 74% (40kg/h) of nominal production capacity by becoming a mandarin and level dropped back so that the average time of staying do not change for 2h.Enter temperature and product temperatur keeps as before.Under setting steady statue, measure the conversion in product.Described it is converted into 54%.Dynamic viscosity by the melt of process viscosity measurement amount is 20Pas.

Entrance backs on 27kg/h lactide (the 50% of nominal production capacity).Now, level keeps as in these cases so that the average time of staying brings up to 3h.In order to balance, decline product temperatur by means of heat carrier.All remaining parameters constant.After correction temperature and after setting stable state, in the case of 143 DEG C, find the conversion in the product of 52%.The dynamic viscosity by process viscometer measurement of melt is 18Pas.

After again the entrance of lactide dropping to 16kg/h (the 30% of nominal production capacity), continue level is kept constant so that the time of staying brings up to 5h.Now, in addition to product temperatur is dropped to 137 DEG C, catalyst concn backs on 22ppm.After setting steady statue, be converted to 51%.The dynamic viscosity by process viscometer measurement of melt is 16Pas.

Example 2: the ROP method in the production scale of the reaction generative capacity with change

The rabble furnace run continuously of the container capacity with 18t lactide has the internal diameter of 2.3m.Described rabble furnace is equipped on the spiral type agitator in the heat exchanger of inside, guiding tube and guiding tube according to Fig. 1Agitator.174m²The area for heat exchange that needs provide by the bundle that is made up of coil pipe, described bundle is arranged around the guiding tube of agitator.The ratio that face and reactor volume are heated or cooled is 11m as in small-scale²/m³.Owing on guiding tube, seamed edge and tube bank are always intended to the requirement being maintained under liquid level, production capacity can be carried out in the time of staying of 2h under conditions of being not less than 50%.The temperature of the heat carrier of liquid sets in the equipment being positioned at outside stove for heating and cooling and heat exchanger by being arranged in stove pumps subsequently.The dual outer housing of stove is maintained in the temperature identical with heat exchanger by means of identical heat carrier.

By means of the gear pump accurately determining dosage, the lactide of 9000kg/h is flowed to stove as nominal production capacity.Lactide has the content of the oh group of 5mmol/kg.The entrance temperature of lactide is adjusted on 130 DEG C by means of the heat exchanger being connected to stove upstream.Product temperatur is maintained on 150 DEG C by the circuit in terms of the regulation optimized, by also having the modulated intervention at a temperature of entering to keep constant at the heat carrier of the heat exchanger for loading.

Stannum (II) thylhexoic acid is continuously delivered to stove as catalyst and lauryl alcohol is continuously delivered to stove as initiator by dispensing pump so that the catalyst concn in product is 25ppmSn and initiator concentration is 10mmol/kg.

The time of staying of product is maintained on 2h by the level(l)ing device in reactor.Gear pump is for discharging product, described product average out to 9000kg/h from reactor.The lactide measured in the product is 53% with converting under the steady statue of reactor time average.The ViscoScopeVA300 of Marimex company it is provided with in product flows out pipeline.It illustrates the average dynamic viscosity of 20Pas of melt.

In the case of lactide conveying is reduced to 4500kg/h (the 50% of nominal production capacity), the level in stove is reduced to by means of emptying pump so that the time of staying is 2h as before.Product temperatur is retained at this on 150 DEG C.With lactide yield simultaneously, catalyst and initiator dosage fall after rise so that its concentration in the product keeps identical.After reaching the steady statue in stove in new level, measure lactide and convert.Described lactide transformation time is 54% fifty-fifty.The dynamic viscosity by process viscometer measurement of melt is 22Pas.

In order to reactor production capacity being reduced to 2250kg/h (the 25% of nominal production capacity), this level in holding furnace so that the time of staying brings up to 4h.Temperature falls back on 142 DEG C, and catalyst is determined dose degradation to the concentration made in product simultaneously is 20ppmSn.Initiator concentration keeps constant.After reaching the steady statue in stove under conditions of changing, measure lactide and convert.Described lactide transformation time is 52% fifty-fifty.The dynamic viscosity by process viscometer measurement of melt is 18Pas.

Example 3: the rabble furnace reactor of lactide ROP

Fig. 1 illustrates the embodiment of the rabble furnace run continuously of the container capacity with 9000kg/h generative capacity and 18t product.Its interior diameter is 2.3m.The bottom of taper has the subtended angle of 90 °.Container cover enough becomes end socket.Described container cover carrying stirring tool driver and motor and driver.Axle feed-through device is equipped with thermal protection portion, and described thermal protection portion runs by the heat carrier of liquid and prevents: under non-stable running status, product is frozen on agitator or axle.

Reactor heats from the outside through by dual outer housing, and described dual outer housing is divided into 3 districts.Chamber wall on maximum horizontal and lid heat with the temperature of 120 DEG C.The mesozone level between maximum horizontal and minimum level in a reservoir is maintained in the temperature identical with producing temperature.When only carrying out in the case of minimum level, temperature identical in setting and covering.District under always remains on product temperatur.

It is made up of horizontally disposed coil pipe for regulating the heat exchanger of product temperatur, described coil pipe circulates the heat carrier of liquid.Melt is pressed downward in the container bottom of taper by the agitator in guiding tube, and the deflection of the most described melt and heat exchanger pipe shove from below.Coil pipe is arranged (" there is gap ") with staggering in the flowing direction, in order to the melt halved tie in realization reactor carries out uniform percolation.Tube bank is upwards closed with the upper seamed edge of guiding tube.On the one hand lowest possible material position in this horizontal lines mark reactor, described material position needs to the entrance in guiding tube and then to be circulated by heat exchanger for realizing melt.On the other hand, this material position is needed to keep heating surface under conditions of being covered by melt and preventing polymeric layer from assembling.

MarlothermFP is used as heat carrier, and it exists to liquid between-10 DEG C and+280 DEG C and is nontoxic.The subflow of required quantity provides with desired temperature and required pressure and flow and flows to reactor from outside outside reactor.Heated conveying is carried out by middle pressure steam, and thermal conductance goes out and carries out by air-cooling apparatus.Heat carrier flows in the circulation of Guan Bi.The regulation of the product temperatur in stove determines the temperature of the subflow of the heat exchanger in reactor.

In the guiding tube that crutcher is centrally disposed.The ratio of the internal diameter of guiding tube and container is 0.33.The axle journal of agitator is 0.98 with the ratio of the internal diameter of guiding tube.Guiding tube is configured to dual outer housing in heatable mode.The intermediate cavity formed between the concentric pipe of guiding tube is also fed to heat exchanger by the heat carrier percolation of liquid, described heat carrier.The temperature of the heat carrier in guiding tube is identical with the temperature in heat exchanger.

In the case of material position minimum and in the case of the lower seamed edge of bootstrap pipe plays the material position of not higher than container diameter of measurement, the agitator in guiding tube be enough to be guaranteed the axial circulation of whole melt volume in container by heat exchanger.

In the case of also realizing good mixing resultant in the case of higher level, the second agitator is arranged on the identical axle on guiding tube.Described second agitator for holding up to maximum horizontal and then also causing mixing in the case of the rated output of reactor by axial recycle stream.Here, so-called section ribbon agitator (Agitator, Chema company) it is used as agitator.Agitator has four arms, and described arm needs for setting up axial stream picture.The carrying of described arm has the panel element tilting 30 ° relative to horizontal line near the wall of 60mm wall spacing, according to being shaped like in the section of the helical interrupted.Melt in wall near zone is upwards transported and then by long for axial curtain coating by described arm, and described axial stream is upwards extruded from heat exchanger.Near stirrer shaft, mixing arm carrying has the panel element of the form of oblique leaf agitator.Described arm have with near wall and via function of transportation downward tilt contrary inclination.Described arm prevents constituting and supporting that the melt of the screw thread agitator in guiding tube carries of the rotation around stirrer shaft, mixing difference melt district.

The two type of stirrer is fixed on identical axle and can run in the range of speeds between 15 and 25/min.Driving power is 59kW in the case of 22/min, and driver torque is 6500Nm.In the case of rated output and rotating speed are 22/min, the upset speed in reactor is enter stream 46 times, and this represents the incorporation time of 2.6 minutes.

Fig. 2 illustrate with Fig. 1 formed objects and the rabble furnace of heat exchanger of same type, but there is different agitators.The Kaplan agitator with 5 blades with 20mm wall spacing works in guiding tube.Described Kaplan agitator transports downwards melt and upwards transports through heat exchanger after deflection at stream in container bottom subsequently.The ratio of the internal diameter of guiding tube and container is 0.39.

Agitator common at wall it is provided with on heat exchanger and guiding tube.Here, it is the ribbon agitator (Paravisc, Ekato company) with two blades, described blade tilts relative to rotational plane so that it upwards applies function of transportation near wall.The ratio of stirrer diameter and stove interior diameter is 0.95.Near axle, the panel element relative to rotational plane inclination 45 ° according to oblique leaf agitator type is placed on axle, in order to realize downward function of transportation.Described stirrer combination produce the axial stream picture similar with the agitator according to Fig. 1 and as produce axial immixture.Propeller agitator needs different rotating speeds with anchor agitator.This makes the coaxial revolvers needing have the rotating speed between the 100 of propeller agitator and 200/min and the 5-20/min of anchor agitator.Coaxial revolvers allows the coordination of the function of transportation of the two agitator to allow for optimizing axial stream picture to avoid radial flow and recirculation zone.In the case of the rotating speed that rotating speed is 150/min and anchor agitator of Kaplan agitator is 16/min, upset speed is 30 times of rated output, and incorporation time is 4 minutes.

Fig. 3 illustrates another variations of the rabble furnace according to the present invention with the rabble furnace formed objects in Fig. 1.Heat exchanger is present in the bundle being made up of vertical pipe, and described pipe and is streamed by heat carrier in outside by product percolation in inside.Pipe, in upper and lower is solded into bottom the pipe of annular, will be separated with product chamber by the mantle cavity of heat carrier percolation and carries central guiding tube simultaneously bottom described pipe.As in FIG, here, heat exchanger is arranged around guiding tube and its height is corresponding to the height of guiding tube.

The propeller agitator (Viscopropeller, Stelzer company) with 45 ° of orientation angles works with narrow wall spacing in guiding tube.Guide tube diameter is 0.46 with the ratio of the internal diameter of stove.The diameter of agitator is 0.98 with the ratio of guiding tube internal diameter.Agitator transports downwards melt and upwards transports through Tube Sheet of Heat Exchanger after deflection in container bottom subsequently.Agitator speed is 130/min.Two other propeller agitators of the identical structure type that there is same diameter with downward function of transportation it are provided with on guiding tube with heat exchanger.There is not agitator common at wall.Axial mixing is the best with the mixed phase ratio of the rabble furnace according to Fig. 1 and 2.Incorporation time is 15min.

When being arranged on the first agitator with guiding tube by the second agitator according to Fig. 4, improve immixture.Incorporation time is 12 minutes.

Fig. 5 illustrates have three variations at the identical propeller agitator axially arranged one above the other, and described propeller agitator works in common guiding tube.Guiding tube is made up of solid slab on the agitator of bottom and the height of heat exchanger, as it is in the embodiment proposed before.The guiding tube being made up of orifice plate is there is on heat exchanger.Described embodiment suppresses radial flow as far as possible, described in radially flow out in the aforesaid variations of present the two and damage immixture.This embodiment is used for the upwardly-directed stream outside guiding tube and the stream being downwardly oriented in guiding tube and is separated from each other by the two stream.Meanwhile, this embodiment allows to enter into the inflow in guiding tube from outside to inside in any level on heat exchanger in stove.Incorporation time is 6 minutes.

Claims (26)

1. a reactor (1), comprising: reactor wall portion (2), described reactor wall portion surround axially extended cylindricality, there is axial design size (h) and be perpendicular to the reactor inner chamber (3) of the diameter (d) that axial design size is measured, wherein said reactor inner chamber (3) has at least one and for the entrance of reactant and has outlet (4) on reactor bottom；

There is at least one agitating element (5) axially transported, axially extended shaft (6), described shaft is incorporated in reactor inner chamber (3) through described reactor wall portion (2) in the upper end of described reactor (1)

It is characterized in that,

Described reactor inner chamber (3) is provided with axially extended cylindricality, there is axial design size (h ') and be perpendicular to external diameter that axial design size measures (d '), the guiding tube (7) that limits guiding tube inner chamber (8), make to constitute chamber (9) between described reactor wall portion (2) and guiding tube (7), wherein said guiding tube (7) and described reactor bottom and spaced apart with the upper end of described reactor inner chamber (3)

Wherein the ratio for the axial design size (h) of axial design size (h ') and the described reactor inner chamber (3) of described guiding tube (7) is suitable for: (h '/h)≤0.9,

The external diameter (d ') of described guiding tube (7) is suitable for the ratio of the diameter (d) of described reactor inner chamber (3): (d '/d)≤0.9,

The described shaft (6) wherein with at least one agitating element (5) extends up in described guiding tube inner chamber (8),

And being provided with within described chamber (9) can be by the heat exchanger (10) of reactant mixture percolation.

nullReactor the most according to claim 1 (1)，It is characterized in that，Described guiding tube (7) separates with described reactor wall portion (2) with its bottom，Make when the shaft (6) with at least one agitating element (5) axially transported runs，Described reactant mixture as described in reactant mixture in the exit coming from described guiding tube (7) and the pressure loss measured to the pressure difference of porch of described chamber (9) be described reactant mixture in heat exchanger described in percolation (10) time as at described reactant mixture in the maximum 10% of the pressure loss entering heat exchanger (10) and the measurement of pressure difference when leaving heat exchanger (10)，And/or the spacing (a) of measurement is 0.001≤a/h≤0.25 relative to axial design size (h) of described reactor inner chamber in the projection on described reactor bottom.

3. according to the reactor (1) according to any one of the claims, it is characterized in that, ratio for the axial design size (h) of axial design size (h ') and the described reactor inner chamber (3) of described guiding tube (7) is suitable for: 0.05≤(h '/h)≤0.5

And/or

The external diameter (d ') of described guiding tube (7) is suitable for the ratio of the diameter (d) of described reactor inner chamber (3): 0.2≤(d '/d)≤0.6.

Reactor the most according to claim 1 and 2 (1), it is characterized in that, described guiding tube inner chamber (8) has the internal diameter (x) being perpendicular to described axial design size measurement, and at least one in described at least one agitating element (5) has the rotating diameter (y) being perpendicular to described axial design size measurement, and wherein ratio y/x is suitable for: 0.9≤(y/x)≤0.99.

Reactor the most according to claim 1 and 2 (1), it is characterised in that described reactor bottom is conically constituted and described outlet (4) is arranged at the tip of cone, the subtended angle of wherein said cone > 50 °.

Reactor the most according to claim 1 and 2 (1), it is characterized in that, described shaft (6) region between the upper end of the upper seamed edge of described guiding tube (7) and described reactor inner chamber (3) in the axial direction has at least one other agitating element (5 ') axially transported, the described other agitating element axially transported is constituted in two style, make to correspond in projection in axial direction in there is the operation of shaft (6) of the agitating element (5 ') that at least one other axis transports the flowing that in the region of described guiding tube inner chamber (8), generation is the most contrary compared with the region corresponding to described chamber (9) in projection in axial direction,

Or only corresponding to the region of described guiding tube inner chamber (8) is constituted in the projection of axial direction,

Or only corresponding to the region in described chamber (9) is constituted in projection in axial direction.

Reactor the most according to claim 6 (1), it is characterized in that, at least one other agitating element (5 ') axially transported described has the design size (z) being perpendicular to axial direction extension, and wherein the ratio for described design size (z) with the diameter (d) of described reactor inner chamber (3) is suitable for: 0.7≤(z/d)≤0.99.

Reactor the most according to claim 6 (1), it is characterized in that, described shaft (6) is constituted coaxially so that described at least one agitating element (5) and the agitating element (5 ') that at least one is other can operate independently of one another.

Reactor the most according to claim 6 (1), it is characterized in that, described agitating element (5) is selected from: triumphant Pulan agitator, oblique leaf agitator, crutcher, propeller agitator, intersection leaf agitator, and/or, at least one other agitating element (5 '; 5 ") be selected from: tiltedly leaf agitator, intersect leaf agitator, there is the agitator that spirals spiraled of continuous print or interruption, ribbon agitator and there is the anchor agitator of the arm tilted relative to rotational plane.

Reactor the most according to claim 1 and 2 (1), it is characterized in that, exist in the region between the upper seamed edge and the upper end of described reactor inner chamber (3) of described guiding tube (7) at least one other guiding tube (7 ') and/or

Described guiding tube has in axial direction at the upwardly extending protuberance in side (7 ") of the upper end towards described reactor inner chamber (3), and described protuberance has perforation and/or is configured to orifice plate.

11. reactors according to claim 1 and 2 (1), it is characterized in that, described guiding tube (7) location in described reactor inner chamber (3) in the axial direction, the mean residence time of 2 hours is there is in the case of making the 50% of the minimum loading of the reactant mixture loading in the nominal production capacity less than described reactor, described minimum loading causes the minimum packed height of described reactant mixture, and in the case of this minimum packed height, the upper seamed edge of described guiding tube (7) sinks in described reactant mixture.

12. reactors according to claim 1 and 2 (1), it is characterised in that described reactor wall portion (2) can be carried out homoiothermic.

13. reactors according to claim 1 and 2 (1), it is characterised in that described heat exchanger (10) is pipe heat exchanger.

14. reactors according to claim 13 (1), it is characterised in that described pipe heat exchanger is:

Including by being perpendicular to the bundle that constitutes of coil pipe that axial direction stretches, under environmental condition and/or service condition, the heat carrier flow influencing meridian of liquid crosses described coil pipe around, wherein said reactant mixture washing-round pipe or coil pipe, or

Including the body closed, described body has the pipe being directed through described body stretched in the axial direction, wherein product stream influencing meridian crosses described pipe, described pipe in the described body closed by environmental condition around and/or service condition under the heat carrier washing-round of liquid, or

Including the pipe stretched in the axial direction or coil pipe, under environmental condition and/or service condition, the heat carrier flow influencing meridian of liquid crosses described pipe or coil pipe around, pipe or coil pipe described in wherein said reactant mixture washing-round.

15. reactor according to claim 2 (1), it is characterized in that, the spacing (a) measured in the projection on described reactor bottom is 0.01≤a/h≤0.2 relative to axial design size (h) of described reactor inner chamber.

16. reactors according to claim 2 (1), it is characterized in that, the spacing (a) measured in the projection on described reactor bottom is 0.05≤a/h≤0.15 relative to axial design size (h) of described reactor inner chamber.

17. reactors according to claim 3 (1), it is characterized in that, the ratio for the axial design size (h) of axial design size (h ') and the described reactor inner chamber (3) of described guiding tube (7) is suitable for: 0.075≤(h '/h)≤0.4.

18. reactors according to claim 3 (1), it is characterized in that, the ratio for the axial design size (h) of axial design size (h ') and the described reactor inner chamber (3) of described guiding tube (7) is suitable for: 0.1≤(h '/h)≤0.25.

19. reactors according to claim 3 (1), it is characterized in that, the external diameter (d ') of described guiding tube (7) is suitable for the ratio of the diameter (d) of described reactor inner chamber (3): 0.3≤(d '/d)≤0.5.

20. reactors according to claim 4 (1), it is characterised in that described ratio y/x is suitable for: 0.95≤(y/x)≤0.98.

21. reactors according to claim 5 (1), it is characterised in that the subtended angle of described cone is 55 ° to 120 °.

22. reactors according to claim 5 (1), it is characterised in that the subtended angle of described cone is 60 ° to 100 °.

23. reactors according to claim 7 (1), it is characterized in that, the ratio for described design size (z) with the diameter (d) of described reactor inner chamber (3) is suitable for: 0.8≤(z/d)≤0.98.

24. reactors according to claim 7 (1), it is characterized in that, the ratio for described design size (z) with the diameter (d) of described reactor inner chamber (3) is suitable for: 0.9≤(z/d)≤0.98.

25. reactors according to claim 12 (1), it is characterised in that described reactor wall portion (2) can be divided into the district of multiple individually energy homoiothermic in axial direction arranged.

26. reactors according to claim 12 (1), it is characterized in that, described reactor wall portion (2) can be divided into the district (I of three individually energy homoiothermics in axial direction arranged, II, III), wherein the district (I) of the first energy homoiothermic constitutes the upper end to described guiding tube (7) at axial direction from described reactor bottom, the district (II) of the second energy homoiothermic is constituted in the axial direction on the upper end of described guiding tube (7), and the district (III) of the 3rd energy homoiothermic constitutes on described secondth district (II) and includes the upper end of described reactor wall portion (2), described upper end is reactor cap.