CN206447803U - A kind of use compound ion liquid catalyst prepares the system and technique of cyclic carbonate - Google Patents
A kind of use compound ion liquid catalyst prepares the system and technique of cyclic carbonate Download PDFInfo
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- CN206447803U CN206447803U CN201621326911.4U CN201621326911U CN206447803U CN 206447803 U CN206447803 U CN 206447803U CN 201621326911 U CN201621326911 U CN 201621326911U CN 206447803 U CN206447803 U CN 206447803U
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Abstract
The utility model provides the system that a kind of use compound ion liquid catalyst prepares cyclic carbonate, including blender；The straight tube tubular reactor being connected is exported with the pipe-line mixer；The flash distillation plant being connected is exported with the straight tube tubular reactor；The vapor seperator being connected with the flash distillation plant liquid-phase outlet；The liquid-phase outlet of the vapor seperator is connected with the import of the blender.The utility model is creative to be refined and is combined, pipe-line mixer is integrated with straight tube tubular reactor, start with terms of mixing, mixed using pipe-line mixer, so as to improve the mass transfer effect of expoxy propane and carbon dioxide later stage in straight tube tubular reactor course of reaction, improve the conversion ratio of epoxide, and then the purity and conversion ratio of cyclic carbonate can be improved, and process stabilizing, industrialized production can be applied to, is a kind of efficient green technique of reusable edible.
Description
Technical field
The utility model is related to cyclic carbonate preparing technical field, is related to a kind of using compound ion liquid catalyst system
The system and technique of standby cyclic carbonate, more particularly to a kind of use compound ion liquid catalyst prepare following for cyclic carbonate
Loop system and circulation technology.
Background technology
As Environmental Factors influence, CO2Utilization be always concerned subject under discussion wide in recent years, due to activation CO2Molecule is needed
Compare high energy, only a small amount of approach is studied at present develops.Wherein CO2Pass through cycloaddition with epoxide
It is one of most successful approach that reaction, which prepares cyclic carbonate,.The preparation of cyclic carbonate is one and efficiently utilizes CO2Mode,
It is one typical " atom economy " and " Green Chemistry " reaction.And cyclic carbonate be widely used in printing and dyeing, weave, it is high
In terms of molecule synthesis and electrochemistry, while also occupying critical role in the synthesis of medicine and fine-chemical intermediate.Such as
Propene carbonate can be used for oil-based solvent, spin solvent, alkene, aromatic hydrocarbons extraction agent, carbon-dioxide absorbent, water-soluble dye and
Dispersant of pigment etc.；Ethylene carbonate is a kind of organic solvent of function admirable, can dissolve multiple polymers, with many excellent
Good performance.It can be as organic intermediate, and substituting oxirane is used for dioxy glycosylation reaction, or carbonate production by transesterification
The primary raw material of dimethyl ester, and can also act as synthesizing raw material, waterglass system slurry, fibre trimmer of furazolidone etc.,
The reactive intermediate of production lubricating oil and lubricating grease is also acted as in industrial production.Especially in recent years, the ethylene of high-purity
Alkene ester is also mainly used in lithium battery electrolytes.It is the solvent of consumption maximum in lithium battery electrolytes, and future is with Soft Roll
The development of electrokinetic cell, the consumption of ethylene carbonate ester solvent can be increasing, and development prospect is wide, but product quality is wanted
Seek naturally also more and more higher therewith.
CO2In the traditional processing technology for preparing cyclic carbonate by cycloaddition reaction with epoxide, mainly adopt
With catalyst such as tetraethylammonium bromide or KIs, not only reaction temperature is high, reaction pressure is high, and epoxide is converted
Rate is low, accessory substance is more, and the purity of reactor product cyclic carbonate is low, final cyclic carbonate poor product quality, can not especially expire
The quality requirement of the high-end fields such as sufficient lithium-ion battery electrolytes solvent.
And ionic-liquid catalyst, it is a kind of novel medium and " soft " grown up in recent years under Green Chemistry framework
Functional material, is made up of organic cation and organic/inorganic anion, is in a liquid state at room temperature in room temperature or be bordering on completely
Organic salt.Compared with traditional inorganic salt and organic molecular solvents, ionic liquid has liquidus behavior and ionic simultaneously, gathers around it
There are traditional inorganic salt and many incomparable excellent properties of organic solvent, as all having well to a large amount of inorganic/organic matters
Solvability；Have the double action of solvent and catalyst concurrently, reaction dissolvent and catalyst active carrier can be used as；It is electrochemically stable
Property height etc..Wherein, the cation of conventional ionic liquid is broadly divided into four kinds：Alkyl imidazolium ion [Cnmim]+, alkyl pyridine from
Son [Cnpy]+, alkyl quaternary ammonium ion [NRxH4-x]+With Wan Ji quaternary phosphine ions [PRxH4-x]+.It is different according to anion, again can by from
Sub- liquid is divided into two classes：1) first generation ionic liquid is halogeno salt+AlCl3(or AlBr3, InCl3, FeCl3) type coordination ion liquid
Body, such as [bmim] Cl-AlCl3Ionic liquid.2) cation of second generation ionic liquid is still based on above-mentioned four kinds, its it is cloudy from
It is sub mainly to include [BF4]-、[PF6]-、[CF3SO3]-、[(CF2SO2)2N]-、[C3F7COO]-、[C4F9SO3]-、[CF3COO]-、
[(CF3SO2)3C]-、[(C2F5SO2)3C]-、[(C2F5SO2)2N]-、[AsF6]-、[SbF6]-、[HSO4]-、[NO2]-、[NO3]-etc..
In the last few years, although have research that ionic-liquid catalyst is used in cyclic carbonate preparation, but due to technique road
The imperfection of line design, it is low still also to there is conversion ratio, purity difference, and cost is high, the problem of stability is poor, it is impossible to realize
Real industrialized production.
Therefore, a kind of cyclic carbonate preparation technology preferably how is obtained, it is possible to increase the purity of cyclic carbonate
And conversion ratio, industrialized production can be applied to, it has also become in field the focus of many line scientific research personnel's extensive concerns it
One.
Utility model content
In view of this, the technical problems to be solved in the utility model is that providing one kind uses compound ion liquid catalyst
The system and technique of cyclic carbonate are prepared, particularly a kind of use compound ion liquid catalyst prepares following for cyclic carbonate
Loop system and circulation technology, the technique and system that prepare cyclic carbonate that the utility model is provided, with higher yield and
Product purity, process stabilizing is a kind of efficient green process system of reusable edible.
The utility model provides the system that a kind of use compound ion liquid catalyst prepares cyclic carbonate, including：
Pipe-line mixer；
The straight tube tubular reactor being connected is exported with the pipe-line mixer；
The flash distillation plant being connected is exported with the straight tube tubular reactor；
The vapor seperator being connected with the flash distillation plant liquid-phase outlet；
The liquid-phase outlet of the vapor seperator is connected with the import of the pipe-line mixer.
It is preferred that, the straight tube tubular reactor is vertical straight tube tubular reactor.
It is preferred that, the straight tube tubular reactor is material filling type straight tube tubular reactor.
It is preferred that, the filler is random packing.
It is preferred that, the random packing includes Raschig ring, Pall ring, cascade ring, helical ring, ceramic ring, steel and fills out circle, saddle type
One or more in expectation, quartz and glass spring.
It is preferred that, the vapor seperator is thin film evaporator.
It is preferred that, the system also includes catalyst surge tank；
The outlet of the catalyst surge tank is connected with the import of the pipe-line mixer.
It is preferred that, the liquid-phase outlet of the vapor seperator is connected with the import of the catalyst surge tank.
It is preferred that, the straight tube tubular reactor outlet is also connected by heat exchanger with the import of the pipe-line mixer
Connect.
It is preferred that, it is additionally provided with the pre- hot charging that goes into operation between the pipe-line mixer outlet and the straight tube tubular reactor
Put.
The utility model additionally provides the technique that a kind of use compound ion liquid catalyst prepares cyclic carbonate, including
Following steps：
1) by compound ion liquid catalyst, carbon dioxide and epoxide after tubular-mix, then straight pipe type is carried out
Reaction, obtains reactant mixture；
The compound ion liquid catalyst includes glyoxaline ion liquid host, halo salt assitant and solvent；
2) reactant mixture for obtaining above-mentioned steps is carried out after flash separation, obtains reaction product；
3) after the reaction product that above-mentioned steps are obtained is separated through pervaporation, cyclic carbonate and regeneration compound ion are obtained
Liquid catalyst；
4) the regeneration compound ion liquid catalyst that above-mentioned steps are obtained is recycled to step 1) in, circulated again sharp
With.
It is preferred that, the step 2) be specially：
The reactant mixture part that above-mentioned steps are obtained is carried out after flash separation, obtains reaction product；
By another part reactant mixture return to step 1) middle progress cycling and reutilization.
It is preferred that, another part reactant mixture return to step 1 after heat exchange) middle progress cycling and reutilization；
Regeneration compound ion liquid catalyst and the compound ion liquid catalyst after buffering, then with dioxy
Change after carbon and epoxide mixing, after tubular-mix, then carry out straight pipe type reaction, obtain reactant mixture.
It is preferred that, the mass percent that the compound ion liquid catalyst accounts for the reaction-ure mixture of the pipe reaction is
0.5%~1%；
The glyoxaline ion liquid host is methylimidazole ionic liquid host；The halo salt assitant is halo zinc
Salt assitant；The solvent is cyclic carbonate；
The mass ratio of the glyoxaline ion liquid host and the halo salt assitant is (4~8)：1.
It is preferred that, the temperature of the straight pipe type reaction is 100~160 DEG C；The time of the straight pipe type reaction is 0.5~2
Hour；The pressure of the straight pipe type reaction is 2.0~6.0MPa；
The pressure of the flash separation is 0.1~0.3MPa；
The evaporation is separated into thin film evaporation separation；The temperature of the evaporation separation is 100~180 DEG C；The evaporation point
From pressure be 1~10KPa.
The utility model provides the system that a kind of use compound ion liquid catalyst prepares cyclic carbonate, including,
Blender；The straight tube tubular reactor being connected is exported with the pipe-line mixer；Phase is exported with the straight tube tubular reactor
The flash distillation plant of connection；The vapor seperator being connected with the flash distillation plant liquid-phase outlet；The liquid phase of the vapor seperator
Outlet is connected with the import of the blender.Compared with prior art, the utility model is for existing cyclic carbonate
Not only reaction temperature is high for preparation method, reaction pressure is high, and epoxide conversion ratio is low, accessory substance is more, reactor product ring
The purity of shape carbonic ester is low, the defect of final cyclic carbonate poor product quality, and selection uses compound ion liquid catalyst system
Standby cyclic carbonate；Ionic-liquid catalyst is used for the design of cyclic carbonate for existing again, still also exists and turns
Rate is low, purity difference, and cost is high, and the problem of stability is poor, it is impossible to realize the defect of real industrialized production is created
Property is refined and combined, and pipe-line mixer and straight tube tubular reactor are integrated, started with terms of mixing, using pipeline
Blender is mixed, so that the mass transfer for improving expoxy propane and carbon dioxide later stage in straight tube tubular reactor course of reaction is imitated
Really, the conversion ratio of epoxide is improved, and then the purity and conversion ratio of cyclic carbonate can be improved, and technique is steady
It is fixed, industrialized production can be applied to, is a kind of efficient green technique of reusable edible.
Test result indicates that, the circulatory system and circulation technology that prepare cyclic carbonate that the utility model is provided, product
Conversion ratio can reach 99.7%, and product purity can reach 99.91%, and process stabilizing, reusable edible degree is high.
Brief description of the drawings
Fig. 1 prepares the work of the cyclic carbonate circulatory system for the use compound ion liquid catalyst that the utility model is provided
Skill general flow chart.
Embodiment
In order to further appreciate that the utility model, preferred embodiment of the present utility model is carried out with reference to embodiment
Description, but it is to be understood that these descriptions are simply to further illustrate feature and advantage of the present utility model rather than to this reality
The limitation required with new patent.
All raw materials of the utility model, originate to it and are not particularly limited, commercially buying or according to this area skill
It is prepared by conventional method known to art personnel.
All raw materials of the utility model, its purity is not particularly limited, and the utility model is preferred to use the pure or ring of analysis
The conventional purity of shape carbonic ester preparation field.
The utility model provides the system that a kind of use compound ion liquid catalyst prepares cyclic carbonate, including：
Pipe-line mixer；
The straight tube tubular reactor being connected is exported with the pipe-line mixer；
The flash distillation plant being connected is exported with the straight tube tubular reactor；
The vapor seperator being connected with the flash distillation plant liquid-phase outlet；
The liquid-phase outlet of the vapor seperator is connected with the import of the blender.
It is preferred that, the straight tube tubular reactor is material filling type straight tube tubular reactor；
The vapor seperator is thin film evaporator.
The pipe-line mixer is not particularly limited the utility model, is mixed with pipeline well known to those skilled in the art
Device, those skilled in the art can be selected and be adjusted according to practical condition, raw material condition and product requirement,
The utility model is improves mixed effect, so as to improve the mass transfer effect of late phase reaction, the pipe-line mixer is preferably straight tube
Formula pipe-line mixer；The import and export of the pipe-line mixer are preferably at the two ends of the pipe-line mixer.The utility model is to institute
The design parameter for stating pipe-line mixer is not particularly limited, and the parameter with pipe-line mixer well known to those skilled in the art is
Can, those skilled in the art can be selected and be adjusted, this reality according to practical condition, raw material condition and product requirement
With it is new for further improve mixed effect, the draw ratio of the pipe-line mixer is preferably 5~30, more preferably 8~20, most
Preferably 10~15.
In the utility model, the system that the use compound ion liquid catalyst prepares cyclic carbonate is also included directly
Pipe tubular reactor.The straight tube tubular reactor is not particularly limited the utility model, is known with those skilled in the art
Straight pipe type tubular reactor, those skilled in the art can according to practical condition, raw material condition and product will
Ask and selected and adjusted, the utility model is engaged, the straight tube tubular reactor is excellent to improve reaction effect with blender
Elect material filling type straight tube tubular reactor, more preferably vertical straight tube tubular reactor, more preferably bottom in and top out formula vertical straight as
The vertical material filling type straight tube tubular reactor of pipe tubular reactor, most preferably bottom in and top out formula.The utility model is to the straight tube
The parameter of tubular reactor is not particularly limited, those skilled in the art can according to practical condition, raw material condition and
Product requirement is selected and adjusted, and the utility model is engaged, the straight tube tubular type is anti-to improve reaction effect with blender
The draw ratio for answering device is preferably 10~60, more preferably 20~50, most preferably 30~40..
The form of the filler is not particularly limited the utility model, with form of bio-carrier well known to those skilled in the art
, those skilled in the art can be selected and be adjusted according to practical condition, raw material condition and product requirement, this
Utility model is engaged, the filler is preferably random packing, the random packing is preferred to improve reaction effect with blender
The one kind filled out including Raschig ring, Pall ring, cascade ring, helical ring, ceramic ring, steel in circle, saddle type expectation, quartz and glass spring
Or it is a variety of, more preferably Raschig ring, Pall ring, cascade ring, helical ring, ceramic ring, steel fill out circle, saddle type expectation, quartz or glass
Spring, most preferably Pall ring, cascade ring or rectangular saddle ring.
The utility model is set by the specific type selecting to pipe reaction, import and export, is especially loaded in inside reactor
Random packing metal packings such as (including) Pall ring, cascade ring, rectangular saddle rings, is favorably improved biography of the material in inside reactor
Matter, heat-transfer effect, stable inside reactor temperature, prevent local overheating from causing side reaction, reduce accessory substance in reaction product
Content, the purity of reaction product cyclic carbonate is improved, while guard catalyst, improves the service life of catalyst, is improved
Mass transfer effect of the material in reactor, between reaction raw materials epoxide and carbon dioxide and reaction raw materials and catalyst
Contact is abundant, is engaged with specific hybrid mode, further improves reaction effect.
In the utility model, the straight tube tubular reactor is connected with pipe-line mixer outlet, i.e., described pipe
The mixed material of road blender is directly entered straight tube tubular reactor by pipeline and reacted.The utility model is raising
The overall integrity and operability of technique, are additionally provided between the pipe-line mixer outlet and the straight tube tubular reactor
Go into operation preheating device, i.e., in technique start-up, the material of the pipe-line mixer outlet, in pipeline after preheating, then
Reacted into straight tube tubular reactor.The preheating device that goes into operation is not particularly limited the utility model, with this area
Pipeline preheating device known to technical staff, those skilled in the art can according to practical condition, raw material condition with
And product requirement is selected and adjusted, the preheating device described in the utility model that goes into operation is preferably the heater of heat conducting oil type.
In the utility model, the system that the use compound ion liquid catalyst prepares cyclic carbonate also includes dodging
Steam device.The flash distillation plant is not particularly limited the utility model, is with flash distillation plant well known to those skilled in the art
Can, those skilled in the art can be selected and be adjusted, this reality according to practical condition, raw material condition and product requirement
It is preferably flash tank with the new flash distillation plant.
In the utility model, the flash distillation plant is connected with straight tube tubular reactor outlet.I.e. described straight tube
The reacted material of tubular reactor by pipeline be directly entered flash distillation plant carry out flash separation, obtain liquid-phase reaction product and
Gas.The utility model is improves the overall integrity and operability of technique, and the pipe-line mixer is exported and the straight tube
Pressure-reducing valve is additionally provided between tubular reactor.The pressure-reducing valve is not particularly limited the utility model, with art technology
Pressure-reducing valve known to personnel, those skilled in the art can be according to practical condition, raw material condition and product requirement
Selected and adjusted, pressure-reducing valve described in the utility model is preferably automatic control relief pressure valve.
Particularly, in the utility model, the straight tube tubular reactor exports the import also with the pipe-line mixer
It is connected, straight tube tubular reactor outlet more preferably is also connected by heat exchanger with the import of the pipe-line mixer
Connect.The i.e. described reacted material of straight tube tubular reactor is partly into flash distillation plant, and another part material is returned by pipeline
Return pipe-line mixer to be circulated, mixed with raw material.
Partial reaction Matter Transfer is entered pipe-line mixer by the utility model, has not only been recycled in reaction mass
Product and catalyst, product are also used as solvent, and can significantly improve mass transfer effect in pipe-line mixer, contribute to
The conversion ratio of epoxide is improved, is to prepare cyclic carbonate while decreasing processing load and the discharge of the three wastes in later stage
Ester system is circulatory system essential condition, is also the first circulation route of the circulatory system.
In the utility model, the system that the use compound ion liquid catalyst prepares cyclic carbonate also includes steaming
Send out separator.The vapor seperator is not particularly limited the utility model, with evaporation point well known to those skilled in the art
From device, those skilled in the art can be selected and be adjusted according to practical condition, raw material condition and product requirement
Whole, vapor seperator described in the utility model is preferably thin film evaporator, is specifically as follows scraper-type evaporator or falling film evaporation
Device.
In the utility model, the vapor seperator is connected with the flash distillation plant liquid-phase outlet.I.e. described flash distillation
Liquid reacting product after unit flashing is directly entered vapor seperator by pipeline to carry out evaporation again and separates, obtain gas and
It is cyclic carbonate crude product, the namely regenerated compound ion liquid catalyst of liquid after the condensation of liquid, wherein gas.
The utility model forms Article 2 circulation route, the steaming to improve the overall integrity and operability of technique
The liquid-phase outlet of hair separator is connected with the import of the blender.The utility model is by the compound ion liquid separated
Catalyst is recycled into system again, has recycled catalyst, reduces processing load and the discharge of the three wastes in later stage, is system
Standby cyclic carbonate system is circulatory system essential condition, is also the second circulation route of the circulatory system.
Further, the utility model is the overall integrity and operability for improving technique, in the utility model, institute
Stating the system for preparing cyclic carbonate using compound ion liquid catalyst preferably also includes catalyst surge tank.The utility model
The surge tank is not particularly limited, with surge tank well known to those skilled in the art, those skilled in the art can be with
Selected and adjusted according to practical condition, raw material condition and product requirement.
In the utility model, the outlet of the catalyst surge tank is connected with the import of the pipe-line mixer.I.e.
The reaction raw materials catalyst is introduced into catalyst surge tank, enters back into pipe-line mixer and is mixed.And the evaporation point
Liquid-phase outlet from device is connected with the import of the catalyst surge tank, i.e., the catalyst that described vapor seperator is separated
Return system, is introduced into catalyst surge tank and enters row buffering, after being mixed with fresh catalyst, enter back into pipe-line mixer, with
Other raw materials are mixed.
The utility model above-mentioned steps provide a set of use compound ion liquid catalyst prepare cyclic carbonate be
System, particularly a set of use compound ion liquid catalyst prepares the circulatory system of cyclic carbonate.It is right that the utility model passes through
Technique is refined and integrated, and pipe-line mixer is integrated with straight tube tubular reactor, is first started with terms of mixing, is used
Pipe-line mixer is mixed, so as to improve the biography of expoxy propane and carbon dioxide later stage in straight tube tubular reactor course of reaction
Matter effect, improves the conversion ratio of epoxide；Then specific tubular reactor, filler and connected mode are selected, is contributed to
Mass transfer, heat-transfer effect of the material in inside reactor are improved, stable inside reactor temperature prevents local overheating from causing secondary anti-
Should, the content of accessory substance in reaction product is reduced, the purity of reaction product cyclic carbonate is improved, while guard catalyst,
The service life of catalyst is improved, mass transfer effect of the material in reactor, reaction raw materials epoxide and two is also improved
Contacted between carbonoxide and reaction raw materials and catalyst fully, be engaged, further improve with specific hybrid mode
Reaction effect；In conjunction with the circulatory system of Two-way Cycle route, the mass transfer effect of mixed process is not only increased, is favorably improved
The conversion ratio of epoxide, while processing load and the discharge of the three wastes in later stage are decreased, and process stabilizing, Neng Gouying
It is a kind of efficient green technique of reusable edible for industrialized production.
The utility model additionally provides the technique that a kind of use compound ion liquid catalyst prepares cyclic carbonate, including
Following steps：
1) by compound ion liquid catalyst, carbon dioxide and epoxide after tubular-mix, then straight pipe type is carried out
Reaction, obtains reactant mixture；
The compound ion liquid catalyst includes glyoxaline ion liquid host, halo salt assitant and solvent；
2) reactant mixture for obtaining above-mentioned steps is carried out after flash separation, obtains reaction product；
3) after the reaction product that above-mentioned steps are obtained is separated through pervaporation, cyclic carbonate and regeneration compound ion are obtained
Liquid catalyst；
4) the regeneration compound ion liquid catalyst that above-mentioned steps are obtained is recycled to step 1) in, circulated again sharp
With.
The utility model to route in the technique and the range of choice and optimum principle of parameter, with it is foregoing using be combined from
The range of choice that sub- liquid catalyst prepares the system of cyclic carbonate is consistent with optimum principle, and this is no longer going to repeat them.
The utility model first by compound ion liquid catalyst, carbon dioxide and epoxide after tubular-mix,
Straight pipe type reaction is carried out again, obtains reactant mixture.
The epoxide is not particularly limited the utility model, with epoxy compound well known to those skilled in the art
Thing, those skilled in the art can be selected and be adjusted according to practical condition, raw material condition and product requirement,
Epoxide described in the utility model preferably includes the one or more in oxirane, expoxy propane and epoxy butane, more
Preferably oxirane, expoxy propane or epoxy butane.
The compound ion liquid catalyst is not particularly limited the utility model, with well known to those skilled in the art
Compound ion liquid catalyst, those skilled in the art can want according to practical condition, raw material condition and product
Ask and selected and adjusted, compound ion liquid catalyst described in the utility model preferably include glyoxaline ion liquid host,
Halo salt assitant and solvent.
The glyoxaline ion liquid host is not particularly limited the utility model, with well known to those skilled in the art
Glyoxaline ion liquid host in compound ion liquid catalyst, those skilled in the art can be according to actual production feelings
Condition, raw material condition and product requirement are selected and adjusted, and glyoxaline ion liquid host described in the utility model is preferably
Methylimidazole ionic liquid host.The solvent is not particularly limited the utility model, is known with those skilled in the art
Compound ion liquid catalyst in common solvent, those skilled in the art can be according to practical condition, raw material
Situation and product requirement are selected and adjusted, and solvent described in the utility model is preferably cyclic carbonate, is more preferably followed
The cyclic carbonate recycled in ring cyclic carbonate, i.e. technique.
Particularly, the utility model is urged by the ratio and compound ion liquid regulated and controled in compound ion liquid catalyst
The ratio of agent and reaction raw materials, with system matched combined, optimizes reaction effect, further improves the purity of final product
And yield, glyoxaline ion liquid host described in the utility model and the mass ratio of the halo salt assitant are preferably (4~8)：
1, more preferably (4.5~7.5)：1, be most preferably (5~6)：1.Compound ion liquid catalyst described in the utility model accounts for institute
The mass percent for stating the reaction-ure mixture of pipe reaction is preferably 0.5%~1%, and more preferably 0.6%~0.9%, it is optimal
Elect 0.7%~0.8% as.
The tubular-mix is not particularly limited the utility model, with tubular-mix well known to those skilled in the art
Concept, those skilled in the art can be selected and be adjusted according to practical condition, raw material condition and product requirement
Whole, tubular-mix described in the utility model preferably refers to be mixed using pipe-line mixer.The utility model is to the straight tube
Formula reaction is not particularly limited, the concept reacted with straight pipe type well known to those skilled in the art, those skilled in the art
It can be selected and be adjusted according to practical condition, raw material condition and product requirement, straight pipe type described in the utility model
Reaction preferably refers to be reacted using straight tube tubular reactor.
The reaction condition that the straight pipe type reacts is not particularly limited the utility model, is known with those skilled in the art
Similar reaction reaction condition, those skilled in the art can be according to practical condition, raw material condition and product
It is required that being selected and being adjusted, the temperature of straight pipe type reaction described in the utility model is preferably 100~160 DEG C, more preferably 105
~145 DEG C, most preferably more preferably 110~140 DEG C, 125~140 DEG C；The time of straight pipe type reaction is preferably 0.5~
2 hours, most preferably more preferably 0.8~1.7 hour, 1.0~1.5 hours；The pressure of the straight pipe type reaction is preferably 2.0
~6.0MPa, more preferably 2.5~5.0MPa, most preferably 3.0~4.5MPa.
The utility model and then the reactant mixture for obtaining above-mentioned steps are carried out after flash separation, obtain reaction product.
The condition of the flash separation is not particularly limited the utility model, with flash distillation well known to those skilled in the art
The condition of separation, those skilled in the art can be selected according to practical condition, raw material condition and product requirement
Select and adjust, the pressure of flash separation described in the utility model is preferably 0.1~0.3MPa, more preferably 0.12~0.27MPa,
Most preferably 0.15~0.25MPa.
The utility model is further improves the mass transfer effect of mixed process, so that the conversion ratio of epoxide is improved,
Reaction effect is improved, the circulation technology of Two-way Cycle route is constituted, processing load and the discharge of the three wastes in later stage, the step is reduced
2) it is particularly preferred as：
The reactant mixture part that above-mentioned steps are obtained is carried out after flash separation, obtains reaction product；By another portion
Divide reactant mixture return to step 1) middle progress cycling and reutilization.
Wherein, more specific preferably another part reactant mixture return to step 1 after heat exchange) in circulated again
Utilize.
The utility model is after then the reaction product that obtains above-mentioned steps is separated through pervaporation, obtain cyclic carbonate and
Regenerate compound ion liquid catalyst.
The evaporation separation is not particularly limited the utility model, with evaporation separation well known to those skilled in the art
Mode, those skilled in the art can be selected and be adjusted according to practical condition, raw material condition and product requirement
Whole, evaporation separation described in the utility model is preferably thin film evaporation separation.
The condition of the evaporation separation is not particularly limited the utility model, with evaporation well known to those skilled in the art
The condition of separation, those skilled in the art can be selected according to practical condition, raw material condition and product requirement
Select and adjust, the temperature of evaporation separation described in the utility model is preferably 100~180 DEG C, more preferably 110~170 DEG C, more excellent
Elect 120~160 DEG C, most preferably 130~150 DEG C as；The pressure of the evaporation separation is preferably 1~10KPa, and more preferably 3
~8KPa, most preferably 5~6KPa.
The regeneration compound ion liquid catalyst that the utility model finally obtains above-mentioned steps is recycled to step 1) in, enter
Row cycling and reutilization.
The utility model further improves the mass transfer effect of mixed process to improve the integrality and stability of integrated artistic
Really, so as to improve the conversion ratio of epoxide, reaction effect is improved, the circulation technology of Two-way Cycle route is constituted, the later stage is reduced
Processing load and the three wastes discharge, be particularly preferred as, regeneration compound ion liquid catalyst and the compound ion liquid
Body catalyst is after buffering, then with carbon dioxide and epoxide after tubular-mix, then carries out straight pipe type reaction, obtains
Reactant mixture.
The utility model above-mentioned steps provide the work that a kind of use compound ion liquid catalyst prepares cyclic carbonate
Skill and system, the technique that the utility model is provided can recycle compound ion liquid catalyst, catalyst reaction with long period
It is active high, improve the conversion ratio of expoxy propane and the selection index of cyclic carbonate；Catalyst uses the catalyst simultaneously
The reaction temperature of synthesizing annular carbonate is low, reaction pressure is low, and the side reaction during reducing occurs, and it also avoid using passing
Unite catalyst can not long-term operation, the problems such as intermediate demand is repeatedly replaced and blocks pipeline fundamentally solve ring-type carbon
Technical barrier in acid esters building-up process；After being mixed using pipe-line mixer to reaction raw materials, catalyst and recycle stock
Enter back into straight pipe type tubular reactor, it is ensured that material is well mixed in the reactor, and save the labour of operation, disappear
Energy consumption cost is consumed.
The specific steps of the utility model integrated artistic system can also be：
The utility model synthesis of cyclic under compound ion liquid catalyst effect using epoxide and carbon dioxide
Carbonic ester, compound ion liquid catalyst is that, using methylimidazole ionic liquid as host, halo zinc salt is the ring-type carbon of auxiliary agent
Acid esters solution.
The utility model reaction mass, catalyst and circulation cyclic carbonate material are entered after being mixed using pipe-line mixer
Straight tube tubular reactor react, reacting rear material a part after cooling return duct blender as reaction solvent, one
Material is divided to isolate the cyclic carbonate that gas phase obtains high-quality after cooling into thin film evaporator after vacuum flashing,
Film liquid phase material is circulation compound ion liquid catalyst, and being transmitted back to reaction system through pump recycles.
Wherein, reaction member：Raw material and compound ion liquid from epoxide storage tank and carbon dioxide storage tank are urged
Agent material is delivered to pipe-line mixer respectively through high-pressure pump, high pressure is entered after being mixed with the cyclic carbonate material of circulation anti-
Device is answered, at a temperature of 100~150 DEG C, successive reaction under 2.0~5.0MPa pressure conditions, it is ensured that material is in reactor
Residence time is 0.5~2 hour, and a reacted material part is transmitted back to pipe-line mixer through pump after condenser is cooled down and made
For the solvent of reaction, another part material enters flash tank after pressure-reducing valve is depressurized.
Catalyst separative element：Reacting rear material enters material flash tank after pressure-reducing valve is depressurized, and is separated off not anti-
The CO answered2Material and a small amount of epoxide material, control the pressure of flash tank between 0.1~0.3MPa.Liquid phase material
Thin film evaporator is delivered to, condensed device is cold again from thin film evaporator discharge after carburation by evaporation for reaction product cyclic carbonate
Cyclic carbonate crude product is obtained after solidifying, compound ion liquid catalyst cyclic carbonate material is in the form of liquid phase from thin film evaporation
The discharge of device bottom returns to recycling catalyst tank.It can be reached by the isolated thick cyclic carbonate feed purity of thin film evaporator
To more than 99.8%, colourity is less than 5, can be taken out directly as industrial goods or straight as the middle product of production dimethyl carbonate
Connect and use.
Specifically actual process step can be：
(1) first process system suppress before going into operation and try close, confirm system without leak source；Injected in recycling catalyst tank
The cyclic carbonate ester solution of compound ion liquid catalyst required for reaction system, wherein compound ion liquid catalyst host
Ratio with auxiliary agent is (4~8)：1, the amount of solvent cyclic carbonate is advisable with energy catalyst-solvent, compound ion liquid catalysis
Addition of the agent in reaction system is 0.5%~1%；Cyclic carbonate thing is injected in the reactor assembly before pressure-reducing valve
Material and compound ion liquid catalyst material, open circulating pump and set up circulation, cyclic carbonate is catalyzed with compound ion liquid
Agent is well mixed in reactor assembly.System is warming up to reaction temperature, carbon dioxide injection and boosts to reaction pressure；
(2) synthesis unit：After the completion of operating reserves, start to feed to reaction system according to the proportioning of reaction raw materials, come from
The material of epoxide storage tank and carbon dioxide storage tank is delivered to pipe-line mixer and recycling catalyst respectively through high-pressure pump
Enter reactor after material and the material mixing of circulation cyclic carbonate and carry out cycloaddition reaction, reacted material goes out from reactor
To return reactor by cooling Posterior circle with rear portion, as the solvent of reaction mass, a part of material subtracts by pressure-reducing valve
Enter flash tank after pressure.
(3) catalyst separative element：Material after pressure-reducing valve is depressurized enters flash tank and carries out flash separation removing not
The carbon dioxide material of reaction and a small amount of cyclic carbonate material, liquid phase material enter thin film evaporator, and thin film evaporator is
Negative-pressure operation, the gaseous phase materials steamed obtain the cyclic carbonate crude product that purity is higher than 99.8% after supercooling, with compound
The liquid phase material of ionic-liquid catalyst is recycled into catalyst circulating tank.
The crude product cyclic carbonate obtained by thin film evaporator directly can be taken out or as production as industrial goods
The raw material of dimethyl carbonate is directly used, and more than 99.99% LITHIUM BATTERY product can be obtained by further refining purification.
Referring to Fig. 1, Fig. 1 prepares cyclic carbonate circulation for the use compound ion liquid catalyst that the utility model is provided
The process flow diagram of system.Wherein, 1 is catalyst surge tank, and 2 be pipe-line mixer, and 3 be the preheating device that goes into operation, and 4 be straight tube
Tubular reactor, 5 be recycle stock cooling heat exchanger, and 6 be pressure-reducing valve, and 7 be flash tank, and 8 be gas phase cooler, and 9 be that film steams
Device is sent out, 10 be reactor product cooler；11 be the epoxide from storage tank, and 12 be the CO from storage tank2, 13 be fresh catalyst
Agent, 14 be cyclic reaction mixture, and 15 be regeneration compound ion liquid catalyst, and 16 be CO2Fixed gas, 17 be cyclic carbonate
Crude product.
The use compound ion liquid catalyst that the utility model is provided prepares the circulation technology system of cyclic carbonate.This
Utility model is integrated pipe-line mixer with straight tube tubular reactor by the way that technique and system are refined and integrated,
First start with terms of mixing, mixed using pipe-line mixer, so as to improve expoxy propane and carbon dioxide later stage in straight tube
The mass transfer effect of tubular reactor course of reaction, improves the conversion ratio of epoxide；Then select specific tubular reactor,
Filler and connected mode, are favorably improved mass transfer, heat-transfer effect of the material in inside reactor, stablize inside reactor temperature,
Prevent local overheating from causing side reaction, reduce the content of accessory substance in reaction product, the purity of reaction product cyclic carbonate
Improve, while guard catalyst, improves the service life of catalyst, also improve mass transfer effect of the material in reactor, instead
Answer contacted between raw material epoxide and carbon dioxide and reaction raw materials and catalyst fully, with specific hybrid mode phase
Coordinate, in conjunction with the refinement and combination of the technological parameter of each reaction process, complement each other, further improve reaction effect
Really；The circulatory system of Two-way Cycle route is had also combined, the mass transfer effect of mixed process is not only increased, is favorably improved epoxidation
The conversion ratio of compound, while processing load and the discharge of the three wastes in later stage are decreased, and process stabilizing, work can be applied to
The big production of industryization, is a kind of efficient green technique of reusable edible.
Test result indicates that, the circulatory system and circulation technology that prepare cyclic carbonate that the utility model is provided, product
Conversion ratio can reach 99.7%, and product purity can reach 99.91%, and process stabilizing, reusable edible degree is high.
In order to further illustrate the utility model, the use compound ion provided with reference to embodiments the utility model
The technique and system that liquid catalyst prepares cyclic carbonate are described in detail, but it is to be understood that these embodiments be
It is lower premised on technical solutions of the utility model to be implemented, detailed embodiment and specific operating process are given, only
It is to further illustrate feature and advantage of the present utility model, rather than the limitation to the utility model claim, this practicality
New protection domain is also not necessarily limited to following embodiments.
Embodiment 1
Propylene carbonate Lipase absobed
According to the process system shown in Fig. 1, pipe-line mixer specification is DN100 × 1000mm, straight tube tubular reactor rule
Lattice are 450 × 20000mm of Φ, and reactor uses the mode of operation of material bottom in and top out, and filler is stainless using 16*16*0.3 metals
Steel Pall ring filler.
The carbonic allyl ester solution of the compound ion liquid catalyst containing 50kg is first injected in recycling catalyst tank, according to work
Skill step completes system and fills propene carbonate and compound ion liquid catalyst, starts after heating, boosting into raw material epoxy third
Alkane and carbon dioxide, the inlet amount of expoxy propane is 500kg/h, and the inlet amount of carbon dioxide is 416kg/h, the reaction of reactor
Temperature is 135~140 DEG C, and reaction pressure is 4.0MPa, and reacting rear material enters flash tank through pressure-reducing valve, controls flash tank pressure
For 0.1~0.2MPa, flash separation removes the carbon dioxide of excess and the expoxy propane of traces of unreacted, steamed by film
Send out the isolated propene carbonate crude product of device.
The system of the utility model embodiment 1 is run continuous samples detection and to enter the propene carbonate crude product of preparation
Row continuous sampling detects that data result is referring to table 1, and table 1 is the systematic sampling testing result and carbonic acid of the utility model embodiment 1
Propylene crude product sampling inspection results.
The systematic sampling testing result and propene carbonate crude product sampling inspection results of the utility model embodiment 1 of table 1
Embodiment 2
Ethylene carbonate Lipase absobed
According to the process shown in Fig. 1, pipe-line mixer specification is DN100 × 1000mm, and pipe-line mixer specification is
Φ400×18000mm.Reactor uses the mode of operation of material bottom in and top out, and filler uses 25*25*0.5 metal stainless steel
Pall ring filler.When noticing that the process is applied to ethylene carbonate Lipase absobed, because the fusing point of ethylene carbonate is 35~38
DEG C, it is necessary to carry out insulation heat tracing to whole system, prevent out, stop work during cause the blocking of pipeline.
The ethylene carbonate ester solution of the compound ion liquid catalyst containing 38kg is first injected in recycling catalyst tank, according to work
Skill step completes system and fills ethylene carbonate and compound ion liquid catalyst, starts after heating, boosting into raw material epoxy second
Alkane and carbon dioxide, the inlet amount of oxirane is 400kg, and the inlet amount of carbon dioxide is 420kg, the reaction temperature of reactor
For 125~135 DEG C, reaction pressure is 4.5MPa, and reacting rear material enters flash tank through pressure-reducing valve, controls the flash tank pressure to be
0.1~0.2MPa, flash separation removes the carbon dioxide of excess and the oxirane of traces of unreacted, by thin film evaporation
The isolated ethylene carbonate crude product of device.
The system of the utility model embodiment 2 is run continuous samples detection and to enter the ethylene carbonate crude product of preparation
Row continuous sampling detects that data result is referring to table 2, and table 2 is the systematic sampling testing result ethylene of the utility model embodiment 2
Alkene ester crude product sampling inspection results.
The systematic sampling testing result and ethylene carbonate crude product sampling inspection results of the utility model embodiment 2 of table 2
The circulation of cyclic carbonate is prepared to a kind of use compound ion liquid catalyst that the utility model is provided above
System and circulation technology are described in detail, and specific case used herein is to principle of the present utility model and embodiment party
Formula is set forth, and the explanation of above example is only intended to help and understands method of the present utility model and its core concept, bag
Best mode is included, and also causes any person skilled in the art to put into practice the utility model, including manufactures and uses
Any device or system, and implement the method for any combination.It should be pointed out that coming for those skilled in the art
Say, on the premise of the utility model principle is not departed from, some improvement and modification can also be carried out to the utility model, these change
Enter and modification is also fallen into the utility model scope of the claims.The scope of the utility model patent protection passes through right
It is required that to limit, and may include those skilled in the art it is conceivable that other embodiment.If these other embodiments have
The structural element of claim character express is not different from, or if they include the character express with claim without reality
The equivalent structural elements of matter difference, then these other embodiments also should be comprising within the scope of the claims.
Claims (10)
1. the system that a kind of use compound ion liquid catalyst prepares cyclic carbonate, it is characterised in that including：
Pipe-line mixer；
The straight tube tubular reactor being connected is exported with the pipe-line mixer；
The flash distillation plant being connected is exported with the straight tube tubular reactor；
The vapor seperator being connected with the flash distillation plant liquid-phase outlet；
The liquid-phase outlet of the vapor seperator is connected with the import of the pipe-line mixer.
2. system according to claim 1, it is characterised in that the straight tube tubular reactor is vertical straight tube pipe reaction
Device.
3. system according to claim 1, it is characterised in that the straight tube tubular reactor is that material filling type straight tube tubular type is anti-
Answer device.
4. system according to claim 3, it is characterised in that the filler is random packing.
5. system according to claim 4, it is characterised in that the random packing includes Raschig ring, Pall ring, ladder
The one or more that ring, helical ring, ceramic ring, steel are filled out in circle, saddle type expectation, quartz and glass spring.
6. system according to claim 1, it is characterised in that the vapor seperator is thin film evaporator.
7. the system according to claim 1~6 any one, it is characterised in that the system also includes catalyst and buffered
Tank；
The outlet of the catalyst surge tank is connected with the import of the pipe-line mixer.
8. system according to claim 7, it is characterised in that the liquid-phase outlet of the vapor seperator and the catalyst
The import of surge tank is connected.
9. the system according to claim 1~6 any one, it is characterised in that the straight tube tubular reactor outlet is also
It is connected by heat exchanger with the import of the pipe-line mixer.
10. the system according to claim 1~6 any one, it is characterised in that the pipe-line mixer outlet with it is described
The preheating device that goes into operation is additionally provided between straight tube tubular reactor.
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| CN201621326911.4U CN206447803U (en) | 2016-12-05 | 2016-12-05 | A kind of use compound ion liquid catalyst prepares the system and technique of cyclic carbonate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106588863A (en) * | 2016-12-05 | 2017-04-26 | 东营市海科新源化工有限责任公司 | System and process for preparing cyclic carbonate by using composite ionic liquid catalyst |
| CN111533914A (en) * | 2020-04-13 | 2020-08-14 | 浙江衢州正邦有机硅有限公司 | Continuous production process of polymethyltriethoxysilane in pipeline mode |
-
2016
- 2016-12-05 CN CN201621326911.4U patent/CN206447803U/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106588863A (en) * | 2016-12-05 | 2017-04-26 | 东营市海科新源化工有限责任公司 | System and process for preparing cyclic carbonate by using composite ionic liquid catalyst |
| CN106588863B (en) * | 2016-12-05 | 2024-04-09 | 东营市海科新源化工有限责任公司 | System and process for preparing cyclic carbonate by adopting composite ionic liquid catalyst |
| CN111533914A (en) * | 2020-04-13 | 2020-08-14 | 浙江衢州正邦有机硅有限公司 | Continuous production process of polymethyltriethoxysilane in pipeline mode |
| CN111533914B (en) * | 2020-04-13 | 2022-08-02 | 郑启波 | Continuous production process of polymethyltriethoxysilane in pipeline mode |
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Address after: 257000 23 Zoucheng Road, Shengli Industrial Park, Dongying District, Dongying City, Shandong Province Patentee after: Shandong Haike Xinyuan material technology Co., Ltd Address before: 257000 No. 23, Zoucheng Road, Dongying District, Shandong, Dongying Patentee before: DONGYING HI-TECH SPRING CHEMICAL INDUSTRY Co.,Ltd. |