专利摘要:
The present invention relates to a method and an apparatus (10, 20) for the continuous preparation of organic peroxides, the reactor comprising at least one flow channel (1, 1a, 1b) designed as a reaction zone; an inlet system (2) which is in fluid communication with a first end of said at least one flow channel and adapted to introduce two or more substances or a combination of substances into said at least one flow channel; an outlet system (3) in fluid communication with a second end of said at least one flow channel, the second end being located downstream of the first end and the outlet system being adapted to extract a reaction product present at the the second end; an oscillatory system (4, 5) arranged to superpose an oscillatory flow to the flow of substances which passes through said at least one flow channel, the oscillatory flow being effected in at least one section of said at least one flow channel; flow; and a controller adapted to implement the control method of the input system to introduce, according to a first feature, at least two substances or a combination of substances into said at least one flow channel, of the system. oscillatory flow to superpose an oscillatory flow at least a portion of the flow of substances passing through said at least one flow channel and the outlet system to continuously extract the reaction product formed in the flow channel of the substances introduced in such a way that the mass flow of output corresponds to the sum of the input mass flow rates.
公开号:FR3042793A1
申请号:FR1560186
申请日:2015-10-26
公开日:2017-04-28
发明作者:Albert Blum；Philippe Maj；Serge Hub
申请人:Arkema France SA；
IPC主号:

专利说明:

SYNTHESIS OF ORGANIC PEROXIDES USING AN OSCILLATORY FLOW Reactive REACTOR
FIELD OF THE INVENTION
The present invention relates to an efficient and safe synthesis of organic peroxides and in particular to a continuous synthesis of organic peroxides under oscillatory flow conditions.
HISTORY OF THE INVENTION
Organic peroxides play an important role as initiators in the preparation of polymers or as oxidants in medical preparations and complex chemical syntheses.
Organic peroxides are thermally sensitive, highly reactive compounds known to decompose in a self-accelerating exothermic reaction when not maintained at a sufficiently low temperature. The start and the evolution of a respective autoaccelated reaction not only depend on the temperature, but also on the heat dissipation conditions in which the respective organic peroxide is maintained. A SADT (Self Accelerating Decomposition Temperature) defining the lowest temperature at which the exothermic decomposition can start therefore does not represent an absolute value but also reflects the conditions under which the respective organic peroxide is maintained. Smaller packages usually have a higher surface area to volume ratio than larger packages and therefore better heat dissipation conditions, resulting in higher SADTs.
Due to their thermal instability, a synthesis of organic peroxides requires a very precise temperature regulation to avoid any serious incidents. Since the respective production or preparation processes use a two-phase or multi-phase immiscible phase reaction, careful mixing of the reaction components is necessary to achieve a satisfactory reaction rate.
Organic peroxides can be produced in batch or continuous processes. In batch processes, the reagents either are all charged to a reactor (batch reaction), or a reagent or catalyst is assayed in the other reactants in a reactor (semi-continuous reaction). The ratio between the reaction volume and the cooling surface available in these reactors is usually high, which makes precise regulation of the temperature difficult and thus limits the amount of organic peroxides that can be safely produced within a batch.
For larger production volumes, therefore, continuous processes of preparation are preferred, wherein feed of the starting materials and extraction of the final product occur on a continuous basis. L. Fritzsche and A. Knorr describe, in "Transformation of the 2nd step of a peroxyester synthesis from semi-batch to continuous mode", Chemical Engineering and Processing 70 (2013) 217-221, a transformation of a synthesis of organic peroxides from a semi-continuous mode to a continuous mode. The reaction is carried out in a continuous flow tubular reactor subjected to ultrasound for improved mixing and an increase in the interface of the phase boundary and thus a better mass transfer between the two phases.
In "Continuing synthesis of a high energetic substance using small scale reactors", Chemical Engineering Transactions, 32 (2013) 685-690, L. Fritzsche and A. Knorr describe a "split-and-recombine" reactor (SAR - division and recombination ), in which two meander channels divide and recombine repeatedly throughout their lengths. The SAR reactor is used for the synthesis of TBPEH (tert-butyl peroxy-2-ethylhexanoate) with ultrasound application.
WO 2008/006666 A1 for example describes a continuous process for the preparation of acyl peroxides using a reactor having two reaction zones. The first reaction zone is designed as a loop reactor, where most of the two-phase reaction mixture is circulated in a cooled loop, while part of it, or more precisely between 20% and 50% of the volume in circulation, is fed into the second reaction zone and replaced by a corresponding amount of newly fed starting materials. The second reaction zone is formed by a stirred cell reactor, wherein two or more reaction cells are connected in series, the contents of each of the reaction cells being mixed with at least one stirrer. The reaction cells are connected to each other in such a way that there is virtually no back-mixing of the reaction mixture of a downstream reaction cell in an upstream reaction cell. Although allowing for continuous preparation of organic peroxides, the treatment in the second reaction zone represents a continuous stirred tank reactor (CSTR) sequence rather than a continuous flow continuous reactor, since the second reaction zone represents a continuous flow tank reactor. The reaction zone is organized into a cascade of cells, each cell treating a certain portion of the total reaction volume for a specified period. Due to the cell treatment, the ratio between the cooling surface and the volume of the reaction mixture is still comparatively low in the second reaction zone, which limits the flow of the reactor or requires a large number of reaction cells. In contrast to a continuous flow reaction, stirring results in remixing portions where the conversion is in an advanced state with portions where the conversion is still low. As a result, CSTRs require many cells to achieve good final conversion. As a further consequence of remixing, mechanical stirrers do not provide a finely dispersed mixture of phases, resulting in a comparatively low conversion and / or a long residence time (time required for the reaction mixture to pass through the reactor).
Continuous flow reactors such as, for example, tubular reactors, plate reactors or the like allow for continuous preparation of organic peroxides in a continuous flow. The continuous flow reactors comprise at least one reactor channel through which the reaction mixture passes, the channels being connectable in parallel and / or in series when more than one reactor channel is used. Due to the continuous flow of the reaction mixture through the reactor channels, a local concentration of reaction components is roughly a function of the distance the reaction mixture passes along the length of the reactor channel (s) to the reaction zone. at the respective position and can be described by means of a plug flow reactor model. In other words, the concentration of constituents of the reaction mixture is assumed to change only along its flow direction, while not having transverse gradients with respect to the direction of flow.
Phase mixing in continuous flow reactors is usually accomplished by creating turbulence, i.e. irregular local flows in different directions relative to the main direction of flow. Turbulence can be created either by means of high flows (usually characterized by a Reynolds number greater than about 3000) or by the introduction of redirection means into the flow path, such as baffles (see example WO 1999/55457 A1), or by irregularities of the channel walls (for example protrusions or helical indentations, as disclosed in WO 2006/092360 A1) or by modifications in the direction of the reaction or reaction channel. the flow path (as for example described in WO 2012/095176 A1) or by division and recombination of the flow (for example herringbone structures, as described in WO 2014/044624 A1). Turbulence not only carefully mixes the immiscible phases present in the synthesis of organic peroxides, but usually also results in smaller maximum droplet sizes than are possible with mechanical agitation means such as stirrers or the like. Larger sizes of smaller droplets in turn achieve larger reaction surfaces, which results in higher reaction rates and thus shorter reaction times. Since a mixture based on turbulence does not require moving parts, the respective reactors are also called static mixers.
The process conditions for the synthesis of organic peroxides can be improved by the use of so-called mini-reactors. Mini-reactors are characterized in that they have flow channel dimensions (transverse to the main direction of flow) in the range of millimeters (milliameners) or even micrometers (microreactors). The use of minireactors significantly reduces the local reaction volume, while at the same time increasing the ratio between the available reactor channel area for cooling and the reactor channel volume. This allows for improved regulation of local reaction temperatures which, together with smaller local volumes, improves the safety of the preparation process.
An example of a DC continuous flow mini-reactor is a plate heat exchanger such as for example described in WO 2007/125091 A1. The plate heat exchanger comprises three plates arranged to form reactor channels and water channels. heat exchange between them. The reactor can be used for the synthesis of organic peroxides for which two reactor channels are connected in series. Two reagents are fed into one of the two reactor channels to form an intermediate product which is then fed into the other of the two reactor channels together with a third reagent to form the final product. A heat transfer fluid flows through the heat exchange channels to dissipate the heat of reaction.
An example of a continuous flow continuous mini-reactor is disclosed in WO 2014/044624 A1. The reactor comprises at least two comb-type structures with inclined teeth. One of the two structures is arranged above the other so that the teeth of the two structures intersect. The structures thus combined are placed in a housing, covering the top and bottom faces to form intersecting paths along which the repetitive change in direction of flow of a fluid is forced. To allow preparation of organic peroxides, the housing is placed in a tube through which a cooling liquid passes.
The continuous flow mini-jet disclosed in WO 2012/095176 A1 uses a reaction channel, the path directions of which change repeatedly. The reaction channel is formed in a plate covered by another plate. To intensify the turbulence and thus improve the mixing of the treated fluid, an oscillatory flow is superimposed on the permanent flow of the fluids. The oscillatory flow is limited to a region between the inlet for the starting materials and the outlet for the final product and causes recurrent high flows within the reactor. The term "oscillatory flow" means a variation of the flow as a function of time, the average flow rate of an oscillatory flow being equal to zero. When superimposing an oscillatory flow to a permanent flow, the average flow is thus given by the speed of the permanent flow. Due to the higher temporary flow rates, however, greater turbulence is created which results in a more efficient mixing of the constituents of the reaction mixture. The residence time of the reaction mixture is not influenced by the oscillatory flow, since the average flow rate is always equal to the steady flow.
A superimposition of an oscillatory flow to a permanent flow has already been described in US Pat. No. 4,271,007 as an appropriate means for preventing solid deposition on the walls of a tubular reactor used for the cracking of high-grade hydrocarbons. temperature. The oscillation frequency used was 115 Hz. WO 2012/095176 A1 discloses the use of oscillatory flow in a mini-reactor, the reactor channel of which is designed with repeated changes of path. The oscillatory flow is superimposed on a steady flow to effectively mix a suspension in treatment, such that deposition of solid material in the reactor is prevented and no concern for sedimentation or sedimentation is required. any fouling or clogging of the reactor.
A preparation of organic peroxides in continuous flow reactors is now carried out under steady flow conditions, where the local flow rates do not change with time. To obtain a required mixture of constituents in the reaction mixture, the flow rate of the reaction mixture must be high enough to cause turbulent flow conditions. In this context, it is noted that, although turbulence introduces chaotic flow conditions, the flow rate through a section of the reactor (a length of the flow channel) does not generally change with time and the The term "steady flow conditions" in this document is therefore also used for turbulent flows, where the profile of fluid motion along the length of the reactor path does not change with time. The term "permanent flow" as used in this specification refers not only to a permanent flow (possibly changing slowly and / or slightly) but also to intermittent, more or less periodic flow characteristics, such as flows. pulses, whose intermission periods are significantly shorter than the reaction time, for example by a factor of ten or more. Since a synthesis of organic peroxides must be carried out at relatively low temperatures, the reaction times required are comparatively long. In order to complete a respective synthesis to the desired extent in a continuous flow reactor used under steady-state conditions, the reaction mixture must remain in the reactor throughout the necessary reaction time. The time elapsing between an introduction of starting materials and the output of a final product synthesized from these starting materials is called the residence time and corresponds to the reaction time above. Together with the flow rate of the reaction mixture, this period of time defines the length of the required reaction path. The higher the flow rate required and the longer the residence time, the longer the flow channel defining the path.
A synthesis of organic peroxides also requires effective regulation of the temperature of the reaction medium. The lateral dimensions of the flow channel, that is to say its transverse dimensions with respect to the direction of the flow that it defines, must therefore be, at least in one direction, sufficiently small to guarantee a transfer. effective thermal. Because of these limitations of the cross-section, a long flow channel implies a high flow resistance. High resistance to flow in turn cause considerable pressure losses which are difficult to handle and which may represent a technical challenge to the implementation of a respective reactor. In addition, long reaction flow channels also involve large reaction volumes which give rise, in the case of peroxides, to serious risks.
There is therefore a desire for a method and apparatus for safe, large scale synthesis of organic peroxides under continuous, continuous flow conditions.
SUMMARY OF THE INVENTION The above object is obtained by the invention as defined in the independent claims.
A respective process for the continuous preparation of organic peroxides includes the step of using a continuous flow reactor having at least one flow channel designed as a reaction zone; an inlet system which is in fluid communication with a first end of said at least one flow channel and which is adapted to introduce two or more substances or a combination of substances into said at least one flow channel; an outlet system in fluid communication with a second end of said at least one flow channel, the second end being located downstream of the first end and the outlet system being adapted to extract a reaction product present at the second end; end; and an oscillatory system designed to superpose an oscillatory flow to the flow of substances that passes through said at least one flow channel, the oscillatory flow being performed in at least one section of said at least one flow channel. The process for continuous preparation of organic peroxides further comprises the steps of introducing, according to a first characteristic, at least two substances or a combination of substances into said at least one flow channel; superimposing, by the use of the oscillatory system, an oscillatory flow to at least a portion of the flow of substances passing through said at least one flow channel to create turbulence in the flow of substances; and extracting the reaction product formed in said at least one flow channel of the introduced substances, the extraction being carried out continuously using the output system, the output mass flow corresponding to the sum of the flow rates input mass.
In this context, it is noted that the terms "including", "comprising", "containing", "presenting" and "with", as well as the corresponding grammatical modifications, used in this specification and in the claims to list characteristics, should generally be considered as specifying a non-exhaustive list of features, such as, for example, process steps, constituents, ranges, dimensions or the like and in no way detract from the presence or addition of a or several other features or one or more groups of other features or additional features. It is further noted that the term "reaction product" as used herein specifies the result of a reaction that has occurred in the reaction zone (s) of the reactor and not only the product of a reaction product. chemical reaction based on the starting materials. It is also understood that the term "substance" is used to specify a starting material in the meaning of a reactant or a reagent as well as in the meaning of a mixture of reactants with one or more other materials, such as for example a solvent or a catalyst or the like, and that the term "flow of substances" includes not only the substances introduced but also possible reaction products already brought into the process. The term "substances" in particular specifies the reactants, additives and solvents necessary and used for the preparation of an organic peroxide. Finally, it is pointed out that the term "continuous" is used in this specification to characterize any process or any operation carried out continuously or intermittently and not in separate parts as is characteristic for batch processing.
Advantageously, the step of using a continuous flow reactor comprises the use of a reactor further having a temperature control system designed to regulate the temperature profile along the length of said at least one channel. and the method further comprising the step of controlling the temperature profile along said at least one flow channel using the temperature control system.
Also, the step of superimposing an oscillatory flow to at least a portion of the flow of substances that passes through said at least one flow channel includes the use of an oscillatory system having a flow generating device. an oscillatory flow in fluid communication with said at least one flow channel at a first position and a hydraulic accumulator in fluid communication with said at least one flow channel at a second position different from the first position.
The process is advantageously carried out in an apparatus designed as a continuous flow reactor which comprises at least one flow channel designed as a reaction zone; an inlet system which is in fluid communication with a first end of said at least one flow channel and adapted to introduce two or more substances or a combination of substances into said at least one flow channel; an outlet system in fluid communication with a second end of said at least one flow channel, the second end being located downstream of the first end and the outlet system being adapted to extract a reaction product present at the second end; end; an oscillatory system designed to superpose an oscillatory flow to the flow of substances which passes through said at least one flow channel, the oscillatory flow being performed in at least one section of said at least one flow channel; and a controller adapted to control the input system to introduce, according to a first feature, at least two substances or a combination of substances into said at least one flow channel, the oscillatory system to superimpose a flow. oscillating at least a portion of the flow of substances passing through said at least one flow channel and the outlet system for continuously withdrawing the reaction product formed in the flow channel of the substances introduced in such a way that the mass output flow corresponds to the sum of the input mass flow rates.
By means of a method of preparation and an apparatus as specified above, the turbulent flow conditions required for thorough mixing of the reaction components can be achieved to a large extent, regardless of the nominal flow rate of the continuous flow reactor. While the nominal flow rate is roughly defined by the average flow capacity of the reactor and therefore by the mass flow introduced via the inlet system, the turbulent flow conditions are defined by the effective flows that are, because of the superimposed oscillatory flow, higher, repeatedly, than the average flow. By obtaining turbulent flow conditions without having to increase the average flow rate of the reaction mixture, shorter continuous flow reactors can be used and the volume of material in the process can be reduced. Since the oscillatory flow supports a reduction in the maximum size of the droplets and an increase in the minimum size of the two-phase mixture droplets, it can also be used to advance the reaction, to reduce the required residence time, to reduce side reactions and avoid the formation of difficult to separate emulsions. While the residence time can now be regulated only by adjusting the flow of substances introduced via the inlet system, the reaction kinetics can be independently controlled by the oscillatory flow conditions.
Since the oscillatory flow rates are adjustable, irrespective of the average flow rate, continuous flow reactors may be used which are free of small jets, baffles, orifices or other obstacles that increase the cost of the reactor, impairing its resistance to corrosion. flow, giving rise to deposits of material and clogging and also resulting in irregular distribution of droplet sizes, which raises the risk of a presence of "dead" zones with very weak reaction and "hot" points with a very strong reaction. fast. Applying an oscillatory flow to the respective continuous flow reactors results in a uniform distribution of droplets, the size of which is defined by the oscillatory flow conditions, and determines the mass transfer occurring in the reaction, thereby permitting ease of regulation of the preparation process with very good space-time yields (quantity of product obtained per reactor unit volume and time unit). Since the ratio of the surface surrounding the reaction mixture to the volume surrounded by the surface is sufficiently high in the continuous flow reactors to allow efficient removal of the heat generated during the chemical conversion process, reaction temperatures greater than 50.degree. the SADT defined for the respective organic peroxide when stored in a container can be used without running a risk which results in shorter reaction times.
Owing to being able to adjust reaction kinetics and residence times, independently of one another, to different reactor architectures, there are no restrictions as to the type of reactor to be used. continuous flow to use, the type of organic peroxides to be produced or the reaction kinetics (fast or slow) to apply. By being able to adjust a process for producing organic peroxides to a given continuous flow reactor architecture and to optimize the process of preparation with regard to maximum possible space-time yield without having to modify the reactor itself or having to operate the reaction process outside the safety constraints, the preparation times as well as the downtimes for the different production cycles can thus be minimized.
Preferred embodiments of the method of preparation further include the step of using a continuous flow reactor that utilizes a temperature control system, designed to regulate the temperature profile along the length of the flow channel. flow, and another process step of controlling the temperature profile along said at least one flow channel using the temperature control system. The other process step is advantageously carried out by the reactor control device which is furthermore designed for controlling the temperature control system to regulate the temperature profile along said at least one flow channel. .
Certain designs of the above-described temperature control system may further allow regulation of the temperature profile in sections such that a temperature profile in a section of said at least one flow channel can be regulated independently a temperature profile in another section of said at least one flow channel. Temperature control systems and respective controllers allow, if necessary, precise adjustment of reaction temperatures, which can also be adjusted to vary along the length of said at least one flow channel.
According to advantageous embodiments, an introduction of said at least two substances according to the first characteristic comprises the introduction of at least one of the two substances in a constant or pulsed manner. The introduction of said one or more substances in a pulsed manner does not influence the reaction process in the reactor and allows the use of pulsed pumps such as diaphragm or piston dosing pumps (with multiple heads) without requiring damper.
Preferred embodiments may include performing the step of superimposing an oscillatory flow on at least a portion of the flow of substances that passes through said at least one flow channel using a oscillatory system comprising a device for generating an oscillatory flow in fluid communication with said at least one flow channel in a first position and a hydraulic accumulator in fluid communication with said at least one flow channel in a second, different position from the first position. The use of a respective oscillatory system allows a rearward and forward displacement of a volume of reaction mixture between the device for generating an oscillatory flow and the hydraulic accumulator and through at least one a portion of said at least one flow channel without influencing the operation of the input and output system.
Preferred embodiments may further include the step of using a continuous flow reactor, wherein at least one flow channel includes a first flow channel and a second flow channel, a first end of first flow channel being in fluid communication with the inlet system and a second end of the first flow channel being in fluid communication with a first end of the second flow channel. A respective reactor further comprises a recirculation system adapted to reintroduce a portion of the reaction mixture exiting the second end of the first flow channel into the first flow channel upstream of its second end. The respective preferred embodiments of the preparation process further include the step of reintroducing a portion of the reaction mixture exiting the second end of the first flow channel into the first flow channel upstream of its second end. using the recirculation system.
Advantageously, the step of using a continuous flow reactor comprises the use of the first flow channel formed by three flow channel modules connected in series, the first flow channel module and the second module. each flow channel being each formed by a "split-and-recombine" reactor while the third flow channel module is formed by a meander channel reactor, and the inlet system being adapted to introduce a first substance in a first inlet of the first flow channel module and for introducing a second substance into a first inlet of the second flow channel module, the outlet of the first flow channel module being in fluid communication with a second inlet of the second flow channel module, the output of the second flow channel module being in fluid communication with the input of the third channel channel module flow and the outlet of the third flow channel module being in fluid communication with a recirculation system adapted to reintroduce a portion of the reaction mixture exiting the third flow channel module into a second inlet of the first flow channel module .
Advantageously, the recirculation system comprises the device for generating an oscillatory flow and the hydraulic accumulator being in fluid communication with the second end of the second flow channel. The step is preferably carried out by the control device, which is furthermore designed for controlling the recirculation system to reintroduce a portion of the reaction mixture exiting the second end of the first flow channel into the first channel. flow upstream of its second end.
In designs of the respective embodiments, the recirculation system advantageously comprises a device for generating an oscillatory flow, the hydraulic accumulator being in fluid communication with the second end of the second flow channel. In these embodiments, the device for generating an oscillatory flow performs both a reintroduction of a portion of the reaction mixture exiting the second end of the first flow channel and a superposition of an oscillatory flow to a flow. permanent in the second flow channel.
In some designs of these embodiments, the step of controlling the temperature profile along said at least one flow channel using the temperature control system further includes the use of a temperature control system. temperature control having a first heat exchange system and a second heat exchange system, the first heat exchange system being designed for heat exchange with the first flow channel and the second heat exchange system being designed for heat exchange with the second flow channel, which allows regulation of the temperature profile along the first flow channel, separately from the temperature profile along the second flow channel. The step is preferably performed by the controller, which is furthermore designed to regulate the temperature profile along the first flow channel separately from the temperature profile along the second flow channel. The respective designs allow optimized adaptation of the temperature profiles to the different reaction conditions present in the two flow channels.
In advantageous embodiments of a process of preparation above, the step of using a continuous flow reactor comprises the use of a reactor which further comprises an additional inlet system designed to introduce one or more substances in said at least one flow channel downstream from its first end, the method further comprising the step of introducing one or more additional substances into said at least one downstream flow channel at its first end, according to a second characteristic, and the output mass flow achieved by the output system further includes also the additional input mass flow rate. The step is preferably performed by the controller, which is furthermore designed to control the additional inlet system to introduce one or more additional substances into the at least one downstream flow channel. its first end, according to a second feature, and to control the output system to achieve the mass output flow to also include the additional input mass flow rate. A respective additional inlet system allows more precise control of the desired reaction processes and increases the versatility of the preparation process.
According to preferred embodiments, the step of using a continuous flow reactor comprises the use of a reactor whose oscillatory system is designed to generate an oscillatory flow having a frequency between 0.1 Hz and 500 Hz more preferably between 1 and 50 Hz and even more preferably between 5 Hz and 25 Hz. The respective oscillation frequencies provide a real oscillatory motion of the reaction mixture which forms the basic condition for creating the turbulence necessary for mixing the mixture.
In preferred embodiments, the step of using a continuous flow reactor may further include using a reactor whose oscillatory system is designed to generate an oscillatory flow having a maximum flow in the range of 1 to 500 times the average flow rate of the first characteristic. A respective oscillatory system allows adjustment of the oscillatory flow to the construction details of said at least one flow channel and the viscosity and other characteristics of the reaction mixture treated in said at least one flow channel.
In other advantageous embodiments, the input system is also in fluid communication with a previous reactor and adapted to transfer a combination of substances representing a pretreated reaction mixture from the preceding reactor into said at least one flow channel and / or or the outlet system is also in fluid communication with a subsequent reactor and adapted to transfer a reaction product present at the second end of said at least one flow channel into the subsequent reactor. The transfer of the substances is carried out by the controller designed to control the input system and the output system as required.
It is noted that the reactor characteristics disclosed above in the context of the process for continuous preparation of organic peroxides are analogously qualified as characteristics of the continuous flow reactor apparatus.
A process and apparatus as described above are favorably used for a preparation of organic peroxides, in pure and / or diluted form, selected from the following classes of peroxides - diacyl peroxides, peroxyesters, peroxycarbonate esters, peroxydicarbonates, hydroperoxides , dialkyl peroxides, ketone peroxides, peroxyketals, monoperoxydecals, peroxycarboxylic acids - and mixtures thereof: diacyl peroxides, such as, for example, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, o-methylbenzoyl peroxide 3,5,5-trimethylhexanoyl peroxide; peroxyesters, such as, for example, 1,1-dimethyl-3-hydroxybutyl peroxyneodecanoate, α-cumyl peroxneodecanoate, α-cumyl peroxneoheptanoate, tert-amyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, tert-butyl peroxypivalate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, tert-amyl peroxy-2-ethylhexanoate, peroxy-2-ethylhexanoate tert-butyl peroxyacetate, tert-butyl peroxyacetate, tert-butyl peroxyacetate, tert-amyl perbenzoate, tert-butyl perbenzoate, tert-butyl peroctoate; peroxycarbonate esters, such as for example 00-tert-amyl-O- (2-ethylhexyl) monoperoxycarbonate, OO-tert-butyl-O-isopropyl monoperoxycarbonate, 100-tert-butyl-1 monoperoxycarbonate; - (2-ethylhexyl), poly (tert-butyl peroxycarbonate) polyether; Peroxydicarbonates, such as, for example, di (n-propyl) peroxydicarbonate, di (sec-butyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate; Hydroperoxides, such as, for example, cumene hydroperoxide, tert-amyl hydroperoxide or tert-butyl hydroperoxide; Dialkyl peroxides, such as for example di-tert-amyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butyl-peroxy) -hexane, 2,5-dimethyl-2,5-di (tert-butyl-peroxy) -hexyne; Ketone peroxides, such as, for example, cyclohexanone peroxide, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide or acetyl acetone peroxide; Peroxyketals, such as, for example, 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (tert-butylperoxy) cyclohexane, 1,1-di (tert- amylperoxy) cyclohexane, 4,4-di (tert-butylperoxy) n-butyl valerate, 3,3-di (tert-amylperoxy) ethyl butyrate, 3,3-di (tert-butylperoxy) butyrate ethyl; Monoperoxy ketals (ether peroxides), such as, for example, 1-methoxy-1- (tert-amylperoxy) cyclohexane; Peroxycarboxylic acids, such as, for example, succinic acid peroxide, perpropionic acid. The invention also relates to a continuous flow reactor, comprising at least one flow channel designed as a reaction zone; an inlet system in fluid communication with a first end of said at least one flow channel and adapted to introduce two or more substances or a combination of substances into said at least one flow channel; an outlet system in fluid communication with a second end of said at least one flow channel, the second end being located downstream of the first end and the outlet system being adapted to extract a reaction product present at the second end; end; an oscillatory system designed to superpose an oscillatory flow to the flow of substances that passes through said at least one flow channel, the off-line oscillatory flow performed in at least one section of said at least one flow channel; and a controller adapted to control the input system to introduce, according to a first feature, at least two substances or a combination of substances into said at least one flow channel, the oscillatory system to superimpose a flow. oscillating at least a portion of the flow of substances passing through said at least one flow channel and the outlet system for continuously withdrawing the reaction product formed in the flow channel of the substances introduced in such a way that the mass output flow corresponds to the sum of the input mass flow rates. Other embodiments are detailed below: - it further comprises a temperature control system, designed to regulate the temperature profile along the length of the flow channel and the control device being furthermore configured to control the temperature control system to regulate the temperature profile along said at least one flow channel; the oscillatory system comprises a device for generating an oscillatory flow mounted in fluid communication with said at least one flow channel in a first position and a hydraulic accumulator mounted in fluid communication with said at least one flow channel in one second position, different from the first position; said at least one flow channel comprises a first flow channel and a second flow channel, a first end of the first flow channel being in fluid communication with the input system and a second end of the first channel flow path being in fluid communication with a first end of the second flow channel, the reactor further comprising a recirculation system adapted to reintroduce a portion of the reaction mixture exiting the second end of the first flow channel into the first channel upstream of its second end and the control device being further adapted to control the recirculation system to reintroduce a portion of the reaction mixture exiting the second end of the first flow channel into the first flow channel upstream of its second end; the first flow channel is formed by three flow channel modules connected in series, the first flow channel module and the second flow channel module being each formed by a split-and-recombine reactor while the third flow channel module is formed by a meander channel reactor, and the input system being adapted to introduce a first substance into a first inlet of the first flow channel module and to introduce a second substance in a first input of the second flow channel module, the output of the first flow channel module being in fluid communication with a second input of the second flow channel module, the output of the second flow channel module flow being in fluid communication with the inlet of the third flow channel module and the outlet of the third flow channel module being in communication fluidic means with a recirculation system adapted to reintroduce a portion of the reaction mixture exiting the third flow channel module into a second inlet of the first flow channel module; the recirculation system comprises the device for generating an oscillatory flow and the hydraulic accumulator being in fluid communication with the second end of the second flow channel; the temperature control system comprises a first heat exchange system and a second heat exchange system, the first heat exchange system being designed for heat exchange with the first flow channel and the second heat exchange system. heat exchange being designed for heat exchange with the second flow channel, and the controller further being adapted to regulate the temperature profile along the first flow channel separately from the temperature profile along the second flow channel; flow channel; it further comprises an additional inlet system adapted to introduce one or more substances into said at least one flow channel downstream from its first end, the control device being further adapted to control the additional inlet system to introduce one or more additional substances into said at least one flow channel downstream from its first end, in accordance with a second characteristic, and to control the output system to realize that the mass output flow includes furthermore the additional input mass flow rate; the oscillatory system is designed to generate an oscillatory flow having a frequency between 0.1 Hz and 500 Hz, preferably between 1 and 50 Hz and more preferably between 2 Hz and 25 Hz; the oscillatory system is designed to generate an oscillatory flow having a maximum flow in the range representing 1 to 500 times the average flow rate of the first characteristic.
Starting materials for the preparation of an organic peroxide using a process according to the present invention are known to those skilled in the art.
The following reaction schemes illustrate the preparation of different classes of peroxides and present the required materials, in a nutshell (diluents and / or other optional / necessary additives are not shown, the acid chlorides could also be anhydrides of acid):
Diacyl peroxides: Acid chlorides and hydrogen peroxide form diacyl peroxides. RC (0) C1 + H2O2 + 2 NaOH / KOH * · RC (0) O00C (O) R + 2 H20 + 2 NaCl / KCl
Peroxyesters: acid chlorides and organic hydroperoxides form peroxyesters. R'C (O) C1 + R "OOH + NaOH / KOH R'C (O) O + R0 + NaCl / KCl
Peroxycarbonate Esters: Organic chloroformates and hydroperoxides form peroxycarbonates.
R'0C (O) C1 + R "OOH + NaOH / KOH R'OC (O) O" + H2O + NaCl / KCl
Peroxydicarbonates: chloroformates and hydrogen peroxide form peroxydicarbonates. 2 ROC (0) Cl + H2O2 + 2 NaOH / KOH * · ROC (0) 00C (0) OR + 2 H2O + 2 NaCl / KCl
Hydroperoxides: alcohols and hydrogen peroxide form hydroperoxides (for example with an acid such as H 2 SO 4 as a catalyst).
ROH + H2O2 ^ ROOH + H2O
Dialkyl peroxides: Alcohols and hydrogen peroxide form hydroperoxides (for example with an acid such as H 2 SO 4 as a catalyst).
2 ROH + H2O2 - * ROOR + H2O
Ketone peroxides: ketones and hydrogen peroxide form ketone peroxides (for example with an acid such as H 2 SO 4 as a catalyst).
R'C (0) R "+ 2 H2O2 * · R'C (OOH) 2R" + H2O
Peroxyketals: ketones and organic hydroperoxides form peroxyketals (for example with an acid such as H 2 SO 4 as a catalyst). R'C (0) R "+ 2 R '" OOH * · R'C (OORm) 2R "+ H20
Monoperoxy ketals (ether peroxides): organic ketones, alcohols and hydroperoxides form monoperoxy ketals (for example with an acid such as H 2 SO 4 as a catalyst).
R'C (0) R "+ R '" OH + R "" OOH * · R'C (OR' ") (OOR" ") R" + HaO
Peroxycarboxylic acids: carboxylic acid and hydrogen peroxide form peracids. RC (O) OH + H2O2 RC (O) 00H + H20 Other features of the invention will flow from the following description of illustrative embodiments, the claims and the accompanying figures. It is noted that embodiments of the present invention may implement the features described below in the context of particular embodiments in combinations different from those used by the illustrative embodiments. The present invention is therefore limited only by the scope of the appended claims and not by any of the illustrative embodiments below.
BRIEF DESCRIPTION OF THE FIGURES
In explaining the present invention in more detail with respect to particular embodiments, reference is made to the accompanying figures, in which
Figure 1 is a schematic representation of a first design of an apparatus using a continuous flow stirred reactor for superposition of oscillatory flow to a steady flow of a reaction mixture.
Figure 2 is a schematic representation of a second design of an apparatus using a continuous flow stirred reactor, where a loop reaction zone is located upstream of another reaction zone designed to superimpose an oscillatory flow to a permanent flow of a reaction mixture.
Figure 3 is a schematic representation of a third apparatus design, wherein a loop reaction zone having three reactor modules is located upstream of another reaction zone designed to superimpose oscillatory flow to a steady flow. a reaction mixture and
Figure 4 is a diagram illustrating the basic steps of a process for continuous preparation of organic peroxides using an oscillatory flow superimposed on a permanent flow of a reaction mixture.
DETAILED DESCRIPTION OF THE INVENTION
In the illustrative embodiments described below, elements having a similar function and structure are referenced, as far as possible, by like reference numerals. Therefore, to understand the characteristics of the individual elements of a specific embodiment, reference should also be made to the description of other embodiments and the summary of the disclosure.
The diagram of FIG. 1 illustrates a first embodiment of an apparatus representing a continuous flow reactor. The substances and / or a combination of substances forming the starting materials are introduced into a reaction zone 1 via an inlet system 2. The substance or substances resulting from a process occurring in the reaction zone 1 are output via an output system 3. The input system 2 and the output system 3 are designed to generate a permanent flow of substances between them. The inlet system 2 is usually designed to actively introduce the starting materials into the reaction zone 1, while the output system 3 may, in some embodiments, be implemented as a passive device, such as the Fig. 1. Other embodiments also show an implementation of the output system as an active device, which actively extracts the reaction product.
As already mentioned above, the term "permanent flow" is intended here to characterize a flow that does not modify its general direction of flow and whose behavior over time, with the exception of the initial and final phases of the flow. preparation procedure, does not change substantially over time, that is, the flow rate is either substantially constant or follows a repetitive pattern as in the case of pulsed flows, such as those from the use a positive displacement pump.
The continuous flow reactor 10 further comprises an oscillatory system designed to superimpose an oscillatory flow to the permanent flow made by the input system in cooperation, either directly or indirectly with the output system. Although any oscillatory system, which moves the fluid back and forth over a certain length within the reactor zone 1, is usable, preferred embodiments of the oscillatory system include a mechanism 4 in combination with an expansion tank 5, such as a hydraulic accumulator or the like. The pressure jumps created by the displacement mechanism 4, for example a diaphragm pump, a piston pump or the like, are absorbed by the expansion tank 5, for example a hydraulic accumulator or the like, and returned from the reservoir. expansion in the suction cycle of the moving mechanism.
The reaction zone comprises at least one flow channel 1 providing fluid communication between its first end upstream and its second end downstream. The inlet system 2 is in fluid communication with the first end of said at least one flow channel. The outlet system 3 is in fluid communication with the second end of said at least one flow channel.
Said at least one flow channel 1 may be formed by a tube, the length of which is roughly defined by the product of the reaction time required for the preparation of a given organic peroxide and the average flow rate of the corresponding reaction mixture. inside the tube. The internal diameter of the tube determines the capacity of the reactor. The inner diameter further depends on the characteristics of the oscillatory flow, i.e., the inner diameter is chosen such that the oscillatory flow conditions generated by the oscillatory system allow turbulence within the which effect the desired mixing of the constituents of the reaction mixture. In other words, the internal diameter of the tube and the characteristics of the oscillatory flow are designed to obtain a flow characterized by a Reynolds number of 3000 or more. For careful mixing of constituents, flows characterized by a Reynolds number of 4000 or more are usually preferred.
To obtain a good mixture of constituents at comparatively lower flow rates, other types of flow channels can also be used such as, for example, those described in published international patent applications WO 2014/044624 A1 or WO 2012 / 095176 A1, where the creation of turbulence is improved by the use of a flow path having several changes of direction. A change in lane direction forces a fluid flow, in this case a reaction mixture for the preparation of an organic peroxide usually a liquid flow, to change direction. The respective directional changes or flow redirections introduce vortices, resulting in turbulence that mixes the constituents of the reaction mixture. The cross-sections of the lanes may have various forms, provided that they do not give rise to the formation of dead zones, where the local flow rate is too low to support the reaction. Preferred embodiments have flow channels having circular, annular, square, or rectangular cross-sectional shapes. The transverse shape may also vary along the flow path. The flow channel (s) can also be made by a set of plate structures, as for example shown in WO 2007/125091 A1. The flow channel (s) can also be formed as a hollow in a plate, several plates that can be sandwiched to form a reaction zone, the individual flow channels being connected in parallel and / or in series. The plates may be heat exchange plates with channels, allowing circulation of a heat transfer fluid, formed therein, or any other plate may be used for the heat exchange fluid while the one or more Remaining plates form the flow channel (s) for the actual reaction zone.
The transverse dimensions of a flow channel influence the heat dissipation or the heat exchange capacity of the latter. The ratio of the boundary area of a flow channel to the volume enclosed by a boundary surface of the flow channel decreases with increasing size of the smaller transverse dimension of the flow channel and results in a higher temperature difference between an innermost site and an outermost location of the drainage channel. The space-time efficiency of a flow channel having a low heat dissipation characteristic will therefore be low. For higher production volumes or production on an industrial scale, several narrower flow channels can therefore be arranged in parallel. Since the pressure drop along a flow channel increases as the cross sectional area of a flow channel decreases, the flow channels should not be designed with too small cross sections; otherwise, a loss of load, which will be too difficult to manage, could result.
The transverse flow channels can be characterized by what is called their hydraulic diameter, which is defined as four times the ratio of the cross sectional area of the flow channel to the wet perimeter of the cross section. The hydraulic diameters are preferably in the range of from 0.5 mm to 100 mm and more preferably from 2 to 50 mm. The ratio of the flow channel surfaces to the internal volume of the flow channel is preferably 20 m 2 / m 3 or more.
The temperature profile along the reaction zone is preferably regulated by means of a thermal transfer fluid in thermal contact with the walls of the reactor surrounding said at least one flow channel 1. The temperature profile can to be adjusted to achieve reaction temperatures below and above the defined SADT for an organic peroxide housed in a custom-sized container, for example a container with a capacity of 25 kg. Reaction temperatures higher than a SADT are possible because of the efficient heat dissipation achieved by the flow channel structures qualified for a continuous flow reactor explained above.
The temperature profile may advantageously be adjusted to the local requirements of the reaction process by the use of more than one loop 6 or a heat transfer fluid circuit along said at least one flow channel 1. The loops 6 of heat transfer fluid are part of a temperature control system (not shown further in the figures) for adjusting the desired temperature profile within said at least one flow channel. The heat transfer fluid (s) may be used for cooling as well as for heating the reaction mixture, that is, for transfer into or out of the reaction mixture.
In the embodiment illustrated in FIG. 1, the oscillatory systems perform an oscillatory flow along the entire length of said at least one flow channel 1. In other embodiments, the oscillatory flow is performed only along a section of the flow channel 1, preferably a downstream section. A respective design can be used to prevent the formation of so-called "hot spots" in the upstream portion of said at least one flow channel, where the concentration of reactants is highest and where a fine dispersion of phases would cause a reaction too fast. When using a displacement mechanism-based system 4 cooperating with an expansion tank or an expansion chamber 5, the displaced volume is preferably selected in such a way that the associated movement of the flow of substances in the reaction zone corresponds to only a part of the length of said at least one flow channel. The oscillatory system preferably provides an oscillatory flow having a frequency of 0.1 Hz or more but not exceeding 500 Hz, more preferably 1 Hz or more but not more than 50 Hz and even more preferably 2 Hz or more but not more than The frequency and the displacement volume are further preferably adjusted to obtain an oscillatory flow whose maximum flow is equal to or corresponds to a multiple of the average flow rate of the permanent flow achieved by the introduction (and possibly extraction) of substances in said at least one flow channel. In preferred embodiments, the multiple may be up to about five hundred times the average flow rate of the permanent flow.
The inlet system 2 preferably has more than one inlet for introducing the starting materials in a well-dosed manner. The inlet system can be formed by positive displacement pumps or other types of dosing systems. Instead of several independent pumps, a multi-head pump can be used, where all the pump mechanisms are actuated simultaneously by a drive, for example an electronically controlled motor. The starting materials that can be introduced using input system 2 depend on the peroxide classes produced as shown above. It is noted that the number of entries depends on the respective process carried out in the reactor and can therefore be different from three entries as illustrated in Figures 1 and 2.
To allow the addition of reactants, additives or diluents, further downstream, in said at least one flow channel or even downstream of the reactor zone, the apparatus 10 or 20 (see FIG. ) may further comprise an additional inlet system 8 (only shown in Figure 2) for adding a respective substance or mixture of substances at the desired position to the flow of substances. It is understood that although the additional input system 8 is illustrated to have only one input, it can also have more than one input, which can be combined to introduce a mixture at a given point in the input. flow channel and / or not combine to add substances or mixtures of substances at different points of said at least one flow channel. The latter can for example be used to distribute the addition of a given reactant along the path of the reaction zone.
The outlet system 3 may be formed by a back flow prevention device, such as a double check valve or other type of pressure retaining device, or any other suitable device, for example a pump , if necessary in combination with a pulse buffer.
The apparatuses 10 and 20 each further comprise a control device (not shown in the figures) for controlling their subsystems, i.e. the input system, in order to introduce the starting materials in a desired manner. , the oscillatory system to produce turbulence to the desired extent, the temperature control system to adjust the reaction temperatures along said at least one flow channel to the desired temperature profile and, where appropriate, the an outlet system for extracting the reaction product at a rate which corresponds to the sum of the input flow rates of the starting materials and, if appropriate, also those of the substances introduced in addition. In other words, the output extracts the reaction product at a rate corresponding to the input flow rates of the substances.
Figure 2 illustrates a second embodiment of an apparatus representing a continuous flow reactor. In contrast to the first embodiment 10, said at least one flow channel 1 is composed of two separate flow channels 1a and 1b connected in series. Line 9 connecting the first flow channel 1a to the second downstream flow channel 1b is derived to form fluid communication between the downstream and upstream ends of the first flow channel 1a. This link 7 serves to recirculate a portion of the reaction mixture exiting the end downstream of the first flow channel 1a. In one design, the recirculation is carried out by a pump disposed in the recirculation line 7, while the displacement mechanism 4 of the oscillatory system is connected to an end upstream of the second flow channel 1b or further downstream thereof end.
Another design, which is shown in FIG. 2 and characterized by a reduced capital expenditure, realizes the recirculation by the displacement mechanism 4 of the oscillatory system disposed in the recirculation pipe 7. The expansion tank 5 of the oscillatory system is , as in the embodiments according to Figure 1, disposed between the downstream end of the second flow channel and the outlet system 3, or in fluid connection with the second flow channel lb somewhere between its ends in upstream and downstream. In the suction cycle, the displacement mechanism 4 draws material from the pipe connecting the downstream end of the first flow channel 1a to the upstream end of the second flow channel 1b. In the evacuation cycle, the displacement mechanism 4 discharges the material into the first flow channel 1a via its upstream end. This results in both a recirculation of a portion of the material flowing through the first flow channel 1a and an oscillatory flow superimposed on the flow of substances which passes through the second flow channel 1b.
The implementation of said at least one flow channel 1 in the form of two separate flow channels 1a and 1b connected in series and leading the first recirculating flow channel form two consecutive reaction sub-zones, serving for different purposes. In the first reaction sub-zone, where the concentration of reactants is highest, part of the reaction mixture flows in a loop allowing, since only the evacuation cycle of the displacement mechanism is used to maintain the recirculation, a good macromixture of the reactants, resulting in uniform distribution of the reactants in the reaction mixture but with droplet sizes large enough to avoid undesired hot spots and to ensure lower reaction kinetics and thus lower heat generation. Due to recirculation, the average flow rate within the first flow channel 1a is greater than the flow rate induced by the inlet system 2 which distributes the heat generated during the reaction more evenly along the flow path. length of the first reaction sub-zone, which allows a better regulation of the temperature at this early stage of the reaction. Since the reaction conditions in the first reaction sub-zone differ from those in the second downstream reaction sub-zone, the first flow channel is, as shown in FIG. 2, preferably equipped with a separate heat exchange system 6a which can be operated independently of the other heat exchange system 6b used for the second reaction sub-zone 1b.
Unlike the first flow channel 1a, the two cycles of the displacement mechanism 4 act on the second flow channel 1b. Because of the cooperation with the hydraulic accumulator 5, the displacement mechanism 4 carries a rearward and forward displacement of the reaction mixture in the second flow channel 1b, which gives rise to a micromixing resulting in finely dispersed droplets of small sizes and increasing reaction kinetics. According to the different kinetics of reaction, the temperature profile in the second flow channel is preferably regulated by a separate heat exchange system 6b, designed for operation independent of the heat exchange system 6a.
As in the embodiments according to FIG. 1, the embodiments according to FIG. 2 also comprise a control device (not represented) for the control of the individual elements of the apparatus 20 in order to realize a method for the preparation of an organic peroxide of a class as described above.
FIG. 3 shows a modification of the apparatus illustrated in FIG. 2. In this embodiment, the flow channel la comprises three flow channel modules lai, laii and lai, the first two modules lai and laii of each flow channel being formed by a "split-and-recombine" reactor whose reaction channels are arranged in a herringbone-like structure similar to that disclosed in WG 2014/044624 A1. A reactor having a structure A meander channel, similar to that disclosed in Figure 6 of WO 2012/095176 A1, forms the third flow channel module laiii. The input system consists of two inputs, a first input 2a for introducing a first starting material into the first flow channel module lai, where it is mixed with the recirculating portion of the output of the third flow channel module laiii, and a second input 2b which introduces a second starting material into the second flow channel module laii, where it is mixed with the output of the first flow channel module lai. The design further enhances temperature control at an early stage of the reaction. It will be understood that the embodiments according to FIG. 3 also include a control device (not shown) for controlling the individual elements of the apparatus 20 to provide a method for the preparation of an organic peroxide of a class as described above. The first starting material may for example be an aqueous potassium tert-butyl hydroperoxide (TBKP) solution, while the second starting material may be 2-ethylhexanoyl chloride (EHC).
The apparatuses illustrated in FIGS. 1 to 3 may be autonomous reactors or may each form a sub-reactor of a more complex multi-stage reactor design. When they are part of a multi-stage reactor, the inlet system 2 is usually part of a previous reactor located upstream of said at least one flow channel 1 and / or the outlet system 3 is usually part of of a consecutive reactor located downstream of said at least one flow channel 1. In designs such as these, only a part of the total reaction is carried out in said at least one flow channel.
The basic steps of a process for preparing an organic peroxide are illustrated in the diagram of FIG. 4. The arrows connecting the individual steps of the procedure are not intended to indicate any chronological order. The arrow rather illustrates the direction of the mass flow or flow of substances in the procedure. Once the process is established, all process steps are performed simultaneously. Step S1, that is to say the introduction of at least two substances or a combination of substances into said at least one flow channel according to a first characteristic, is carried out by the control device of the apparatus 10 or 20 which acts on the input system. Step S2, i.e. superposition of an oscillatory flow to at least a portion of the flow of substances that passes through said at least one flow channel, is performed by the controller of the apparatus 10 or 20 which acts on the oscillatory system. Step S3, that is to say the extraction, continuously, of the reaction product formed in the at least one flow channel of the substances introduced, is carried out by the control device of the apparatus 10. or 20 which acts on the output system. Most reactions need step S4 which is also performed by the device controller 10 or 20, this time acting on the temperature control system to regulate the temperature profile along the length. said at least one flow channel, the different sections of the flow channel or the different sub-reaction zones being controllable independently of one another.
The potential of the present invention is illustrated by the example below, using an apparatus having two reaction sub-zones according to the types of embodiments characterized by FIG. 3. The apparatus used is a glass reactor having a hydraulic diameter of 1 mm. The total volume of the first reaction zone is about 1.5 ml and represents the sum of the volumes of the first flow channel module (0.2 ml), the second flow channel module (of new 0.2 ml) and the third flow channel module (1.1 ml), that of the second reaction zone is 1.1 ml; the recirculation and oscillation flows are both performed by a piston pump disposed in the recirculation loop as shown in Figure 3 below. The pump is operated at a speed of 1000 rpm and thus the frequency of the oscillation flow is about 17 Hz. The ratio of the maximum oscillatory flow to the constant flow is about 14.
The starting materials used are an aqueous solution of potassium tert-butyl hydroperoxide (TBKP) and 2-ethylhexanoyl chloride (EHC). The TBKP is introduced using a 7.93 mmol / min continuous flow syringe pump at the upper end of the first reactor sub-zone. The EHC is introduced using a syringe pump at a steady flow of 6.15 mmol / min between the two split-and-recombine reactors of the first reactor sub-zone. For the regulation of the temperature, the reactor system is introduced into a bath. The reaction temperature is set at 47 ° C and the general residence time is about 1 minute. The reaction product, tert-butyl peroxy-2-ethylhexanoate (TBPEH), was separated after leaving the second reaction sub-zone at a steady stream of 5.86 mmol / min. This represents a yield of more than 95% based on TBKP and is comparable to the yields obtained in documents DD 128663 (approximately 90%) and WO 2008/006666 A1 (98.5%). To a total reaction volume of 3.7 ml (2 * 0.2 ml + 2 * 1.1 ml + 1.1 ml for the pipes), the space-time yield calculated is 20 kg / l-h. This represents eight times the space-time yield obtained with a reactor according to WO 2008/006666 A1 (2.5 kg / lh) and about five times the space-time yield obtained with a reactor according to document DD 128663 (3, 6 kg / lh). The conversion of EHC is 100% and the selectivity for TBPEH is greater than 95%. Compared to the results disclosed by Fritzsche and Knorr in the publications cited above, better selectivity, better conversion and better yield are obtained.
While the above description explains the present disclosure by reference to a number of illustrative embodiments, it is obvious that many alternatives, modifications, and variations will be apparent to those skilled in the art. Accordingly, the illustrative embodiments of the disclosure presented herein serve to illustrate the disclosure and are not intended to limit it in any way. Various modifications may be made to the described embodiments without departing from the spirit and scope of the present disclosure as defined in the claims below.

权利要求:
Claims (23)
[1" id="c-fr-0001]
claims
A process for continuous preparation of organic peroxides, comprising the steps of: using a continuous flow reactor (10, 20) having: at least one flow channel (1, 1a, 1b) designed as a reaction zone; an inlet system (2) in fluid communication with a first end of said at least one flow channel (1, 1a, 1b) and adapted to introduce two or more substances or a combination of substances into said at least one flow channel; flow; an output system (3) in fluid communication with a second end of said at least one flow channel (1, 1a, 1b), the second end being located downstream of the first end and the output system being adapted to extract reaction products present at the second end; and an oscillatory system (4, 5) arranged to superpose an oscillatory flow to the flow of substances which passes through said at least one flow channel (1, 1a, 1b), the oscillation being effected in at least one section of said at least one flow channel; (51) introducing, according to a first characteristic, at least two substances or a combination of substances into said at least one flow channel (1, 1a, 1b) using the input system (2), (52) ) superimposing, by means of the oscillatory system (4, 5), an oscillatory flow to at least a portion of the flow of substances which passes through said at least one flow channel (1, 1a, 1b) for creating turbulence in the flow of substances, (S3) extracting, continuously and with the aid of the outlet system (3), the reaction products formed in the at least one flow channel (1, la, lb) introduced substances, the mass flow output corresponding to the sum of input mass flow rates.
[2" id="c-fr-0002]
The method of claim 1, the step of using a continuous flow reactor (10) comprising using a reactor further having a temperature control system (6, 6a, 6b) designed for regulating the temperature profile along the length of said at least one flow channel (1, 1a, 1b) and the method further comprising the step (S4) of regulating the temperature profile along said at least one a flow channel (1, 1a, 1b) using the temperature control system (6, 6a, 6b).
[3" id="c-fr-0003]
3. Method according to claim 1 or 2, the introduction of said at least two substances according to the first characteristic comprising the introduction of at least one of the two substances in a constant or pulsed manner.
[4" id="c-fr-0004]
4. The method of claim 1, 2 or 3, the step of superposition of an oscillatory flow to at least a portion of the flow of substances that passes through said at least one flow channel (1) comprising use of an oscillatory system having a device for generating (4) an oscillatory flow in fluid communication with said at least one flow channel at a first position and a hydraulic accumulator (5) in fluid communication with said at least one a flow channel in a second position, different from the first position.
[5" id="c-fr-0005]
5. Method according to any one of the preceding claims, the step of using a continuous flow reactor comprising the use of a reactor (20) of which at least one flow channel (1) comprises a first flow channel (1a) and a second flow channel (1b), a first end of the first flow channel being in fluid communication with the inlet system (2) and a second end of the first flow channel being in fluid communication with a first end of the second flow channel (1b), the reactor further comprising a recirculation system (9, 7, 4) adapted to reintroduce a portion of the reaction mixture exiting the second end of the first channel in the first flow channel upstream of its second end, and the method comprising the step of reintroducing a portion of the reaction mixture exiting the second end of u first flow channel in the first flow channel upstream of its second end using the recirculation system.
[6" id="c-fr-0006]
6. The method of claim 5, the step of using a continuous flow reactor comprising the use of the first flow channel (la) formed by three flow channel modules connected in series, the first module. (lai) and the second flow channel module (laii) are each formed by a "split-and-recombine" reactor while the third flow channel module (laiii) is formed by a meander channel reactor, and the inlet system (2a, 2b) being adapted to introduce a first substance into a first inlet of the first flow channel module (lai) and to introduce a second substance into a first inlet of the second flow channel module (laii), the output of the first flow channel module (lai) being in fluid communication with a second input of the second flow channel module (laii), the output of the second module ( laii) of ec canal said element being in fluid communication with the inlet of the third flow channel module (laiii) and the outlet of the third flow channel module (laiii) being in fluid communication with a recirculation system adapted to reintroduce a portion of the mixture reaction from the third flow channel module (laiii) into a second inlet of the first flow channel module (lai).
[7" id="c-fr-0007]
7. The method of claim 5 or 6, when dependent on claim 4, the recirculation system (9, 7, 4) comprising the device (4) for generating an oscillatory flow and the hydraulic accumulator (5). ) being in fluid communication with the second end of the second flow channel.
[8" id="c-fr-0008]
8. The method of claim 5, 6 or 7, when dependent on claim 2, the step of regulating the temperature profile along said at least one flow channel using the control system of the temperature comprising the use of a temperature control system (6) having a first heat exchange system (6a) and a second heat exchange system (6b), the first heat exchange system being designed to a heat exchange with the first flow channel (1a) and the second heat exchange system being designed for heat exchange with the second flow channel (1b), to regulate the temperature profile along the first flow channel; flow, separately from the temperature profile along the second flow channel.
[9" id="c-fr-0009]
A process according to any one of the preceding claims, wherein the step of using a continuous flow reactor comprising using a reactor further comprising an additional inlet system (8) adapted to introduce one or more several substances in said at least one flow channel (1) downstream from its first end, the method further comprising the step of introducing one or more additional substances into said at least one flow channel downstream from its first end, in accordance with a second feature, and the output mass flow achieved by the output system further including also the additional input mass flow rate.
[10" id="c-fr-0010]
A process according to any one of the preceding claims, wherein the step of using a continuous flow reactor comprises using a reactor whose oscillatory system is designed to generate an oscillatory flow having a frequency between 0, 1 Hz and 500 Hz, more preferably between 1 and 50 Hz and even more preferably between 5 Hz and 25 Hz.
[11" id="c-fr-0011]
The method of any one of the preceding claims, wherein the step of using a continuous flow reactor comprises using a reactor whose oscillatory system is designed to generate an oscillatory flow having a maximum flow in the reactor. range from 1 to 500 times the average flow rate of the first characteristic.
[12" id="c-fr-0012]
A method according to any one of the preceding claims, the input system further being in fluid communication with a previous reactor and adapted to transfer a combination of substances representing a pretreated reaction mixture from the preceding reactor into said at least one reaction channel. flow, and / or the outlet system further being in fluid communication with a subsequent reactor and adapted to transfer a reaction product present at the second end into the subsequent reactor.
[13" id="c-fr-0013]
13. Process according to any one of the preceding claims, the prepared organic peroxides being chosen from one of the following classes of peroxides: diacyl peroxides, peroxyesters, peroxycarbonate esters, peroxydicarbonates, hydroperoxides, dialkyl peroxides, ketone peroxides, peroxyketals, monoperoxydecals, peroxycarboxylic acids and mixtures thereof.
[14" id="c-fr-0014]
A continuous flow reactor, comprising: at least one flow channel (1, 1a, 1b) configured as a reaction zone; an inlet system (2) in fluid communication with a first end of said at least one flow channel and adapted to introduce two or more substances or a combination of substances into said at least one flow channel; an outlet system (3) in fluid communication with a second end of said at least one flow channel, the second end being located downstream of the first end and the outlet system being adapted to extract a reaction product present at the the second end; an oscillatory system (4, 5) arranged to superpose an oscillatory flow to the flow of substances which passes through said at least one flow channel, the oscillation being carried out in at least one section of said at least one channel of flow; and a controller adapted to control the input system to introduce, according to a first feature, at least two substances or a combination of substances into said at least one flow channel, the oscillatory system to superimpose a flow. oscillatory to at least a portion of the flow of substances that passes through said at least one flow channel, and the outlet system for continuously withdrawing the reaction product formed in the flow channel substances introduced in such a way that the mass output flow corresponds to the sum of the input mass flow rates.
[15" id="c-fr-0015]
The continuous flow reactor of claim 14, further comprising a temperature control system (6, 6a, 6b) adapted to regulate the temperature profile along the length of the flow channel and the flow control device. control being further adapted to control the temperature control system for controlling the temperature profile along said at least one flow channel.
[16" id="c-fr-0016]
Continuous flow reactor according to Claim 14 or 15, the oscillatory system comprising a device (4) for generating an oscillatory flow mounted in fluid communication with the at least one flow channel in a first position and a hydraulic accumulator. (5) mounted in fluid communication with said at least one flow channel at a second position different from the first position.
[17" id="c-fr-0017]
17. Continuous flow reactor according to any one of claims 14 to 16, said at least one flow channel (1) comprising a first flow channel (1a) and a second flow channel (1b), a first end of the first flow channel being in fluid communication with the inlet system and a second end of the first flow channel being in fluid communication with a first end of the second flow channel, the reactor further comprising a system recirculation device (9, 7, 4) adapted to reintroduce a portion of the reaction mixture exiting the second end of the first flow channel into the first flow channel upstream of its second end, and the control device being furthermore adapted to control the recirculation system to reintroduce a portion of the reaction mixture exiting the second end of the first flow channel into the first flow channel upstream of its second end.
[18" id="c-fr-0018]
The continuous flow reactor of claim 17, the first flow channel (1a) being formed by three flow channel modules connected in series, the first flow channel module (lai) and the second flow channel module (1a). laii) are each formed by a split-and-recombine reactor while the third flow channel module (laiii) is formed by a meander channel reactor, and the inlet system ( 2a, 2b) being adapted to introduce a first substance into a first inlet of the first flow channel module (lai) and to introduce a second substance into a first inlet of the second flow channel module (laii), the outlet the first flow channel module (lai) being in fluid communication with a second inlet of the second flow channel module (laii), the outlet of the second flow channel module (laii) being in fluid communication with the flow channel 'input ee of the third flow channel module (laiii) and the outlet of the third flow channel module (laiii) being in fluid communication with a recirculation system adapted to reintroduce a portion of the reaction mixture exiting the third module (laiii) flow channel in a second inlet of the first flow channel module (lai).
[19" id="c-fr-0019]
19. Continuous flow reactor according to claim 17 or 18, when dependent on claim 16, the recirculation system comprising the device (4) for generating an oscillatory flow and the hydraulic accumulator (5) in communication. fluidic with the second end of the second flow channel.
[20" id="c-fr-0020]
20. Continuous flow reactor according to any one of claims 17 to 19, when dependent on claim 15, the temperature control system (6) comprising a first heat exchange system (6a) and a second heat exchange system (6b), the first heat exchange system being designed for heat exchange with the first flow channel and the second heat exchange system being designed for heat exchange with the second flow channel and the control device being further adapted to regulate the temperature profile along the first flow channel separately from the temperature profile along the second flow channel.
[21" id="c-fr-0021]
The continuous flow reactor according to any one of claims 14 to 20, further comprising at least one additional inlet system (8) adapted to introduce one or more substances into said at least one downstream flow channel. its first end, the control device being further adapted to control the additional input system to introduce one or more additional substances into said at least one flow channel downstream from its first end, in accordance with a second characteristic and to control the output system to realize that the mass output flow further includes also the additional input mass flow rate.
[22" id="c-fr-0022]
22. Continuous flow reactor according to any one of claims 14 to 21, the oscillatory system being designed to generate an oscillatory flow having a frequency between 0.1 Hz and 500 Hz, more preferably between 1 and 50 Hz and even more preferably between 2 Hz and 25 Hz.
[23" id="c-fr-0023]
23. Continuous flow reactor according to any one of claims 14 to 22, the oscillatory system being designed to generate an oscillatory flow having a maximum flow in the range of 1 to 500 times the average flow rate of the first characteristic.

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公开号 | 公开日

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JP2018538234A|2018-12-27|

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EP3368209A1|2018-09-05|

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FR3042793B1|2019-12-27|

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EP3838399A1|2021-06-23|

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CN108136361A|2018-06-08|

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CN108136361B|2020-07-07|

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JP6854802B2|2021-04-07|

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US10449509B2|2019-10-22|

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MX2018004424A|2018-05-11|

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US20180304227A1|2018-10-25|

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EP3368209B1|2021-03-17|

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WO2017072190A1|2017-05-04|

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2017-04-28| PLSC| Search report ready|Effective date: 20170428 |

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优先权:

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申请号 | 申请日 | 专利标题

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FR1560186|2015-10-26|

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FR1560186A|FR3042793B1|2015-10-26|2015-10-26|SYNTHESIS OF ORGANIC PEROXIDES USING AN AGITED OSCILLATORY FLOW REACTOR|FR1560186A| FR3042793B1|2015-10-26|2015-10-26|SYNTHESIS OF ORGANIC PEROXIDES USING AN AGITED OSCILLATORY FLOW REACTOR|

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PCT/EP2016/075834| WO2017072190A1|2015-10-26|2016-10-26|Synthesis of organic peroxydes using an oscillatory flow mixing reactor|

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MX2018004424A| MX2018004424A|2015-10-26|2016-10-26|Synthesis of organic peroxydes using an oscillatory flow mixing reactor.|

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EP16787846.1A| EP3368209B1|2015-10-26|2016-10-26|Synthesis of organic peroxydes using an oscillatory flow mixing reactor|

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EP21156602.1A| EP3838399A1|2015-10-26|2016-10-26|Synthesis of organic peroxydes using an oscillatory flow mixing reactor|

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US15/768,684| US10449509B2|2015-10-26|2016-10-26|Synthesis of organic peroxydes using an oscillatory flow mixing reactor|

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JP2018504154A| JP6854802B2|2015-10-26|2016-10-26|Synthesis of organic peroxides using a vibrating flow mixing reactor|