CN108250176A - A kind of quick continuous flow synthesis technology of fluorinated ethylene carbonate - Google Patents

A kind of quick continuous flow synthesis technology of fluorinated ethylene carbonate Download PDF

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CN108250176A
CN108250176A CN201711330777.4A CN201711330777A CN108250176A CN 108250176 A CN108250176 A CN 108250176A CN 201711330777 A CN201711330777 A CN 201711330777A CN 108250176 A CN108250176 A CN 108250176A
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gas
reaction
continuous flow
fluorinated
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马兵
潘帅
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Shanghai Hui And Huade Biotechnology Co Ltd
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Shanghai Hui And Huade Biotechnology Co Ltd
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Priority to PCT/CN2017/116959 priority Critical patent/WO2018113628A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/42—Halogen atoms or nitro radicals

Abstract

The present invention relates to a kind of fluorinated ethylene carbonate quick continuous flow synthesis technology and realize the integrated continuous flow reactor of the technique, the continuous flow synthesis technology is using raw material to be fluorinated and fluorine gas as reactant, continuously disperse successively through mixing, fluorination reaction, gas-liquid separation step obtains fluorinated ethylene carbonate, the synthesis technology carries out in an integrated continuous flow reactor, raw material and fluorine gas to be fluorinated are uninterruptedly added in the feed inlet of the integrated continuous flow reactor, fluorinated ethylene carbonate is uninterruptedly obtained in the integrated continuous flow reactor discharge port, reaction time is equal to or less than 600s.This technique is a kind of continuous synthesis technology of fluorinated ethylene carbonate that is quick, safe efficient, versatile and being easy to large-scale production.

Description

A kind of quick continuous flow synthesis technology of fluorinated ethylene carbonate
Technical field
The present invention relates to chemical fields, and in particular to a kind of quick continuous flow synthesis technology of fluorinated ethylene carbonate.
Background technology
Fluorochemical (especially organofluorine compound, i.e., partially and fully fluorinated organic compound) is that performance is excellent Different, great commercial value chemicals.Fluorochemical can show that inertia, nonpolarity, hydrophobicity, oleophobic property etc. are various Performance, thus have very extensive purposes.Fluoro organic carbonate is that a kind of important organofluorine compound is (organic referred to as organic Fluoride), the solvent and solvent additive of lithium ion battery are may be used as, forms solid electrolyte interface film (SEI films) Performance it is more preferable, tight structure layer can be formed but do not increase impedance, while electrolyte can be prevented further to decompose and have Fire retardation improves the cryogenic property of electrolyte so that the cycle life of battery dramatically increases, and the security performance of battery obtains It improves.Wherein fluorinated ethylene carbonate is important a product.
The synthesis route of fluorinated ethylene carbonate mainly includes following several：
The industrial electrochemical fluorination of organofluorine compound, is put to industrialized production by 3M companies earliest.This fluorine Change method is commonly referred to as " Simons electrochemical fluorinations ", and technical process needs will contain anhydrous liquid hydrogen fluoride and organic compound The electrolyte solution of raw material is electrolysed, and shortcoming is high energy consumption and needs to use anhydrous hydrogen fluoride.Another electrochemical fluorine Changing rule is electrolysed in molten salt bath (such as potassium fluoride/hydrogen fluoride melt), is referred to as Philips's technique.BASF Europe Continent company improves this kind of method in CN103261484A, substitutes anhydrous hydrogen fluoride using fluorination hydrogen complex or molten salt bath is made For the fluorization agent in electrolyte, and it is applied to and prepares fluoro organic carbonate, but still need to consume a large amount of electricity in technical process Can, it is of high cost.
Another method of industrial production fluoro organic carbonate is halogen exchange method, that is, passes through Finkelstein halogen The method of exchange reaction (Finkelstein Reaction) synthesizing fluoro organic carbonate.Such method is usually that will organise Chloro organic carbonate is made after closing the chlorination of object elder generation, is reacted again with fluorination reagent (HF or KF) after purified and fluoro organic carbon is made Acid esters.For example, the route that a fluorinated ethylene carbonate is synthesized using halogen exchange method is as follows：
Wherein first step chlorination has more report, and technique is relatively ripe, easily operated relative to fluoro-reaction And control.But since the route synthesizing fluoroethylene carbonate need to undergo two-step reaction, and in order to reduce halogen exchange reaction Impurity, obtain the fluoro organic carbonate of high-purity, intermediate chlorocarbonic acid vinyl acetate need to be carried out including washing, neutralize, The more purifications process such as drying, rectifying so that technical process is cumbersome, reduces production efficiency.In addition, according to existing report one As two-step reaction prepare the total recovery of a fluorinated ethylene carbonate 60~65%, it is unsatisfactory.
Patent CN105541783A relates to a kind of production method of fluorinated ethylene carbonate, using ethylene carbonate as raw material Fluorinated ethylene carbonate is made in experience chloro, elimination and addition three-step reaction, and process route is as follows, intermediate chlorocarbonic acid Vinyl acetate and vinylene carbonate be required to by purification process (need rectifying obtain chlorocarbonic acid vinyl acetate, decompression be refining to obtain carbon Sour vinylene) it can be only used for reacting in next step, compare direct fluorination, and reaction step and processing step all increase not Few, production efficiency declines, and fluorinated ethylene carbonate yield does not have improvement compared with halogen exchange method, with chlorocarbonic acid ethylene Ester meter is only 56.5%.
It is direct fluorination that synthesizing fluoroethylene carbonate, which also has a feasible process route, i.e., using fluorine gas or fluorine gas Substitution reaction synthesizing fluoroethylene carbonate is directly carried out with ethylene carbonate with the mixed gas of inert gas (such as nitrogen), For example, the route that a fluorinated ethylene carbonate is synthesized using direct fluorination is as follows：
Compared to halogen exchange method, this method experience single step reaction, process route is more succinct, and reaction is prone to condition temperature With due to the high reaction activity of fluorine gas, theoretically fluoro-reaction can be rapidly completed at relatively low temperature, production efficiency Higher.But this method also has a deficiency, such as raw material fluorine gas toxicity is big；The reactivity height of fluorine gas causes process very exothermic, The pressure being easy to cause in reactor is higher, occurs dangerous；Fluorine gas corrosivity is strong, consersion unit is required very high.Due to these Reason is caused using direct fluorination technique report seldom, and industrial applications are also extremely restricted.
Fluorine gas is hypertoxicity gas, can stimulate eye, skin, respiratory mucosa.When Funing tablet be 5~10ppm when, to eye, The mucous membranes such as nose, throat begin with stimulation, and when long action time can also cause pulmonary edema.It can cause hair with skin contact Burning, contact site coagulation necrosis, epithelial tissue carbonization etc..Chronic exposure can cause osteopetrosis and ligament calcification.To protect Personnel safety is demonstrate,proved, aerial maximum permissible concentration is 0.1ppm (0.2mg/m3).Thus using the direct fluorination of fluorine gas Method is very high to device and process safety requirement, needs to include anti-leak and vent gas treatment facility.
The element fluorine element most strong as electronegativity, the chemical property of gas simple substance fluorine gas is very active, the overwhelming majority Element including certain inert gases, can react with it to form compound.Fluorine gas have strong oxidizing property, at room temperature can with it is big Most oxidizable substances or organic matter kickback and burn, for example, alkali metal can explode in fluorine gas, it is many it is nonmetallic as silicon, Phosphorus, sulphur etc. can also burn in fluorine gas, and with reacting for fluorine gas combustion explosion easily occurs for most of organic compounds.It organises It closes object and fluorine gas generation substitution reaction thermal discharge is very big, if for example, a fluoro-reaction occurs with fluorine gas, exothermic heat of reaction is about 482kJ/mol, and for a chlorine substitution reaction similar with bromine generation, exothermic heat of reaction respectively may be about 101kJ/mol and 34kJ/ The thermal discharge of mol, i.e. fluoro-reaction are nearly 5 times of similar chlorination, and more order of magnitude greater than similar bromo-reaction, such as Fruit is more fluoro-reactions, and thermal discharge can increase (for example, two fluoro exothermic heat of reaction are about 964kJ/mol) into multiple.Thus with The mixed gas of fluorine gas or fluorine gas and inert gas is the fluoro-reaction of raw material, compared to similar substitution reaction (such as chloro, bromine Generation etc.), have the characteristics that thermal discharge is big, it is very high to the thermal transmission requirement of technical process, increase the difficulty of process exploitation.This Outside, the technique of existing synthesizing fluoroethylene carbonate can't be realized using similary a set of reactor only by simply adjusting work Skill parameter can arbitrarily synthesize a variety of different fluorinated ethylene carbonates and its mixture (for example, using ethylene carbonate as original Material synthesizes a fluorinated ethylene carbonate；Or using ethylene carbonate as raw material, difluorinated ethylene carbonate is synthesized；Or with one Fluorinated ethylene carbonate is raw material, synthesizes three fluorinated ethylene carbonates).
The substitution reaction of fluorine gas and organic compound is prone to and process is violent, and bad reaction is controlled to be easy to excessively lead Selectivity is caused to reduce, the mixture of a variety of different degree of fluorination products is generated, reduces target product yield, also increase separation Refined difficulty.In general, raw material to be fluorinated occur a fluorine substitution reaction selectively compared to the substitution of other number fluorine (for example, Two fluoro, three fluoro, four fluoro) reaction can be more preferable, and corresponding process conditions are also easy to control, for example, Chinese patent CN1810764A and CN201080042843A reports, using ethylene carbonate as one fluorinated ethylene ester of Material synthesis carbonic acid selectivity Selectively higher than two fluoro vinyl acetate of carbonate synthesis, carbonic acid ethylene trifluoride ester, carbonic acid tetrafluoroethylene ester, the former is more than 95%, latter three is no more than 80%.And then ratio of the target product in reacting coarse product is also higher, has been reported and prepares carbon The selectivity of a sour fluorinated ethylene ester reaches as high as 95%, but prepare two fluoro vinyl acetate of carbonic acid, carbonic acid ethylene trifluoride ester, carbon Sour tetrafluoroethylene ester not more than 75%.That is, existing method can not also well solve direct fluorination reaction choosing Select sex chromosome mosaicism.
The corrosivity of fluorine gas is very strong, most metals and it is nonmetallic can all be corroded, thus direct fluorination to reaction set Standby material and structural requirement are very high, while fluorine gas in technical process is required to consume as far as possible completely, improve the conversion ratio of fluorine gas, subtract Little waste reduces vent gas treatment risk.
The direct fluoro-reaction of ethylene carbonate and fluorine gas is the heterogeneous reaction of a gas-liquid two-phase, and this kind of reaction is logical It is often the synthesis of mass transport process and reaction process, Global reaction Rate is by intrinsic reaction rate and the common shadow of mass transfer rate It rings.The fluoro-reaction of ethylene carbonate and fluorine gas belongs to fast reaction, thus Global reaction Rate is affected by mass transfer factor, The good mixing that comes into full contact with of gas-liquid two-phase is advantageous rapid reaction completely.It is generally considered that, in heterogeneous reaction, The close two-phase mixtures of volume, mixed effect can be preferable.But in gas-liquid two-phase reaction, general gas phase and liquid phase volume gap are huge Greatly.For example, a fluoro-reaction occurs for ethylene carbonate and fluorine simple substance (pure fluorine gas), according to theoretical molar ratio, gas-liquid two-phase Volume ratio is as high as 336:1.If carrying out more fluoro-reactions, the volume differences of gas phase and liquid phase will be away from that will be multiplied, for example, carbonic acid With fluorine simple substance (pure fluorine gas) two fluoro-reactions occur for vinyl acetate, and according to theoretical molar ratio, the volume ratio of gas-liquid two-phase is then 672:1.Or fluorination reagent is using the mixed gas of fluorine gas and inert gas, the volume differences of gas phase and liquid phase are away from will bigger. For example, with fluorine simple substance and the mixed gas of nitrogen that volumetric concentration is 20% one fluoro-reaction occurs for ethylene carbonate, according to reason By molar ratio, then the volume ratio of gas-liquid two-phase is as high as 1680:1.Gas-liquid two is generally weighed using gas liquid dispersion specific surface area The mixed effect of phase, gas liquid dispersion specific surface area is bigger, and gas-liquid two-phase mixing is better.
To sum up, by direct fluorination synthesizing fluoroethylene carbonate, although have theoretic reaction advantage (fluorine it is anti- Should activity it is high, can at low temperature can fast reaction, that reaction step lack production efficiency is high), but this method there are the shortcomings that It is also apparent from：1) controllability of reaction is very poor, shows that thermal discharge is very big, and reaction is easily out of control, dangerous big；2) due to being body Heterogeneous reaction of the product moment away from huge gas-liquid two-phase, gas phase and liquid phase are difficult to realize uniform mixing, and the reaction is to reaction system Mass transfer requirement it is very high, otherwise be difficult to realize fully reaction；3) process selectivity is poor, flexibility is low, the difference of same raw material The thermal discharge of the fluoro-reaction (for example, a fluoro-reaction, two fluoro-reactions, three fluoro-reactions, four fluoro-reactions etc.) of degree Gentle liquid volume ratio is widely different, and the physical property of different material is (for example, molten boiling point, thermal conductivity, thermal capacitance, solubility Etc.) and reactivity it is also very different, thus the condition that corresponding fluoro-reaction occurs is also widely different, it is difficult to control some degree Fluoro-reaction occur with high selectivity, and a reactor is difficult to meet a variety of fluoro product synthesis conditions simultaneously.
In the prior art, there are no develop the reaction advantage that can either give full play to direct fluorination, and can overcome this The technique of the three of the above shortcoming of method, i.e.,：Heat transfer, mass transfer problem are fully solved, also takes into account different material physical property (example Such as, boiling point, thermal conductivity, thermal capacitance, solubility etc. are melted) and reactivity difference, process selectivity and flexibility problem are solved, is made It is highly controllable to obtain direct fluorination reaction, and reaction efficiency is high (being swift in response, target product yield height), equipment universality is good (using same reactor can be with the product of high efficiency production difference fluoro degree).
In existing industrial production, direct fluorination synthesizing fluoroethylene carbonate uses batch technology more, i.e.,：To filling one In the reaction kettle of fixed number content of starting materials, the mode for being passed through the mixed gas bubbling of fluorine gas or fluorine gas and inert gas is realized, example Such as, above-mentioned this batch tank technique mistake has been described in detail in patent CN1747946A, CN100343245C and JP2000309583A Journey.Other than the problem of intrinsic production efficiency of batch technology is low, cumbersome, using the mode for being passed through gas sparging come into Promoting the circulation of qi liquid two phase reaction, since gas-liquid two-phase contact is limited, the conversion ratio there are reaction efficiency and fluorine gas is all relatively low, selecting response The problems such as property is poor, and the reaction time is longer.Chinese patent CN1810764A improves this, is being supplied into ethylene carbonate F2/N2During mixed gas, adjust the size of bubble using the bubble adjustable column filled with filler and optimize reactor shape, increase Time of contact and the contact area of gas-liquid two-phase are added, reaction efficiency increases, and there is corresponding shortening in the reaction time.On 50 DEG C of left sides The right side, FEC yields are up to 82%.But this reaction is batch technology and the reaction time still needs to a few hours, and every batch of is after reaction It all needs to use N2Gas removes residual gas in reactor, this all limits the whole production efficiency of fluorinated ethylene carbonate.
Batch technology (batch process) is after adding raw materials into reactor, waits for certain time (including each step Time of reaction, temperature fall time, heating-up time, soaking time and interval stand-by period for respectively operating etc.), reaction reaches one After provisioning request, once draw off product, i.e. the mode of production of product is partitioned into batch, and every batch of can only produce it is limited The product of fixed quantity (its quantity depends on the size of reactor volume).Refer to the reaction total time of batch technology from raw material to The total time of product is made, includes the feed time of each step, reaction time, the discharge time turns to expect the time, temperature fall time, Heating-up time, soaking time and interval stand-by period for respectively operating etc..Material (packet in reactor in batch technology operating process Include intermediate product, final product) the state parameters such as composition, temperature can change over time, be transient, production process and Product quality has very big uncertainty, and the quality for directly resulting in downstream product is unstable, it is difficult to control.
The most important feature of batch technology has at 2 points, first, there is " stop " or " interruption " in the process, second is that production It is spaced apart, i.e., there are the products that batch and a batch production can only obtain fixed quantity for product.It is, for every A batch of production, the raw material of fixed quantity are reacted according to the sequence of reaction step, finally obtain limited fixed quantity Product (product)；Then the raw material of fixed quantity is put into again, the reaction of next batch is carried out according to similary step, and being made has The product of the fixed quantity of limit.
There are two types of the modes that batch technology is realized：1) it is realized respectively with multiple reactors (for example, flask, reaction kettle etc.), It is carried out in a reactor per single step reaction；2) it is realized with a reactor (for example, flask, reaction kettle etc.), in the reaction Every step reaction is sequentially completed in device, needs to add multiple raw materials successively according to reaction process, that is, each step in reaction process It after reaction, just has " stop ", waits for the raw material of further addition subsequent reactions.Some documents are also mode 2) it is referred to as continuously (continuous), essence is also interval, because there is " stop " in the process, needs to wait for feeding or needs to be next Step reaction is adjusted to suitable temperature (for example, heating, cooling or heat preservation).
By the improvement of existing apparatus and process, in direct fluorinated continuation method, there are also trials, only portion Decomposition determines but is only to solve above-mentioned three kinds of shortcomings to a certain extent, however it remains reaction time length, low production efficiency, technique The problem of with device flexibility, poor selectivity.
Chinese patent CN1075313A be related to one kind make can fluorinated cyclic annular or non-cyclic carbonate be directly fluorinated synthesis phase It answers fluorocarbons acid esters and the fluorocarbons acid esters of generation is reacted into the corresponding fluorinated functional compounds of synthesis with active nucleophilic agent Method.This method can by batch, it is semicontinuous or continuous in a manner of carry out, reaction unit is not done for a controlled temperature reactor Fluorinated ethylene carbonate synthesis is not specifically mentioned in detailed description.Since different material physical property is (for example, molten boiling point, heat conduction Property, thermal capacitance, solubility etc.) and reactivity there are larger differences, it is corresponding specific to certain raw material and a certain reaction process Process conditions and parameter will be different, therefore this method can be not necessarily used to fluorinated ethylene carbonate synthesis.Though this method is realized Serialization, but there are still following main problems：First, technological operation very complicated, need to fill inert fluid in advance in reactor Reaction medium needs to keep the inertia liquid mass of medium in reactor by supplementing liquid (recycling or new) in the process In constant level；Second is that the reaction time is long, reaction efficiency is low, be only only completed the fluorination process of hectogram grade sample need to inject it is several small When even ten a few houres, strongly limit production-scale expansion.United States Patent (USP) US5420359A, US20020027172A1, US6863211B2, US6491983B2 are directed to similar technique with US20030166487A1, and there are identical deficiencies.In short, The technical process and its device are substantially only simply to connect each step in original interval, and one is the failure to solve work The problem of time-consuming for skill process, flexibility is poor, low production efficiency can not complete direct fluoro in a short time (within 10 minutes) Reaction, also without solving the problems, such as poor controllability existing for direct fluorination, mass transfer, flexibility and poor selectivity；Second is that technique Process is not continuous flow process, the continuous flow process refer to material in production process (include raw material, intermediate, product, The reaction mixture of solvent etc.) it is continuously to flow, waiting is not stopped, i.e. product is continuously produced.Certainly, it is literary In all mention, compared to batch and semi-continuous method, continuous method can usually provide higher yield, preferable product matter The more effective utilization of amount and fluorine.
Chinese patent CN1104930A is related to a kind of method of fluorinated organic compound direct in a tubular reactor.This method is By raw material and inert liquid medium after upstream line mixes, tubular reactor is delivered to, and at it by fluid conveying device In mixed with fluorine gas, recycle fluorinated product needed for the generation of sufficiently long time.Wherein embodiment does not refer to fluorinated ethylene carbonate Synthesis.The problem of being primarily present is that reaction mixture recycles fluorination overlong time in the reactor, needs a few hours to a couple of days, Even the time of several weeks, reaction efficiency is very low, can not complete direct fluoro-reaction (within 10 minutes) in a short time, also not have Solve the problems, such as poor controllability, mass transfer, flexibility and poor selectivity existing for direct fluoro method.
Chinese patent CN102548949A is related to one kind and is used to continuously prepare correspondence by ethylene carbonate and dimethyl carbonate Fluorinated ethylene carbonate and fluoro dimethyl carbonate method and realize this method device.In reaction process reactant with F2/N2Mixed gas is continually introduced into reactor cascade, and reaction mixture is detached after being extracted out from reactor cascade by continuous still Go out target product.In the range of 10~70 DEG C, the conversion ratio of organic carbonate is up to 70%.The technique is primarily present following ask Topic：
First, its core reaction equipment is the multiple reactor cascades of (2-5) with demarcation strip, it is the institute simply connected It calls " continuous ", material still has stop to wait in each reactor, not continuous flow reactor；In addition include in device additional Cooler cycle through a part of reaction mixture to remove a large amount of reaction heat generated in fluorination reaction；While in order to make Reaction mixture is sufficiently mixed, and needing, which makes fluorine gas be previously threaded through a kind of frit, obtains finely dispersed form introducing reactor. I.e. the reaction unit has installed a variety of ancillary equipments additional, integration degree is low, and structure is multiple to meet fluoro-reaction heat and mass requirement It is miscellaneous.In short, the reaction unit is not integrated continuous flow reactor and it is necessary to could be completed instead by multiple reactor cascades It should.
Second is that the residence time is still longer, the reaction time of this method is at least 30 minutes.
Third, technical process is complicated for operation, for example, it is mentioned that each material demand reaches certain " quiet in reaction mixture Only concentration ", reaction just can be carried out successfully, each in reaction mixture when so-called " resting levels " refer to that reaction is smoothed out The fixed concentration that material demand is kept, reaction need certain time to be possible to reach wanting for this " resting levels " after starting It asks；The extraction mixture from each cascade reactor is needed in reaction process, and extracts the quantity and each group of mixture out Concentration is divided to need to keep certain proportionate relationship with inlet amount；In the process material need in each reactor stop wait for and It is different to stop the time waited for, and discontinuous flow moves, and is not continuous flow process process；Same reactor is synthesizing not With degree of fluorination fluorinated ethylene carbonate when material heat release wherein stop the stand-by period and also differ.In addition these above-mentioned techniques It is required that both increase integrated artistic control difficulty and production scene operation difficulty.
Chinese patent CN201080042843A be related to using similar above-mentioned reactor cascade realize polyfluoro generation (two fluoro, Three fluoro and four fluoro) ethylene carbonate and respective mixtures synthesis, device and technical process equally exist above three and ask Topic, for example, material need to stop in each reactor wait for and stop waiting time it is different and same anti- The device stop stand-by period of material wherein in the fluorinated ethylene carbonate for synthesizing different degree of fluorination is answered also to differ.In short, Although above-mentioned technical process and its device have used reactor cascade to realize technique continuous, but reaction mixture is in cascade reaction Still there is stop waiting in device and discontinuous flow moves, be not continuous flow process process, simultaneous reactions are simultaneously unhappy, and the reaction time reaches 30 Minute or more.
In addition, the technique of the prior art, whether batch technology or semicontinuous, continuous technique or reactor grade The technique of connection, all unavoidably there are enlarge-effects, this brings many uncertainties for further industrial applications.Amplification effect It answers (Scaling up Effect), refers to that carrying out chemical process (i.e. small-scale) using mini-plant tests (such as laboratory rule Mould) result of study that obtains, the result obtained under the same operating conditions with large production equipment (such as industrially scalable) Often there is very big difference.Influence in relation to these difference is known as enlarge-effect.Its reason is mainly in small-scale experimental facilities Temperature, concentration, residence time of material distribution with large-scale equipment in difference.That is, under identical operating condition, nothing Method repeats the result of study of small scale experiments completely on industrially scalable；To be obtained on industrially scalable and small-scale reality It tests identical or approximate as a result, it is desirable to by optimizing and revising, changes technological parameter and operating condition.For chemical process, Enlarge-effect is a problem of difficulty is larger and in the urgent need to address.If do not solved, production process and product can be caused Quality has very big uncertainty, first, the quality for directly resulting in downstream product is unstable, it is difficult to control；It is second is that uncertain Production process technology parameter fluctuation can be brought, and then leads to not effectively control production process so that production security cannot obtain To guarantee, many security risks are buried for production process.
To sum up, direct fluoro-reaction has device and technique mass transfer, heat transfer, safety etc. more harsh requirement, is limited In device and technique, the prior art leads to the reaction time all there are the problem of different degrees of device is complicated, technique is cumbersome The problem of long, low production efficiency, technique and device flexibility, poor selectivity.For the fluoro carbonic acid second of different degree of fluorination The synthesis of enester has not yet to see and develops the reaction advantage that can either give full play to direct fluorination, and can overcome this method The production technology of three of the above shortcoming, i.e.,：Fully solve heat transfer, mass transfer problem, also take into account different material physical property (for example, Molten boiling point, thermal conductivity, thermal capacitance, solubility etc.) and reactivity difference flexibility and selective problems.
Invention content
In view of the deficiencies of the prior art, the technical problem to be solved by the invention is to provide it is a kind of quick, flexibly, efficiently, The continuous flow synthesis technology of fluorinated ethylene carbonate that is safe and being easy to large-scale production and the device that can realize the technique.
For the huge thermal discharge of direct fluoro-reaction, needed in process exploitation design optimization and equipment material and structure, The technological parameter that the physicochemical properties and reaction detailed process of material (raw material, intermediate and product etc.) match, balance are anti- The relationship of heat release, system heat transfer and equipment heat exchange is answered, under the premise of production safety and efficiency is ensured, is removed in time a large amount of anti- Should heat, it is higher to cross thermal pressure to prevent system, leads to runaway reaction.For example, different material physical property is (for example, molten boiling point, heat conduction Property, thermal capacitance, solubility etc.) and reactivity can differ greatly, technological parameter is just needed according to specific raw material and specific reaction Process is adjusted and is optimized to do accordingly.In order to the charging of flexible adaptation different material and the production of different degrees of fluorinated product Demand, process exploitation just need the reactivity based on raw material and intermediate, the target product produced and reaction mechanism, flexibly Optimize reaction condition and technological parameter, be allowed to match with reacting detailed process, improve the selectivity of respective objects product.For Gas-liquid two-phase heterogeneous reaction needs in process exploitation to optimize device structure and technological parameter enhancing gas-liquid two-phase mixed effect, Promote two-phase mass transfer, the mass transfer effect of gas-liquid two-phase in reactor is weighed using the specific surface area of gas/liquid dispersion, compares table Area is bigger, and mass transfer effect is better.In addition, in addition to the larger impact by mass transfer factor, fluoro-reaction is also by kinetic factor It influences, mainly includes various physics, chemical factor (for example, gas density, solubility, molten boiling point, critical-temperature, critical pressure Medium, catalyst, flow field and thermal field distribution, residence time destribution in power, system temperature, system pressure, concentration, reaction system Deng) and corresponding reaction mechanism, i.e., can also there be rush to the conversion ratio and selectivity of reaction according to the intensifying method of these factors Into effect.
Continuous synthesis technology (continuous processing, continuous process) refers to that production system respectively produces in production process It is mutually linked between step, ensures continuous service on the whole, but allow to stop in each step and wait for.Continuous flow synthesis technology (continuous flow process, continuous-flow process) has that the used time is short, effect as a kind of continuous processing rapidly and efficiently The features such as rate is high, easy to operate, uninterruptedly adds in raw material in the process, uninterruptedly produces and product is made, in the process Material (reaction mixture for including raw material, intermediate, product, solvent etc.) continuously flows, and is not interrupted, does not stop Waiting is stayed, i.e. product is continuously produced, and is a kind of chemical process of " assembly line " formula.When technological operation reaches To during stationary state, the state parameters such as the composition of material, temperature not time to time change on any position, is stable state mistake in reactor Journey, thus production process and product quality are all stable.In the technique for including multistep reaction, if wherein certain several step Rapid to be continuous or only simply connect each step in original batch technology, which is properly termed as continuous work Skill；And only all steps are all continuous and material continuously flows in entire technical process, that is, are continuously added to original Material, continuously obtains product, could be known as continuous flow process.
Difference based on above-mentioned continuous flow process and batch technology and other continuous processings, continuous flow process is to technical process Control requirement compared with conditional parameter after be both very different, the batch technology of identical product or other continuous processing items Part can not be used for reference or is transplanted in continuous flow process, needed to redesign and be developed.Therefore relative to batch technology and other continuous Technique, continuous flow process are completely new technical process, and often continuous flow process condition is that can not realize in other techniques.
Reaction time in continuous processing, refer to from raw material enter total needed for reactor to output of products reactor when Between.The reaction time is different in continuous processing, and the control requirement and conditional parameter that can cause technical process differ greatly, identical product The process conditions in long reaction time can not be used for reference or are transplanted in the technique of short reaction time, when shortening the reaction of continuous processing Between, it is necessary to redesign development technology process.Therefore relative to the long reaction time continuous processing, short reaction time it is continuous The continuous flow process of technique, especially reaction time in seconds is completely new technical process, and often continuous flow process condition It is that can not realize in other techniques.
The technical issues of to solve the present invention, the present invention adopts the following technical scheme that：
A kind of continuous flow synthesis technology of fluorinated ethylene carbonate, using raw material to be fluorinated and fluorine gas as raw material, continuously successively Fluorinated ethylene carbonate is obtained through mixing dispersion, fluorination reaction and gas-liquid separation step, the continuous flow synthesis technology relates to And to process route view see Fig. 1.
Shown in Fig. 1, fluorinated ethylene carbonate continuous flow synthesis technology of the present invention and corresponding integration are even Afterflow reactor can realize following building-up process：
Using ethylene carbonate as one fluorinated ethylene ester of Material synthesis carbonic acid, carbonic acid two fluoro vinyl acetates (carbonic acid -4,4- difluoros For vinyl acetate, the cis- two fluoro vinyl acetates of -4,5- of carbonic acid, the trans- two fluoro vinyl acetates of -4,5- of carbonic acid), carbonic acid ethylene trifluoride Ester, carbonic acid tetrafluoroethylene ester any one or it is arbitrary a variety of；
Using one fluorinated ethylene ester of carbonic acid as two fluoro vinyl acetate of Material synthesis carbonic acid (two fluoro vinyl acetates of carbonic acid -4,4-, carbon The cis- two fluoro vinyl acetates of -4,5- of acid, the trans- two fluoro vinyl acetates of -4,5- of carbonic acid), carbonic acid ethylene trifluoride ester, carbonic acid tetrafluoro For vinyl acetate any one or it is arbitrary a variety of；
With two fluoro vinyl acetates of carbonic acid -4,4- and/or the cis- two fluoro vinyl acetates of -4,5- of carbonic acid and/or carbonic acid trans- -4, Bis- fluoro vinyl acetates of 5- for Material synthesis carbonic acid ethylene trifluoride ester, carbonic acid tetrafluoroethylene ester any one or it is arbitrary more Kind；
Using carbonic acid ethylene trifluoride ester as Material synthesis carbonic acid tetrafluoroethylene ester.
Herein, term " fluorine gas " is understood to be diluted or not by the diluted fluorine list of inert gas by inert gas Matter.Preferably, step (a) fluorine gas will the application in the form of fluorine simple substance is diluted.Preferred diluent is inert gas, especially It is selected from nitrogen, rare gas or its mixed gas.The mixed gas refers to the mixture of nitrogen and rare gas, institute The rare gas stated refers to the simple substance of 18 race's elements on the periodic table of elements.The mixed gas of fluorine gas and nitrogen is preferred.Fluorine The concentration of gas is to be more than 0% by volume.It is preferably equal to or more than 5% by volume.More preferably it is equal to by volume Or more than 12%.The concentration of fluorine gas is preferably equal to or less than 25% by volume.Excellently, it is to be equal to or less than by volume 18%.Preferably, fluorine gas is included in the admixture of gas with by volume 12% to 18% range.While it may be possible to Fluorine simple substance with various concentration is introduced in these different reactors or with different inert gas or diluted and not dilute The gas with various mixture for the fluorine gas released, but due to actual cause preferably for all reactors using a kind of only spy Fixed gas or admixture of gas.
" degree of fluorination " as described herein refers to the number containing fluorine atom in compound molecule, for example, ethylene carbonate Degree of fluorination is 0, and the degree of fluorination of one fluorinated ethylene ester of carbonic acid is 1, two fluoro vinyl acetate of carbonic acid (bis- fluoro vinyl acetate of carbonic acid -4,4-, Carbonic acid is cis- -4,5-, bis- fluoro vinyl acetates, carbonic acid is trans- -4,5-, bis- fluoro vinyl acetates) fluoro degree be 2, three fluoro second of carbonic acid The degree of fluorination of enester is 3, and the degree of fluorination of carbonic acid tetrafluoroethylene ester is 4.
Wherein, by raw material to be fluorinated in the liquid phase with simple substance fluoride (F2) react to form fluorinated ethylene carbonate, that is, treat fluorine The degree of fluorination of change raw material is less than and/or the degree of fluorination equal to product, the raw material to be fluorinated are selected from：Ethylene carbonate, carbonic acid one Fluorinated ethylene ester, two fluoro vinyl acetate of carbonic acid (the cis- two fluoro vinyl acetates of -4,5- of two fluoro vinyl acetates of carbonic acid -4,4-, carbonic acid, The trans- two fluoro vinyl acetates of -4,5- of carbonic acid), carbonic acid ethylene trifluoride ester, carbonic acid tetrafluoroethylene ester or their arbitrary two kinds Or arbitrary a variety of mixture.
" fluorinated ethylene carbonate " as described herein is selected from：One fluorinated ethylene ester of carbonic acid, two fluoro vinyl acetate (carbon of carbonic acid The cis- two fluoro vinyl acetates of -4,5- of two fluoro vinyl acetates of acid -4,4-, carbonic acid, the trans- two fluoro vinyl acetates of -4,5- of carbonic acid), carbonic acid Ethylene trifluoride ester, carbonic acid tetrafluoroethylene ester any one or it is arbitrary a variety of.
Preferably, direct fluorination reaction can carry out in the presence of suitable atent solvent, and the atent solvent refers to The solvent not reacted with fluorine gas, atent solvent can be straight chain or cricoid perfluocarbon, such as Solvay Solexis are sold Fluorinated ether, carbonic acid tetrafluoroethylene ester or hydrogen fluoride etc..The raw material to be fluorinated can include or molten not comprising inertia Agent.Preferably, it is described to be fluorinated not include atent solvent.
The present invention provides a quick continuous flow synthesizing fluoro carbonic acid that is versatile, only being realized with a reactor The technique of vinyl acetate, i.e.,：Two kinds of reactants of raw material and fluorine gas to be fluorinated are constantly in input reactor, and continuously collect reaction Product.The fluorinated ethylene carbonate is selected from one fluorinated ethylene ester of carbonic acid, carbonic acid two fluoro vinyl acetates (carbonic acid -4,4- difluoros For vinyl acetate, the cis- two fluoro vinyl acetates of -4,5- of carbonic acid, the trans- two fluoro vinyl acetates of -4,5- of carbonic acid), carbonic acid ethylene trifluoride In ester, carbonic acid tetrafluoroethylene ester any one or it is arbitrary a variety of.Reactor the being integrated continuous flow reactor, institute The continuous flow reactor stated includes three functional units：Mix dispersal unit, fluorination reaction unit and gas-liquid separation unit.By The collaboration that the optimization set with process conditions such as temperature and/or pressure and three functional units are divided in functional unit warm area is made With without additional post processing or purification step in technique pilot process, technique total time foreshortening in 10 minutes, greatly promote The efficiency of technique.Especially be available with a reactor only can neatly be synthesized by simple adjusting process parameter it is more The fluorinated ethylene carbonate and its mix product of the different degree of fluorination of kind, and various degree of fluorination can be synthesized with high selectivity Target product, technique strong applicability, makes industrial production be suitable for the market demand.
The synthesis process of the fluorinated ethylene carbonate is without enlarge-effect, and iodine scale is to reaction conversion ratio, mesh Mark product yield and selectivity do not influence.The present invention overcomes prior art preparation fluorinated ethylene carbonates enlarge-effect Defect is very suitable for industrialization large-scale production.
First purpose of the present invention provides a kind of quick continuous flow synthesis technology of fluorinated ethylene carbonate, and feature exists In：The synthesis technology is using raw material to be fluorinated and fluorine gas as reactant, continuously successively through mixing dispersion, fluorination reaction, gas-liquid Separating step obtains fluorinated ethylene carbonate, and the synthesis technology carries out in an integrated continuous flow reactor, in institute The feed inlet for stating integrated continuous flow reactor uninterruptedly adds in raw material and fluorine gas to be fluorinated, is reacted in the integrated continuous flow Device discharge port uninterruptedly obtains fluorinated ethylene carbonate, and the reaction time is equal to or less than 600s.
Further, the reaction time is 20~600s, it is preferable that the reaction time is 30~480s, it is highly preferred that instead It is 40~300s between seasonable.
Further, the synthesis technology is without enlarge-effect.
Further, the integrated continuous flow reactor includes mixing dispersal unit, fluorination reaction unit and gas-liquid point From unit, the mixing dispersal unit is used to mix raw material to be fluorinated or atent solvent with fluorine gas and disperse fluorine gas In the liquid phase, this mixture is then delivered to fluorination reaction unit；Or the mixing dispersal unit is for will be to be fluorinated Raw material mixes with fluorine gas and makes fluorine gas dispersion that preliminary fluorination reaction occur simultaneously in the liquid phase, then conveys this mixture To fluorination reaction unit；The fluorination reaction unit reacts generation fluorinated ethylene carbonate with fluorine gas simultaneously for raw material to be fluorinated It is transported to gas-liquid separation unit；The gas-liquid separation unit is used for the separation of liquid and gas.
Further, in the mixing dispersal unit, fluorine gas only contacts mixing simultaneously with raw material to be fluorinated or atent solvent In the liquid phase, then into fluorination reaction unit fluorination reaction occurs for dispersion；In the mixing dispersal unit, fluorine gas is with treating fluorine Change raw material contact to be mixed and dispersed in liquid phase, while with raw material to be fluorinated preliminary fluorination reaction occurs for fluorine gas, then into fluorine Change reaction member and further fluorination reaction occurs.
Further, the mixing dispersal unit or fluorination reaction unit further have point of liquids and gases From function.Wherein, the gas after gas-liquid separation can recycle, and can also pass through exhaust gas processing device.
Further, the synthesis technology is carried out equal to or more than under environmental pressure, preferably equal to or more than 5bar Pressure under carry out, more preferably carried out under the pressure equal to or more than 10bar, the pressure is relative pressure.
Further, the pressure of each unit may be the same or different.
Further, the synthesis technology carries out under gradient pressure, and the mixing dispersal unit pressure is more than fluorination Reaction member pressure, fluorination reaction cell pressure are more than gas-liquid separation unit pressure.The mixing dispersal unit pressure uses high Pressure can increase the solubility of fluorine gas in the liquid phase, reduce fluorine gas gaseous phase volume, promote the gas-liquid of raw material and fluorine gas to be fluorinated Two-phase mixtures, this is conducive to fluorination reaction progress；Fluorination reaction cell pressure is less than mixing dispersal unit, can reduce reaction production The solubility of raw hydrogen fluoride gas in the liquid phase, while fluorination reaction cell pressure cannot be too low to ensure fluorine gas in the liquid phase Enough solubility, fluorination reaction unit use pressure to make both solubility reach balance can just effectively facilitate react into Row；Gas-liquid separation unit applies smaller pressure, the solubility of hydrogen fluoride gas in the liquid phase is further reduced, convenient for reacting Gas-liquid separation after helps to reduce the residual of hydrogen fluoride in product fluorinated ethylene carbonate, improves product quality.Due to this The synthetic reaction of invention is heterogeneous reaction, in order to promote the progress of reaction, needs to increase the solubility of fluorine gas in the liquid phase, separately On the one hand, it needs to reduce the solubility of the hydrogen fluoride gas for reacting generation in the liquid phase, mixing dispersal unit, fluorination reaction list The gradient pressure coordinated that member, gas-liquid separation unit are formed, reaches the best of fluorine gas, hydrogen fluoride gas solubility in the liquid phase Balance, promotes the progress of reaction, realizes fully reaction in a short time, and high efficiency completes reaction in high quality.
Further, the pressure of the mixing dispersal unit is 5~18bar, preferably 10~15bar；Fluorination reaction unit Pressure be 3~18bar, preferably 5~15bar；The pressure of gas-liquid separation unit is 0~10bar, preferably 2~7bar.
Further, the integrated continuous flow reactor feed mouth is one or more, the integrated continuous flow reaction Device discharge port is one or more.
Further, each unit independently includes more than one reactor module or reactor module group, Wherein reactor module group is made of multiple reactor module serial or parallel connections, is serially connected between each unit.
Further, each unit corresponds to a warm area, and each warm area independently includes more than one reaction Device module or reactor module group, wherein reactor module group are made of multiple reactor module serial or parallel connections, each warm area it Between be serially connected.
Further, between the reactor module, between reactor module group, reactor module and reactor module It is respectively serial or parallel connection between group.
Further, the reactor module can optionally realize the reaction unit of continuous flow process from any one, excellent Choosing, the reaction unit is selected from microreactor (Microreactor), series connection coil reactor (Tandem loop Reactor), tubular reactor (Tubular reactor) any one or it is arbitrary a variety of.The microreactor, also known as Micro-structured reactor or micro passage reaction are that a kind of chemical reaction wherein is happened at universal lateral dimensions in 1mm and following Finite region in equipment, this kind of most typical form of finite region is miniature sizes channel.Series connection coil reactor, i.e., Be together in series coil reactor with pipeline the reactor of composition, and wherein coil reactor is that tubular reactor is made coil pipe Form.Tubular reactor be occur the middle of last century it is a kind of in a tubular form, the very big continuous manipulation reactor of draw ratio.It is this Reactor can be very long；It can also multitube parallel with single tube；It can be managed with blank pipe or filling.Preferably, reaction unit Can be one or more.
Further, the reaction unit has flow channel.
Further, the flow channel is by resistance to F2It is made with the material of HF, it is the preferred stainless steel of the material, resistance to F2It is (partly or fluoridized with alloy (Monel is containing gold, inconel, Ha Site nickel-base alloys), the polymer material of HF Polymer poly, alkylen polymers), other kinds of polymer (polytetrafluoroethylene (PTFE), perfluoroalkoxyalkanes copolymer), ceramics (silicon carbide) or it is coated with resistance to F2With the material of HF.
Further, the flow channel specific surface area is more than or equal to 2000m2/m3, heat transfer coefficient is greater than or equal to 1.5MW/m3K, gas liquid dispersion specific surface area are more than or equal to 47000m2/m3.The flow channel has larger specific surface area (it is greater than or equal to 2000m2/m3), it can obtain more than or equal to 1.5MW/m3The heat transfer coefficient of K, system heat transfer property are outstanding；Object Material can all be forced to mix along the entire flow process of flow channel, and gas liquid dispersion specific surface area may be up to 47000m2/m3, Gas-liquid mass transfer is had excellent performance.
Further, the raw material to be fluorinated is selected from ethylene carbonate, one fluorinated ethylene ester of carbonic acid, two fluorinated ethylene of carbonic acid Ester (the cis- two fluoro vinyl acetates of -4,5- of two fluoro vinyl acetates of carbonic acid -4,4-, carbonic acid, trans- two fluorinated ethylenes of -4,5- of carbonic acid Ester), carbonic acid ethylene trifluoride ester, in carbonic acid tetrafluoroethylene ester any one or it is arbitrary a variety of, the raw material to be fluorinated Degree of fluorination is less than or equal to product fluorinated ethylene carbonate.
Further, the raw material to be fluorinated includes atent solvent, and the atent solvent refers to fluorine gas not occur The solvent of chemical reaction.
Further, the atent solvent is selected from straight chain or cricoid perfluocarbon, preferred fluorinated ether, four fluoro of carbonic acid In vinyl acetate, hydrogen fluoride any one or it is arbitrary a variety of.
Further, the fluorinated ethylene carbonate is selected from one fluorinated ethylene ester of carbonic acid, two fluoro vinyl acetate (carbon of carbonic acid The cis- two fluoro vinyl acetates of -4,5- of two fluoro vinyl acetates of acid -4,4-, carbonic acid, the trans- two fluoro vinyl acetates of -4,5- of carbonic acid), carbonic acid In ethylene trifluoride ester, carbonic acid tetrafluoroethylene ester any one or it is arbitrary a variety of.
Further, the synthesis technology can carry out in the absence of atent solvent.
Further, the continuous flow synthesis technology carries out in the integrated continuous flow reactor comprising 3 warm areas, The mixing dispersal unit corresponds to warm area 1, and the fluorination reaction unit corresponds to warm area 2, the gas-liquid separation unit pair Warm area 3 is answered, the continuous flow synthesis technology includes the following steps：
(a) raw material or atent solvent to be fluorinated contact mixing in warm area 1 with fluorine gas and make fluorine gas dispersion in the liquid phase, then This mixture is delivered to warm area 2；Or raw material to be fluorinated contacts mixing in warm area 1 with fluorine gas and makes fluorine gas dispersion in the liquid phase Preliminary fluorination reaction occurs simultaneously, this mixture is then delivered to warm area 2；
(b) raw material to be fluorinated reacts generation fluorinated ethylene carbonate in warm area 2 with fluorine gas and is delivered to reaction mixture Warm area 3；
(c) reaction mixture enters the separation that warm area 3 carries out gas and liquid.
Further, the temperature of the warm area 1 is -40~20 DEG C, preferably -20~10 DEG C.
Further, the temperature of the warm area 2 is 10~100 DEG C, preferably 30~80 DEG C, more preferable 40~60 DEG C.
Further, the temperature of the warm area 3 is 30~80 DEG C, preferably 40~60 DEG C.
Further, the synthesis technology is carried out equal to or more than under environmental pressure, preferably equal to or more than 5bar Pressure under carry out, more preferably carried out under the pressure equal to or more than 10bar.
Further, the pressure of each warm area may be the same or different.
Further, the synthesis technology carries out under gradient pressure, and 1 pressure of warm area is more than 2 pressure of warm area, temperature 2 pressure of area is more than 3 pressure of warm area.Three warm area gradient pressure coordinateds, reach fluorine gas, hydrogen fluoride gas dissolves in the liquid phase The optimum balance of degree promotes the progress of reaction, realizes fully reaction in a short time, and high efficiency completes reaction in high quality. Preferably, further combined with the synergistic effect of three warm area Temperature Distributions, more high efficiency, in high quality completion reaction.
Further, the pressure of warm area 1 is 5~18bar, preferably 10~15bar；The pressure of warm area 2 is 3~18bar, excellent Select 5~15bar；The pressure of warm area 3 is 0~10bar, preferably 2~7bar.
Further, the fluorine gas is diluted or not by the diluted fluorine simple substance of inert gas by inert gas, described Inert gas is selected from nitrogen, rare gas or its mixed gas, and the mixed gas refers to the mixing of nitrogen and rare gas Object, the rare gas refer to the simple substance of 18 race's elements on the periodic table of elements.The preferred fluorine simple substance of the fluorine gas and nitrogen Mixed gas.
Further, the concentration of fluorine simple substance is more than 0%, preferably equal to or greater than 5% by volume in fluorine gas, more preferably etc. In or more than 12%；The concentration of fluorine simple substance is preferably equal to or less than 25%, preferably equal to or smaller than 18% by volume in fluorine gas, Most preferably, in fluorine gas fluorine simple substance a concentration of 12% to 18%.
It has to be noticed that in c h bond and F2Reaction process in each C-F keys for being formed, form a molecule HF. Thus, it is supposed that ethylene carbonate (EC) and fluorine (F2) between be a stoichiometric reaction, then require F2The ratio between/EC is 4, i.e., If using 1 mole of ethylene carbonate as raw material to be fluorinated, 4 moles of F is needed in stoichiometry2To realize carbonic acid second Enester it is fully fluorinated.Therefore, in the present invention, it is specified that F for the sake of stating simplicity2The ratio between/H expressions：In raw material to be fluorinated It will each be substituted and be formed the corresponding F of H atom of C-F keys2Molecular number, i.e., the H of fluorine substitution reaction will each occur Atom is averaged corresponding F2Equivalents.That is, F2Equivalent proportion with raw material to be fluorinated is to multiply substituted H atom number With F2The ratio between/H, for example, with ethylene carbonate (EC) for Material synthesis carbonic acid ethylene trifluoride ester, using F2/ H ratios are 1.15:1 Condition, due to by substituted H atom number be 3, then F2With the equivalent proportion F of raw material to be fluorinated2/ EC is 3.45:1.
Further, the F2The ratio between/H is 1.0~2.0:1, preferably 1.05~1.50:1, more preferable 1.10~ 1.25:1。
The method of the present invention comes synthesizing fluoroethylene carbonate, the fluoro in a manner of a kind of quick and high universalizable Ethylene carbonate is selected from one fluorinated ethylene ester of carbonic acid, (two fluoro vinyl acetates of carbonic acid -4,4-, carbonic acid are suitable for two fluoro vinyl acetate of carbonic acid The trans- two fluoro vinyl acetates of -4,5- of two fluoro vinyl acetates of formula -4,5-, carbonic acid), carbonic acid ethylene trifluoride ester, four fluoro second of carbonic acid In enester any one or it is arbitrary a variety of.In preferred embodiments, one fluorinated ethylene ester of carbonic acid, two fluorinated ethylene of carbonic acid Ester, carbonic acid ethylene trifluoride ester, carbonic acid tetrafluoroethylene ester any one or arbitrary a variety of selectivity manufacture are feasible.
The continuous flow synthesis technology of the present invention has considerable flexibility, versatile, only can be fast with a reactor Fast continuous flow synthesizing fluoroethylene carbonate, and the target product of various degree of fluorination can be synthesized with high selectivity.Preferably, The reaction conversion ratio of the synthesis technology is more than 90%, it is furthermore preferred that reaction conversion ratio is more than 95%；The fluoro carbonic acid The yield of vinyl acetate is more than 85%, it is furthermore preferred that the yield of fluorinated ethylene carbonate is more than 90%.
It should be noted that the concentration of fluorine in practical synthesis used in (including in laboratory, pilot scale, actual production process) Have the deviation of ± 3 percentage points of bulk concentration；F2The ratio between/H has ± 0.05 deviation；Warm area temperature has ± 5 DEG C inclined Difference；Warm area pressure has the deviation of ± 1bar；Reaction time has the deviation of ± 10s.
Second object of the present invention is to provide a kind of quick continuous synthesis technology for being exclusively used in fluorinated ethylene carbonate Integrated reactor, to meet the condition of the continuous processing, the present invention develops special integrated reactor.The reaction Device can be modular structure, need to design organizational form, the quantity of module, the module that each warm area includes, it is also necessary to develop Targetedly process conditions and parameter, division and temperature setting including each warm area, the setting of pressure and pressure and temperature Comprehensive synergistic effect occurs for collaboration setting, any of the above factor so that this continuous processing is achieved.It can also be further It with reference to each temperature and material concentration, material proportion and material flow, is allowed to match with reaction process, obtains preferably reacting effect Fruit.Each intermediate product of the material comprising each raw material, reaction process, concentration of the material concentration comprising each raw material, The concentration of each intermediate product, the material proportion include the matching of each raw material, the concentration of each intermediate product, the material stream The flow velocity of flow velocity of the speed comprising each raw material, each intermediate product.
A kind of integrated reactor of continuous flow synthesis technology for being exclusively used in fluorinated ethylene carbonate of the present invention, it is described Integrated reactor use modular construction, the integrated reactor use modular construction, including mixing dispersal unit, Fluorination reaction unit and gas-liquid separation unit, the mixing dispersal unit are used for raw material to be fluorinated or atent solvent and fluorine gas Contact mixes and makes fluorine gas dispersion in the liquid phase, this mixture then is delivered to fluorination reaction unit；Or the mixing Dispersal unit is anti-for raw material to be fluorinated with fluorine gas to be mixed and made fluorine gas dispersion preliminary fluorination occurs simultaneously in the liquid phase Should, this mixture is then delivered to fluorination reaction unit；The fluorination reaction unit is anti-for raw material to be fluorinated and fluorine gas Fluorinated ethylene carbonate should be generated and be transported to gas-liquid separation unit；The gas-liquid separation unit is used for liquid and gas Separation.
Further, the mixing dispersal unit or fluorination reaction unit further have point of liquids and gases From function.
Further, the integrated continuous flow reactor feed mouth is one or more, the integrated continuous flow reaction Device discharge port is one or more.
Further, each unit independently includes more than one reactor module or reactor module group, Wherein reactor module group is made of multiple reactor module serial or parallel connections, is serially connected between each unit.
Further, each unit corresponds to a warm area, and each warm area independently includes more than one reaction Device module or reactor module group, wherein reactor module group are made of multiple reactor module serial or parallel connections, each warm area it Between be serially connected.
Further, between the reactor module, between reactor module group, reactor module and reactor module It is respectively serial or parallel connection between group.
Further, the reactor module can optionally realize the reaction unit of continuous flow process from any one, excellent Choosing, the reaction unit is selected from microreactor, coil reactor of connecting, tubular reactor any one or it is arbitrary more Kind.Preferably, reaction unit can be one or more.
Further, the reaction unit has flow channel.
Further, the flow channel specific surface area is more than or equal to 2000m2/m3, heat transfer coefficient is greater than or equal to 1.5MW/m3K, gas liquid dispersion specific surface area are more than or equal to 47000m2/m3。
Further, the flow channel is by resistance to F2It is made with the material of HF, it is the preferred stainless steel of the material, resistance to F2It is (partly or fluoridized with alloy (Monel is containing gold, inconel, Ha Site nickel-base alloys), the polymer material of HF Polymer poly, alkylen polymers), other kinds of polymer (polytetrafluoroethylene (PTFE), perfluoroalkoxyalkanes copolymer), ceramics (silicon carbide) or it is coated with resistance to F2With the material of HF.
Preferably, the mixing dispersal unit corresponds to warm area 1, and the fluorination reaction unit corresponds to warm area 2, described Gas-liquid separation unit corresponds to warm area 3.
The present invention compared with the prior art, has the beneficial effect that：
1st, the efficient continuous flow synthesis of fluorinated ethylene carbonate is realized on integrated continuous flow reactor.That is, reaction Object continuously in input reactor, in the process without additional post processing or purification step, continuously collects reaction Product.By means of the setting of gradient pressure and the division of different warm areas, the efficiency of technique is greatly improved.Reaction time is at most 10 minutes.
2nd, method of the invention allows selectively to manufacture one fluoro second of carbonic acid in a manner of a kind of quick and high universalizable In enester, two fluoro vinyl acetate of carbonic acid, carbonic acid ethylene trifluoride ester, carbonic acid tetrafluoroethylene ester any one or it is arbitrary more Kind.Process selectivity is good and device flexibility is strong, only can be flexible by simple adjusting process parameter using a reactor The fluorinated ethylene carbonate and its mix product of a variety of different degree of fluorination of ground synthesis, technique and device strong applicability, make industry Production is suitable for the market demand.
3rd, process safety significant increase, the relatively small liquid holdup of continuous flow reactor and excellent heat and mass are special Property, the shorter reaction time (in 10 minutes) is so that the technical process is safer in addition.The wherein described reactor liquid holdup Refer to the total volume for the reaction mass when operation reaches stationary state, having in any moment reactor.
4th, fluorination reaction needs to increase gas-liquid two-phase contact to promote to react as gas-liquid two-phase reaction, the work of the prior art In order to reach appropriate yield in skill, need to reduce raw material flow rate or the multiple cycle of raw material is several to increase the contact of gas-liquid two-phase Rate, so as to also just extend the reaction time, but this will obviously reduce the efficiency of fluorination reaction.And the technical process of the present invention can be It is carried out under gradient pressure, the mixing dispersal unit pressure is more than fluorination reaction cell pressure, and fluorination reaction cell pressure is more than Gas-liquid separation unit pressure.The mixing dispersal unit pressure can increase the solubility of fluorine gas in the liquid phase using high pressure, Reduce fluorine gas gaseous phase volume, raw material and fluorine gas gas-liquid two-phase to be fluorinated is promoted to mix, this is conducive to fluorination reaction progress；Fluorination is anti- Cell pressure is answered to be less than mixing dispersal unit, the solubility of the hydrogen fluoride gas of reaction generation in the liquid phase can be reduced, simultaneously Fluorination reaction cell pressure cannot be too low to ensure fluorine gas enough solubility in the liquid phase, and the pressure that fluorinated units use will make Both solubility, which reach balance, can just effectively facilitate reaction progress；Gas-liquid separation unit applies smaller pressure, further reduces The solubility of hydrogen fluoride gas in the liquid phase convenient for gas-liquid separation after completion of the reaction, helps to reduce product fluoro carbonic acid The residual of hydrogen fluoride in vinyl acetate improves product quality.It is anti-in order to promote since the synthetic reaction of the present invention is heterogeneous reaction The progress answered needs to increase the solubility of fluorine gas in the liquid phase, on the other hand, the hydrogen fluoride gas for reducing reaction generation is needed to exist Solubility in liquid phase, the gradient pressure coordinated that mixing dispersal unit, fluorination reaction unit, gas-liquid separation unit are formed, Reach the optimum balance of fluorine gas, hydrogen fluoride gas solubility in the liquid phase, promote the progress of reaction, realize fill in a short time Divide reaction, high efficiency completes reaction in high quality.
5th, the setting of cooperation gradient pressure is also divided to accelerate reaction speed by warm area in this technique, shortens the reaction time. High pressure is coordinated to increase the solubility of fluorine gas in the liquid phase by low temperature in dispersal unit is mixed, while high pressure increases reactor The concentration of fluorine gas in unit volume promotes the mixing mass transfer of raw material and fluorine gas to be fluorinated, can obtain up to 95% high conversion With 90% yield so that the reaction time greatly shorten, in typically 10 minutes can the reaction was complete, production it is highly efficient.
6th, according to the mass transfer of fluorination reaction and demanding kinetics and use raw material (including raw material to be fluorinated and fluorine gas) Physics, chemical property devise three functional units in an integrated continuous flow reactor.Wherein mixing dispersal unit is used In being mixed raw material to be fluorinated or atent solvent with fluorine gas and making fluorine gas dispersion in the liquid phase, then this mixture is conveyed To fluorination reaction unit；Or the mixing dispersal unit is used to that raw material to be fluorinated with fluorine gas to be mixed to and made fluorine gas point It dissipates and preliminary fluorination reaction occurs simultaneously in the liquid phase, this mixture is then delivered to fluorination reaction unit；The fluorination is anti- Unit is answered to react generation fluorinated ethylene carbonate with fluorine gas for raw material to be fluorinated and is transported to gas-liquid separation unit；It is described Gas-liquid separation unit for liquid and gas separation.It is acted synergistically by three functional units so that reaction only needs 10 points Clock or even shorter time are completed.A reactor is only needed to complete reaction process, integration degree is high.
7th, in integrated continuous flow reactor, due to flow speed stability, stable production process, thus product quality it is stable, Favorable reproducibility.
8th, the technique still completed reaction, product content and yield and laboratory rule on industrially scalable in 10 minutes It is essentially identical during mould, enlarge-effect is not found, solves the problems, such as the industrialization amplification of fluorinated ethylene carbonate continuous flow process.
9th, the reactor can meet fluorination reaction to device and technique without additional cooling or gas dispersion adjustment equipment The rigors of mass transfer, heat transfer, safety, corrosion resistant etc., technological operation is simple, energy saving, and integration degree is high, volume Small, floor space is small, has greatly saved workshop land used.
Description of the drawings
Fig. 1 is fluorinated ethylene carbonate continuous flow synthesis technology schematic diagram of the present invention；
Fig. 2 is the schematic diagram of integrated reactor of the present invention.
Wherein, the temperature of warm area 1 is T1；The temperature of warm area 2 is T2；The temperature of warm area 3 is T3.
Specific embodiment
With reference to specific embodiment, the present invention is further explained.It should be understood that these embodiments are merely to illustrate this hair It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after the content of instruction of the present invention has been read, this field skill Art personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims institute The range of restriction.
Embodiment 1
Fluorinated ethylene carbonate embodiment：
Material concentration to be fluorinated in the present embodiment is mass concentration, and the concentration of fluorine simple substance is that volume is dense in fluorine gas Degree, the purity of product are detected using gas-chromatography (GC).
Wherein, the temperature of warm area 1 is T1；The temperature of warm area 2 is T2；The temperature of warm area 3 is T3.
Raw material 1 (ethylene carbonate) is conveyed by constant flow pump, 2 (20%F of raw material2And 80%N2Gaseous mixture) drawn by pipeline Enter, the two flows through warm area 1 and be sufficiently mixed simultaneously initial reaction in the contact of warm area 1.The mixture of outflow warm area 1 enters warm area 2 In, it flows through warm area 2 and the corresponding fluorinated ethylene carbonate of fluorination reaction occurs, until the reaction is complete.Flow out warm area 2 reaction solution into Enter warm area 3 and carry out gas liquid separation, obtain the reaction mother liquor containing one fluorinated ethylene ester of carbonic acid.Collect reaction mother liquor.Mother liquor Distillation, cooling etc., you can obtain one fluorinated ethylene ester of carbonic acid.Each response parameter and result are as follows：
* average value
Embodiment 2-6
Using the operating method of embodiment 1, investigate and one fluorinated ethylene ester of carbonic acid, each parameter are prepared under differential responses parameter Condition and the results are shown in table below.
* average value
Embodiment 7-11
Using the operating method of embodiment 1, investigate and two fluoro vinyl acetate of carbonic acid, each parameter are prepared under differential responses parameter Condition and the results are shown in table below.
* average value
Embodiment 12-14
Using the operating method of embodiment 1, investigate and carbonic acid ethylene trifluoride ester, each parameter are prepared under differential responses parameter Condition and the results are shown in table below.
* average value
Embodiment 15-18
Using the operating method of embodiment 1, investigate and carbonic acid tetrafluoroethylene ester, each parameter are prepared under differential responses parameter Condition and the results are shown in table below.
* average value.

Claims (10)

1. a kind of quick continuous flow synthesis technology of fluorinated ethylene carbonate, it is characterised in that：The synthesis technology is to treat fluorine It is reactant to change raw material and fluorine gas, continuously obtains fluoro ethylene carbonate through mixing dispersion, fluorination reaction, gas-liquid separation step successively Ester, the synthesis technology carry out in an integrated continuous flow reactor, the integrated continuous flow reactor into Material mouth uninterruptedly adds in raw material and fluorine gas to be fluorinated, and fluoro carbon is uninterruptedly obtained in the integrated continuous flow reactor discharge port Vinyl acetate, reaction time are equal to or less than 600s.
2. continuous flow synthesis technology according to claim 1, it is characterised in that：The reaction time is 20~600s, Preferably 30~480s, more preferable 40~300s.
3. continuous flow synthesis technology according to claim 1 or 2, it is characterised in that：The integrated continuous flow reactor Including mixing dispersal unit, fluorination reaction unit and gas-liquid separation unit, the mixing dispersal unit is used for original to be fluorinated Material or atent solvent mix with fluorine gas and make fluorine gas dispersion in the liquid phase, this mixture then is delivered to fluorination reaction list Member；Or the mixing dispersal unit is same in the liquid phase for raw material to be fluorinated with fluorine gas to be mixed and made fluorine gas disperse The preliminary fluorination reactions of Shi Fasheng, are then delivered to fluorination reaction unit by this mixture；The fluorination reaction unit is used to treat Fluorinated materials react generation fluorinated ethylene carbonate with fluorine gas and are transported to gas-liquid separation unit；The gas-liquid separation list Member is used for the separation of liquid and gas.
4. according to claim 1-3 any one of them continuous flow synthesis technologies, it is characterised in that：The synthesis technology equal to Or carried out more than under environmental pressure, it is preferably carried out under the pressure equal to or more than 5 bar, more preferably equal to or more than 10 It is carried out under the pressure of bar, the pressure is relative pressure.
5. according to claim 1-3 any one of them continuous flow synthesis technologies, it is characterised in that：The mixing dispersal unit, Each unit in fluorination reaction unit and gas-liquid separation unit independently includes more than one reactor module or reactor Module group, wherein reactor module group are made of multiple reactor module serial or parallel connections, are serially connected between each unit.
6. according to claim 1-3 any one of them continuous flow synthesis technologies, it is characterised in that：The mixing dispersal unit, Each unit in fluorination reaction unit and gas-liquid separation unit corresponds to a warm area, and each warm area independently includes more than one Reactor module or reactor module group, wherein reactor module group be made of multiple reactor module serial or parallel connections, respectively It is serially connected between warm area.
7. according to claim 1-6 any one of them continuous flow synthesis technologies, it is characterised in that：The continuous flow synthesis work Skill carries out in the integrated continuous flow reactor comprising 3 warm areas, and the mixing dispersal unit corresponds to warm area 1, described Fluorination reaction unit corresponds to warm area 2, and the gas-liquid separation unit corresponds to warm area 3, and the continuous flow synthesis technology is included such as Lower step：
（a）Raw material or atent solvent to be fluorinated contact mixing in warm area 1 with fluorine gas and make fluorine gas dispersion in the liquid phase, then by this Mixture is delivered to warm area 2；Or raw material to be fluorinated contacts mixing in warm area 1 with fluorine gas and fluorine gas is made to disperse in the liquid phase simultaneously Preliminary fluorination reaction occurs, this mixture is then delivered to warm area 2；
（b）Raw material to be fluorinated reacts generation fluorinated ethylene carbonate in warm area 2 with fluorine gas and reaction mixture is delivered to warm area 3；
（c）Reaction mixture enters the separation that warm area 3 carries out gas and liquid.
8. continuous flow synthesis technology according to claim 7, it is characterised in that：The concentration of fluorine simple substance is by volume in fluorine gas More than 0%, preferably equal to or greater than 5%, more preferably equal to or greater than 12%；The concentration of fluorine simple substance is preferably by volume etc. in fluorine gas In or less than 25%, preferably equal to or smaller than 18%, most preferably, a concentration of the 12% to 18% of fluorine simple substance in fluorine gas.
9. continuous flow synthesis technology according to claim 7, it is characterised in that：F2The ratio between/H is 1.0~2.0:1, preferably 1.05~1.50:1, more preferable 1.10~1.25:1, the F2The ratio between/H refers to：Will be each substituted in raw material to be fluorinated and Form the corresponding F of H atom of C-F keys2Molecular number.
10. a kind of integrated reactor for being exclusively used in any one of the claim 1-9 continuous flow synthesis technologies, feature exist In：The integrated reactor uses modular construction, including mixing dispersal unit, fluorination reaction unit and gas-liquid separation list Member, the mixing dispersal unit are used to mix raw material to be fluorinated or atent solvent with fluorine gas and fluorine gas is made to be dispersed in liquid Then this mixture is delivered to fluorination reaction unit by Xiang Zhong；Or the mixing dispersal unit is used for raw material to be fluorinated It is mixed with fluorine gas and makes fluorine gas dispersion that preliminary fluorination reaction occur simultaneously in the liquid phase, this mixture is then delivered to fluorine Change reaction member；The fluorination reaction unit for raw material to be fluorinated reacted with fluorine gas generation fluorinated ethylene carbonate and by its It is delivered to gas-liquid separation unit；The gas-liquid separation unit is used for the separation of liquid and gas.
CN201711330777.4A 2016-12-19 2017-12-13 A kind of quick continuous flow synthesis technology of fluorinated ethylene carbonate Pending CN108250176A (en)

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CN110437202A (en) * 2019-08-27 2019-11-12 许兆石 A kind of chloridization process of ethylene carbonate
CN111187169A (en) * 2019-08-27 2020-05-22 福建永晶科技股份有限公司 Process for producing fluorobenzene derivative and hypofluorite benzoate derivative
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WO2019034004A1 (en) * 2017-08-12 2019-02-21 上海惠和化德生物科技有限公司 Online full continuous flow production process for directly preparing organic peroxide with hydrogen peroxide as raw material
US10947189B2 (en) 2017-08-12 2021-03-16 Shanghai Hybrid-Chem Technologies Online continuous flow process for the synthesis of organic peroxides using hydrogen peroxide as raw material
CN111285838A (en) * 2018-12-10 2020-06-16 浙江蓝天环保高科技股份有限公司 Continuous preparation method of fluoroethylene carbonate
CN110437202A (en) * 2019-08-27 2019-11-12 许兆石 A kind of chloridization process of ethylene carbonate
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