WO2015182732A1 - 環状カーボネートの製造装置及び製造方法 - Google Patents
環状カーボネートの製造装置及び製造方法 Download PDFInfo
- Publication number
- WO2015182732A1 WO2015182732A1 PCT/JP2015/065492 JP2015065492W WO2015182732A1 WO 2015182732 A1 WO2015182732 A1 WO 2015182732A1 JP 2015065492 W JP2015065492 W JP 2015065492W WO 2015182732 A1 WO2015182732 A1 WO 2015182732A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- reactor
- epoxide
- carbon dioxide
- cyclic carbonate
- mixing
- Prior art date
Links
Images
Classifications
-
- 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
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
- C07D317/38—Ethylene carbonate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
- B01J8/0449—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
- B01J8/0457—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds the beds being placed in separate reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/02—Processes carried out in the presence of solid particles; Reactors therefor with stationary particles
- B01J2208/023—Details
- B01J2208/027—Beds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Definitions
- the present invention relates to an apparatus and method for producing cyclic carbonate. More particularly, the present invention relates to an apparatus and a method for producing cyclic carbonate in which an epoxide and carbon dioxide are reacted in the presence of a heterogeneous catalyst.
- Cyclic carbonates are used as organic solvents, synthetic fiber processing agents, pharmaceutical raw materials, cosmetic additives, and recently as electrolyte solvents for lithium batteries, and are also used for the synthesis of alkylene glycols and dialkyl carbonates, etc. , One of the important compounds used in a wide range of applications.
- this cyclic carbonate has been synthesized by reacting epoxide and carbon dioxide in the presence of a homogeneous catalyst under appropriate pressure conditions.
- a homogeneous catalyst halides such as alkali metals and onium salts such as quaternary ammonium salts have long been known (Patent Document 1) and are also used industrially.
- Patent Document 1 halides such as alkali metals and onium salts such as quaternary ammonium salts
- separation operation by distillation of the reaction mixture and the catalyst is usually required, which not only complicates the production process, but also decomposes and produces byproducts of the catalyst in the separation process. There is also the problem of generating things.
- a heterogeneous catalyst in which a quaternary phosphonium group having a halide ion as a counter ion is immobilized on a carrier such as silica gel has been proposed, and the immobilization catalyst was used.
- a method of producing propylene carbonate a method of continuously producing propylene carbonate by mixing propylene oxide and supercritical carbon dioxide and supplying it to a reaction tube filled with the above-mentioned immobilized catalyst is disclosed (Patent Document 2) .
- the immobilized catalyst has low activity compared to the homogeneous catalyst, it is necessary to use a large amount of catalyst, especially when the production of cyclic carbonate is to be carried out on an industrial scale. Is a problem.
- the catalyst can not be functioned sufficiently.
- drifting within the system also causes hot spots (local overheating of the catalyst), which significantly accelerates catalyst deterioration.
- Patent Document 2 uses a mixture of propylene oxide and supercritical carbon dioxide, as described in Non-Patent Document 1, propylene carbonate which is a product causes phase separation with supercritical carbon dioxide. Therefore, in order to sufficiently dissolve carbon dioxide in the reaction liquid and to suppress phase separation in the reactor, complete mixing is required, and a large-sized accessory equipment such as a stirring tank is required.
- the reaction between epoxide and carbon dioxide is an exothermic reaction involving a relatively large heat of reaction (eg, ethylene oxide and dioxide
- the heat of reaction of the reaction of carbon is about 100 kJ / mol)
- removal of the heat of reaction at the time of cyclic carbonate synthesis is a problem.
- a method of removing the heat of reaction a method using a heat exchange type reactor such as a jacketed reactor or a multitubular reactor is generally used.
- the heat removal by the jacketed reactor that circulates the heat medium in the jacket is that when the reactor is enlarged, the heat removal area becomes smaller than the amount of catalyst, and only the immobilized catalyst near the heat removal surface can remove heat.
- a basic problem There is a basic problem.
- the catalyst is filled in the reaction tubes to carry out the reaction, while the heat of reaction generated by circulating the heat medium in the reaction tube shells is Because of the removal, the heat removal area can be increased.
- a catalyst immobilized on a carrier such as silica gel
- the flow rate of the liquid is extremely small compared to the amount of this catalyst, so the reaction tube is made extremely thin and long to obtain sufficient heat removal efficiency. Need to make the device complex and bulky. In addition, maintenance becomes complicated. Furthermore, there is also a problem that it is difficult to uniformly charge the catalyst in a plurality of reaction tubes.
- the problem of the present invention is that scale-up is easy without the need for a large-sized reactor or excessive ancillary equipment even when using an immobilized catalyst as a catalyst and producing on an industrial scale. It is an object of the present invention to provide an economical and industrially producible continuous production apparatus and method for cyclic carbonate which can produce cyclic carbonate without impairing the catalyst efficiency and catalyst life.
- an adiabatic reactor filled with a heterogeneous catalyst for reacting an epoxide and carbon dioxide A circulation path for returning at least a portion of the liquid mixed fluid flowing out of the outlet of the reactor to the reactor; Carbon dioxide supply means for continuously supplying carbon dioxide in a liquid or supercritical state into the circulation path; And an epoxide supply means for continuously supplying liquid or solution epoxide into the circulation path,
- the above circulation route is Heat exchange means for removing heat from the circulating fluid (liquid mixed fluid flowing into the circulation path) by indirect heat exchange; Mixing means for mixing the carbon dioxide supplied by the carbon dioxide supply means with the circulating fluid in a path; A gas-liquid separation unit that decompresses a circulating fluid containing carbon dioxide obtained by the mixing unit and performs gas-liquid separation processing; Pressure boosting means for boosting the circulating fluid after the gas-liquid separation process to a predetermined pressure; Mixing means for mixing the epoxide supplied by the epoxide
- this invention solves the said subject, [2] the fixed bed in which the said reactor was connected in series two or more adiabatic reactors in the manufacturing apparatus of cyclic carbonate of said [1].
- Configured as a multi-stage reactor The manufacturing apparatus is provided, wherein the circulation path is provided to return at least a portion of the liquid mixed fluid flowing out of the outlet of the last stage reactor to the first stage reactor.
- the production apparatus of the above [2] is easy to increase the production capacity by adding more reactors.
- the present invention continuously supplies a raw material mixed fluid containing [3] epoxide and carbon dioxide to an adiabatic reactor filled with a heterogeneous catalyst, and the above reactor A method for producing cyclic carbonate, wherein at least a part of the liquid mixed fluid flowing out of the outlet of the A heat exchange step of removing heat from the circulating fluid (liquid mixed fluid flowing into the circulation path) by indirect heat exchange;
- a carbon dioxide supply step of continuously supplying carbon dioxide in a liquid or supercritical state into the circulation path;
- a gas-liquid separation step of reducing the pressure of the circulating fluid containing carbon dioxide obtained by the mixing step and separating the gasified excess carbon dioxide by gas-liquid separation;
- An epoxide supply step of continuously supplying liquid or solution epoxide into the circulation path; Including a mixing step
- the present invention in order to solve the above problems, in the method for producing a cyclic carbonate of [4] above [3], wherein the above reactors are fixed in which two or more adiabatic reactors are connected in series. It is configured as a floor multistage reactor,
- the production method is provided, wherein the circulation path is to return at least a portion of the liquid mixed fluid flowing out of the outlet of the last stage reactor to the first stage reactor.
- the production method of the above [4] can easily increase the production capacity by increasing the number of reactors.
- the epoxide used in the present invention is not particularly limited as long as it is a compound containing at least one epoxy ring (a three-membered ring consisting of two carbon atoms and one oxygen atom) in its structural formula, for example ethylene oxide, propylene oxide, Butylene oxide, isobutylene oxide, vinyl ethylene oxide, trifluoromethyl ethylene oxide, cyclohexene oxide, styrene oxide, butadiene monoxide, butadiene dioxide, 2-methyl-3-phenylbutene oxide, pinene oxide, tetracyanoethylene oxide and the like can be mentioned.
- ethylene oxide and propylene oxide are more preferable.
- R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, carbon
- R 3 and R 4 each independently represent a hydrogen atom, a cyano group or an aryl group having 6 to 12 carbon atoms. Show. However, any one of R 3 and R 4 may form a cycloalkyl group with any one of R 1 and R 2 .
- the carbon number of the alkyl group or haloalkyl group represented by the above R 1 and R 2 is preferably 1 to 4.
- the alkyl group include a methyl group, an ethyl group, a propyl group and a butyl group, preferably a methyl group and an ethyl group, and more preferably a methyl group.
- the carbon number of the alkenyl group or haloalkenyl group represented by R 1 and R 2 is preferably 2 to 4, and specific examples include a vinyl group.
- a halogen atom in the haloalkyl group and the haloalkenyl group chlorine, bromine, iodine and the like can be mentioned.
- a phenyl group is preferable.
- R 1 and R 2 a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a haloalkyl group having 1 to 6 carbon atoms are preferable. Moreover, as R 3 and R 4 , a hydrogen atom is preferable.
- heterogeneous catalyst As the heterogeneous catalyst used in the present invention, an immobilized catalyst having activity for cyclic carbonate synthesis from epoxide and carbon dioxide is preferable, and a solid catalyst in which an ionic organic compound is immobilized on a carrier is more preferable.
- ionic organic compounds include quaternary organic onium salts selected from quaternary organic ammonium salts having a halide anion as a counter ion and quaternary organic phosphonium salts having a halide anion as a counter ion. Be As a halide anion, a fluorine anion, a chlorine anion, a bromine anion, and an iodine anion are mentioned.
- quaternary organic onium salts include tetraalkyl ammonium salts such as tetraalkyl ammonium chloride and tetra alkyl ammonium bromide; and tetraalkyl phosphonium salts such as tetraalkyl phosphonium chloride and tetra alkyl phosphonium bromide.
- tetraalkyl phosphonium salts are preferred.
- the carbon number of the alkyl group in the above tetraalkyl ammonium salt and tetraalkyl phosphonium salt is preferably 1 to 8, more preferably 1 to 6, and still more preferably 2 to 4.
- methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclohexyl group and the like can be mentioned.
- carrier an inorganic oxide support
- the shape is preferably particulate, and is preferably porous.
- Preferred specific examples of the inorganic oxide support include silica gel (gelled silica), mesoporous silica, ceramics, zeolite, and porous glass. Among them, silica gel and mesoporous silica are preferable.
- organic polymer carrier polystyrene, polystyrene copolymer, poly (meth) acrylate, poly (meth) acrylamide, polyimide, polybenzimidazole, polybenzoxazole, polybenzothiazole, polyethylene glycol, polypropylene glycol, or these polymers Copolymers, polymer blends, etc. which contain as a main component.
- the cyclic carbonate obtained in the present invention has a structure in which the epoxy ring of the above epoxide is converted to a carbonate ring (a five-membered ring having an O-CO-O bond), for example, ethylene carbonate and propylene carbonate And butylene carbonate, isobutylene carbonate, trifluoromethyl ethylene carbonate, vinyl ethylene carbonate, cyclohexene carbonate, styrene carbonate, butadiene monocarbonate, butadiene dicarbonate, chloromethyl carbonate, pinene carbonate, tetracyanoethylene carbonate and the like.
- a suitable cyclic carbonate is represented by the following formula (2).
- R 1 to R 4 are as defined above.
- FIG. 1 is a figure which shows typically an example of the manufacturing apparatus of the cyclic carbonate which concerns on 1st Embodiment of this invention.
- an adiabatic reactor 1 filled with a heterogeneous catalyst for reacting an epoxide and carbon dioxide, and a liquid mixture flowing out of the reactor outlet 1a It comprises a circulation path 2 for returning part of the fluid to the reactor 1 and a discharge path 3 for discharging the remaining part of the liquid mixed fluid and sending it to the next step as needed.
- the liquid mixed fluid from the reactor outlet 1a mainly contains cyclic carbonate generated in the reactor 1 and unreacted carbon dioxide, and depending on the reaction conditions, it also contains unreacted epoxide.
- the reactor 1 may be an adiabatic reactor configured to be capable of being charged with a heterogeneous catalyst for reacting an epoxide and carbon dioxide, but a tubular reactor is preferable.
- the material which comprises the reactor 1 is not specifically limited, From the point which is excellent in corrosion resistance, SUS is preferable. Further, by using an inexpensive adiabatic reactor as the reactor 1, it is possible to greatly reduce the equipment cost.
- glass beads or the like may be loaded before and after the catalyst.
- the reactor 1 is also provided with a reactor inlet 1 b.
- the reactor inlet 1 b is configured to allow the circulating fluid to flow from the circulation path 2 into the reactor 1, and the circulating fluid supplied and mixed with carbon dioxide and epoxide in the circulation path 2 is a raw material mixture It is supplied into the reactor 1 as a fluid from the reactor inlet 1 b.
- the manufacturing apparatus of the present embodiment continuously supplies carbon dioxide in the circulation path 2 with carbon dioxide in a liquid or supercritical state continuously, and continuously forms liquid or solution epoxide in the circulation path 2.
- an epoxide supply means 8 for supplying Carbon dioxide as the reaction raw material is continuously supplied to the circulating fluid in a liquid or supercritical state by the carbon dioxide supplying means 6, and the epoxide as the reaction raw material is in a liquid or solution state and the circulating fluid is continuously supplied in a liquid or supercritical state.
- these configurations control the carbon dioxide and epoxide supply rates.
- Examples of the carbon dioxide supply means 6 and the epoxide supply means 8 include a pump.
- a pump By employing a pump as these means, it is possible to control the amount of carbon dioxide and epoxide supplied easily. In addition, it is also possible to greatly reduce the equipment cost.
- epoxide is dissolved in a solvent and supplied in the form of a solution in the epoxide supply means 8, it is preferable to use a cyclic carbonate synthesized from the epoxide as the solvent.
- the solvent is preferably ethylene carbonate.
- the manufacturing apparatus of this embodiment may be equipped with the additive supply means 7 which supplies additives etc. other than the reaction raw material in the circulation route 2.
- the additive supply means 7 supplies the additive into the circulation path 2 while the supply amount is controlled.
- the additives may be supplied continuously or discontinuously.
- the additive may be supplied neat or may be dissolved in a solvent and supplied as a solution. When the solvent is dissolved and supplied, the solvent is preferably a cyclic carbonate.
- the additive supply means 7 includes a pump.
- examples of the additive include halogenated alcohols such as bromoethanol and bromopropanol. The halogenated alcohol suppresses desorption of the catalyst component and acts as a catalyst deterioration inhibitor.
- the manufacturing apparatus of the present embodiment includes the circulation path 2.
- the heat exchange means 4, the first mixing means 9, the gas-liquid separation means 11, the pressure raising means 12, and the second mixing means 10 are directed from the reactor outlet 1a toward the reactor inlet 1b.
- the heat exchange means 4, the first mixing means 9, the gas-liquid separation means 11, the pressure raising means 12, and the second mixing means 10 are provided in this order.
- a part of the liquid mixed fluid which has flowed out from the reactor outlet 1a is circulated to the reactor 1 by the circulation route 2, and as a result, the flow rate in the reactor 1 becomes large and the temperature rise in the reactor 1 is appropriate.
- the circulation path 2 is configured as any suitable pipe. Although the material which comprises piping is not specifically limited, From the point which is excellent in corrosion resistance, SUS is preferable.
- the circulation path 2 includes heat exchange means 4 for removing heat from the circulation fluid by indirect heat exchange. Since heat of reaction can be easily removed by providing the heat exchange means 4 in the circulation path 2, the temperature in the reactor 1 can be easily controlled to a desired range (substantially the reaction temperature). . When the heat exchange means 4 is not provided, the heat of reaction can not be sufficiently removed, so the temperature in the reactor 1 may rise and the catalyst life may be extremely shortened. Any heat exchanger can be used as the heat exchange means 4 as long as the temperature of the circulating fluid passing through the means can be lowered to remove the heat of reaction.
- multi-tubular cylindrical heat exchangers include multi-tubular cylindrical heat exchangers, double-pipe heat exchangers, plate heat exchangers, air coolers, irrigation coolers, coiled heat exchangers, and spiral heat exchangers.
- Double-pipe heat exchangers, air coolers and irrigation coolers are particularly suitable and preferred because of the relatively low flow rate and high pressure operation of the circulating fluid.
- the overall heat transfer coefficient of these heat exchangers is preferably about 200 kcal / (m 2 hrK) or more.
- the space between the reactor outlet 1 a and the heat exchange means 4 be constituted only by the circulation path 2. With such a configuration, the circulating fluid flowing out of the reactor outlet 1a is quickly removed.
- the carbon dioxide inflow part into which the carbon dioxide supplied by the carbon dioxide supply means 6 flows may be in any place in the circulation path, although not particularly limited, carbon dioxide has low thermal conductivity. Also, since the lower the temperature, the higher the solubility, it is preferable to supply it to the circulating fluid after heat removal and mix it promptly, therefore it is provided between the heat exchange means 4 and the mixing means 9 Is preferred.
- the circulation path 2 is a mixing means 9 for mixing the carbon dioxide supplied by the carbon dioxide supply means 6 and the circulation fluid which flows into the circulation path 2 and is removed by the heat exchange means 4 in the path. Mixing means).
- the carbon dioxide supplied is uniformly mixed with the other components by the mixing means 9. It is preferable to use an in-line mixer such as a static mixer as the mixing means 9 because the device is simple. By providing the circulation path 2 with an in-line mixer, carbon dioxide and other components can be efficiently mixed in the flow path, and a uniform circulating fluid can be obtained.
- a pressure control means 13 for controlling the opening degree of the circulation path 2 be provided between the mixing means 9 and the gas-liquid separation means 11.
- the pressure control means 13 includes a back pressure valve.
- the circulation path 2 includes a gas-liquid separation unit 11 that decompresses the circulation fluid containing carbon dioxide obtained by the mixing unit 9 and performs gas-liquid separation processing. Excess gasified carbon dioxide is separated by the gas-liquid separation means 11, and as a result, uneven flow due to gasification of the circulating fluid is suppressed, and insufficient wetting of the heterogeneous catalyst in the reactor 1 is eliminated. The catalyst can be used efficiently because it can be done.
- the gas-liquid separation means 11 include a gas-liquid separation tank capable of separating the supplied gas-liquid two-phase flow into gas and liquid, and capable of storing liquid.
- the gas-liquid separation tank By using the gas-liquid separation tank, it is possible to put the circulating fluid into the gas-liquid separation tank and circulate it to establish the circulation between the reactor 1 and the circulation path 2 at the start of operation of the apparatus. In addition, it is possible to store circulating fluid even after the end of operation.
- the gas-liquid separation means 11 is provided with a gas discharge path for discharging the separated gas above the portion where the circulation path 2 is connected.
- pressure control means 14 for controlling the internal pressure of the gas-liquid separation means 11 is provided in the gas discharge path.
- the pressure control means 14 includes a back pressure valve. By adjusting the pressure control means 13 and 14, a predetermined pressure difference can be provided between the gas-liquid separation means 11 and the mixing means 9, and excess carbon dioxide can be gasified and separated. it can.
- the circulation path 2 includes a pressure raising means 12 which raises the pressure of the circulating fluid subjected to gas-liquid separation processing by the gas-liquid separation means 11 to a predetermined pressure.
- the circulation flow rate can be properly controlled by the pressure raising means 12, and the pressure is raised to a predetermined pressure (substantially the reaction pressure).
- a predetermined pressure substantially the reaction pressure
- the circulating fluid substantially does not contain a gas phase, and the gasification of carbon dioxide in the reactor 1 can be suppressed.
- Examples of the pressure raising means 12 include a circulation pump and the like.
- the epoxide inflow portion into which the epoxide supplied by the epoxide supply means 8 flows in prevents the epoxide from being entrained in carbon dioxide gasified by the gas-liquid separation treatment, so that the vapor-liquid separation means 11 is preferably provided downstream of 11 and is more preferably provided at a position close to the inlet of the reactor in order to suppress side reactions, so that it is provided between the pressure raising means 12 and the mixing means 10 Particularly preferred.
- the circulation path 2 one provided with the heat exchange means 5 is preferable.
- the temperature of the reactor inlet 1b can be adjusted by the cyclic carbonate / epoxide circulation ratio at the reactor inlet 1b, but the heat exchange means 5 preheats the raw material mixed fluid passing through the reactor inlet 1b, and the reactor inlet 1b The temperature can be adjusted more easily.
- the heat exchange means 5 can be used when preheating the inside of a system before reaction start (before epoxide introduction).
- the heat exchange means 5 may be of any type that can be temperature-controlled by indirect heat exchange, but a double-pipe heat exchanger having a simple structure due to high pressure operation and a corresponding heat exchange efficiency is preferable.
- the heat exchange means 5 may be located anywhere in the circulation path and is not particularly limited. However, in order to suppress the vaporization of carbon dioxide due to heating, the heat exchange means 5 is preferably provided downstream of the gas-liquid separation tank 11.
- the additive inflow portion into which the additive and the like supplied by the additive supply means 7 flow may be in any part of the circulation path, and is not particularly limited. Since the amount of additive supplied is usually small, it is not necessary to prepare a separate mixing means if it is supplied upstream of the mixing means 10.
- the circulation path 2 is a mixing means 10 (second mixing means) for mixing the epoxide supplied by the epoxide supply means 8 and the circulation fluid which flows into the circulation path 2 and is pressurized by the pressure raising means 12 in the path.
- the mixing means 10 uniformly mixes the supplied epoxide with the other components. It is preferable to use an in-line mixer such as a static mixer as the mixing means 10 because the device is simple. By providing the circulation path 2 with an in-line mixer, the epoxide and other components can be efficiently mixed in the flow path, and a uniform circulating fluid can be obtained.
- the circulating fluid uniformly mixed by the mixing means 10 is supplied as a raw material mixed fluid from the reactor inlet 1b to the adiabatic reactor 1 filled with the catalyst, and as a result, carbon dioxide and epoxide are contained in the reactor 1
- the reaction produces cyclic carbonate.
- the supply amount (flow rate) of the epoxide introduced into the reactor 1 is preferably 0.001 to 10 kg / hr, more preferably 0.01 to 1.0 kg / hr, and more preferably 0.05 to 1 kg per 1 kg of the catalyst. 0.5 kg / hr is more preferable.
- the carbon dioxide content of the raw material mixed fluid introduced into the reactor 1 is preferably 1 to 20, more preferably 1.1 to 10, particularly preferably 1.2 to 5 in the carbon dioxide / epoxide ratio (molar ratio). preferable.
- the amount of catalyst charged into the reactor 1 can be any amount within the range satisfying the flow rate according to the required production amount of cyclic carbonate.
- the cyclic carbonate / epoxide ratio (mass ratio) recycled to the reactor 1 is preferably 1 or more, more preferably 10 or more, still more preferably 12.5 or more, particularly preferably 15 or more, and preferably Is 100 or less, more preferably 80 or less, still more preferably 60 or less, further preferably 50 or less, still more preferably 40 or less, particularly preferably 30 or less.
- the temperature of the reactor inlet 1b can be adjusted.
- the raw material mixed fluid since the raw material mixed fluid does not substantially contain a gas phase, it may flow from the upper part to the lower part of the reactor 1 (down flow method), or may flow from the lower part to the upper part of the reactor 1 (up flow method) Although it is good, the upflow method is preferable because the air bubbles are easily released even when air bubbles are generated.
- the liquid mixed fluid from the reactor outlet 1a mainly contains cyclic carbonate generated in the reactor 1 and unreacted carbon dioxide, and depending on reaction conditions, contains unreacted epoxide. A part thereof may be led to the circulation path 2 as described above, and the remainder discharged from the discharge flow path 3 may be sent to, for example, separation / purification means (not shown) or the like.
- the discharge path 3 is configured as any suitable pipe. Although the material which comprises piping is not specifically limited, From the point which is excellent in corrosion resistance, SUS is preferable. Further, a control valve 15 is provided in the discharge path 3. The control valve 15 can adjust the amount of liquid introduced to the circulation path 2 and circulated in the system and the amount of liquid discharged from the discharge path 3.
- the production apparatus of the present embodiment includes a fixed bed multistage reactor in which two or more adiabatic reactors similar to the reactor 1 are connected in series, and in the production apparatus, the circulation path is a fixed bed multistage reaction. At least a portion of the liquid mixed fluid flowing out of the outlet of the last stage reactor contained in the vessel is returned to the first stage reactor contained in the fixed bed multistage reactor.
- the amount of catalyst relative to the amount of cyclic carbonate production is substantially constant regardless of the number of reactors. For this reason, the production apparatus of the present embodiment can easily increase the production capacity by adding a reactor.
- an epoxide supply means for continuously supplying liquid or solution epoxide to at least one flow path among flow paths connecting the reactors contained in a fixed bed multistage reactor, and
- the apparatus further comprises mixing means for mixing the epoxide supplied by the epoxide supply means and the liquid mixed fluid flowing into the flow path in the flow path.
- liquid or solution epoxides are continuously supplied in all the channels connecting between each reactor, mixed in all channels connecting each reactor, and mixed in the inlet of the next stage reactor. It is more preferable to adopt such a configuration because the introduction of the reaction can disperse the heat generated by the reaction to all the reactors.
- At least one of the flow paths connecting the reactors included in the fixed bed multi-stage reactor indirectly heat-exchanges the liquid mixed fluid that has flowed into the flow path. It is preferable to have heat exchange means for removing heat.
- the heat of reaction generated in the first stage reactor can be easily removed, and the temperature in the next stage reactor can be easily set to the desired range (substantially the reaction temperature). Can be controlled.
- heat removal can be performed more efficiently by cooling by indirect heat exchange and removing reaction heat in all the channels connecting between the reactors, such a configuration is adopted. Is more preferred.
- FIG. 2 is a figure which shows typically an example of the manufacturing apparatus of cyclic carbonate which used the fixed-bed multistage reactor based on 2nd Embodiment of this invention.
- the apparatus for producing cyclic carbonate shown in FIG. 2 includes a fixed bed multistage reactor in which three adiabatic reactors (reactor 1, reactor 21 and reactor 31) are connected in series, and the fixed bed multistage reaction
- the flow path 22 from the outlet 1a of the first stage reactor (reactor 1) to the inlet 21b of the second stage reactor (reactor 21), and the third stage reaction from the second stage reactor outlet 21a A flow path 32 to the inlet 31 b of the vessel (reactor 31) is provided.
- a portion of the liquid mixed fluid that has flowed out of the third stage reactor outlet 31a is led to the first stage reactor inlet 1b via the circulation path 2 in the same manner as the process shown in FIG.
- the flow path 22 and the flow path 32 are configured as any appropriate piping.
- the material which comprises piping is not specifically limited, SUS is preferable from the point which is excellent in corrosion resistance.
- the reactor 21 and the reactor 31 may be of any type as long as they can be packed with a heterogeneous catalyst for reacting an epoxide and carbon dioxide, as in the reactor 1, but a tubular reaction Vessel is preferred.
- a heterogeneous catalyst for reacting an epoxide and carbon dioxide as in the reactor 1, but a tubular reaction Vessel is preferred.
- the material which comprises the reactor 21 and the reactor 31 is not specifically limited, SUS is preferable from the point which is excellent in corrosion resistance. Further, by using an inexpensive adiabatic reactor as the reactor 21 and the reactor 31, it is possible to greatly reduce the equipment cost. Further, when the heterogeneous catalyst is charged into the reactor 21 and the reactor 31, glass beads or the like may be filled before and after the catalyst.
- the manufacturing apparatus of the cyclic carbonate shown in FIG. 2 is equipped with the epoxide supply means 8 which continuously supplies the liquid or solution epoxide similarly to the manufacturing apparatus of 1st Embodiment.
- control valves 16, 26 and 36 are disposed in the flow path 22 and the flow path 32 so that epoxide is supplied into the flow path.
- the epoxide which is a reaction raw material is supplied to the liquid mixed fluid flowing in the circulation path 2, the flow path 22 and the flow path 32 in a liquid or solution state.
- the supply amount of the epoxide supplied to the reactors 1, 21, 31 can be controlled by the control valves 16, 26, 36, respectively.
- an epoxide supply means may be arranged individually in each flow path. In this case, the supply amount of epoxide supplied to each reactor can be respectively controlled by separate epoxide supply means.
- the flow paths 22 and 32 are respectively provided with heat exchange means 24 and 34 for removing the heat of the liquid mixed fluid flowing into the flow paths by indirect heat exchange.
- the heat exchange means 24 and 34 in the flow paths 22 and 32, the heat of reaction generated in the reactor in the former stage can be easily removed, and the temperature in the reactor in the next stage can be in a desired range (substantially Reaction temperature) can be easily controlled.
- any heat exchanger can be used as the heat exchange means 24, as long as the temperature of the liquid mixed fluid passing through the means can be lowered to remove the heat of reaction.
- multi-tubular cylindrical heat exchangers include multi-tubular cylindrical heat exchangers, double-pipe heat exchangers, plate heat exchangers, air coolers, irrigation coolers, coiled heat exchangers, and spiral heat exchangers.
- Double-pipe heat exchangers, air coolers and irrigation coolers are particularly suitable and preferred because of the relatively low flow rate and high pressure operation of the circulating fluid.
- the overall heat transfer coefficient of these heat exchangers is preferably about 200 kcal / (m 2 hrK) or more.
- the flow paths 22 and 32 are provided with mixing means 20 and 30, respectively.
- the mixing means 20, 30, the supplied epoxide and the liquid mixed fluid which has flowed into the flow path are mixed in the flow path.
- an in-line mixer such as a static mixer because the device is simple.
- the heat exchange means 24, the epoxide inflow part, and the mixing means 20 in the flow path 22 are from the outlet 1a of a 1st stage reactor to the inlet 21b of a 2nd stage reactor.
- the heat exchange means 24, the epoxide inflow portion, and the mixing means 20 are provided in this order.
- the heat exchange means 34, the epoxide inflow portion, and the mixing means 30 in the flow path 32 are the heat exchange means 34, the epoxide inflow portion, from the outlet 21a of the second stage reactor toward the inlet 31b of the third stage reactor.
- the mixing means 30 are provided in order.
- the liquid mixed fluid can be efficiently removed of heat, mixed with epoxide uniformly and efficiently, and supplied to the next reactor. Moreover, with such a configuration, the temperature difference between the outlet temperature and the inlet temperature of each reactor can be increased within the range where catalyst deterioration does not occur, and the reaction can be efficiently performed at a high reaction rate in all reactors. It will be possible to do.
- FIG. 2 illustrates a manufacturing apparatus using a fixed-bed multistage reactor in which three adiabatic reactors 1, 21 and 31 are connected in series
- the number of adiabatic reactors is two or more.
- the number of adiabatic reactors contained in the fixed bed multistage reactor is preferably 2 to 10, more preferably 2 to 6 and still more preferably 2 to 4.
- mold reactor and, thereby, it is possible to adjust a production quantity suitably, Furthermore, replacement of a catalyst is continued, continuing production. Is possible.
- connection order of the reactors by appropriately changing the flow path between the reactors, and it is possible to react in an order optimized according to the deterioration state of the catalyst.
- the supply amount of epoxide introduced to each adiabatic reactor, the carbon dioxide content of the raw material mixed fluid, the amount of catalyst charged to each adiabatic reactor, cyclic carbonate / epoxide circulated to each adiabatic reactor The ratio (mass ratio) of is the same as that of the first embodiment.
- a raw material mixed fluid containing epoxide and carbon dioxide is continuously supplied to the adiabatic reactor packed with the heterogeneous catalyst, and the reactor outlet (in the case of a fixed bed multistage reactor, the final stage reactor At least a portion of the liquid mixed fluid that has flowed out from the outlet) is circulated to the circulation path returned to the reactor, the heat of reaction is removed in the circulation path, epoxide and carbon dioxide are continuously supplied to the circulation fluid, and It is done while mixing.
- the inlet temperature (reaction temperature) of the adiabatic reactor is the reaction rate, From the viewpoint of reaction efficiency, it is preferably 60 ° C. or more, more preferably 70 ° C. or more, still more preferably 80 ° C. or more, still more preferably 90 ° C. or more, still more preferably 100 ° C. or more, particularly preferably 110 ° C. or more From the viewpoint of suppressing thermal decomposition and preventing deactivation of the catalyst life, preferably 160 ° C. or less, more preferably 150 ° C. or less, still more preferably 140 ° C. or less, still more preferably 130 ° C. or less, particularly preferably 120 ° C. or less is there.
- the temperature at the outlet of the adiabatic reactor is preferably 80 ° C. or more, more preferably 90 ° C. or more, still more preferably 100 ° C. or more, preferably 180 ° C. or less, more preferably 160 ° C. or less, further Preferably it is 140 degrees C or less.
- the temperature difference between the reactor outlet temperature and the inlet temperature is preferably 10 ° C. or more, more preferably 20 ° C. or more, still more preferably 30 ° C. or more, preferably 80 ° C. or less, more preferably 70 ° C. or less More preferably, it is 60 ° C. or less, particularly preferably 50 ° C. or less. Moreover, it is preferable to set it as outlet temperature> inlet temperature.
- the calorific value per production amount is constant (for example, in the case of ethylene carbonate synthesis from ethylene oxide and carbon dioxide, the reaction heat is about 100 kJ / mol), so the inlet temperature of the adiabatic reactor and the above temperature difference are It can be adjusted by the flow ratio of epoxide and cyclic carbonate to be circulated.
- the reaction pressure is preferably 1 to 15 MPa from the viewpoint of preventing gasification of carbon dioxide and epoxide and making the equipment economical. Furthermore, it is preferable to react in the vicinity of the critical pressure (7.38 MPa) of carbon dioxide from the point of cyclic carbonate yield, and in order to suppress the partial flow in the reactor by the gasification of carbon dioxide, It is more preferable to make it react. Specifically, the reaction is preferably performed at 7 to 10 MPa, and more preferably at 7.4 to 9 MPa.
- cyclic carbonate is first circulated to the production apparatus of the present invention described above to establish circulation between the reactor 1 and the circulation path 2
- the preferred method is As cyclic carbonate, the previous lot of circulating fluid (for example, circulating fluid after gas-liquid separation) or cyclic carbonate produced by the process of the present invention can be used, and commercially available cyclic carbonate may be used.
- a method of establishing the above-mentioned circulation specifically, a cyclic carbonate which has been heated in advance is stuck in the gas-liquid separation means 11, which is transferred by the pressure raising means 12 to the heat exchange means 5, reactor 1, circulation path 2, heat.
- a method of feeding and circulating to the exchange means 4 may be mentioned.
- the circulating fluid of the previous lot may be stored in the gas-liquid separating means 11 and used. In any case, it is preferable to adjust the reactor inlet temperature by the heat exchange means 5.
- carbon dioxide is supplied into the circulation path 2 while the supply amount is controlled by the carbon dioxide supply means 6.
- the carbon dioxide is stirred by the mixing means 9 and circulated in the process in a state of being completely mixed, ie, completely dissolved, in the cyclic carbonate.
- Excess carbon dioxide which is not dissolved in the cyclic carbonate is separated by the gas-liquid separation means 11.
- the excess carbon dioxide is exhausted from the upper part of the gas-liquid separation means 11, but the pressure of the gas-liquid separation means 11 is higher than the pressure of the reactor 1 (therefore, the pressure of the mixing means 9) It is controlled to a low pressure.
- the differential pressure between the gas-liquid separation means 11 and the reactor 1 is preferably 0.1 MPa or more, more preferably 0.3 MPa or more, still more preferably 0.5 MPa or more, and preferably 1.0 MPa or less.
- the circulation liquid after gas-liquid separation is pressurized to a desired pressure (substantially the reaction pressure) to supply an epoxide and, if necessary, an additive.
- the epoxide is supplied into the circulation path while controlling the supply amount by the epoxide supply means 8 and stirred by the mixing means 10, whereby a uniform raw material mixed fluid is formed.
- the additive is supplied into the circulation path while controlling the supply amount by the additive supply means 7.
- the feed position of the additive is not particularly limited, the feed amount of the additive is usually small, so if it is fed upstream of the mixing unit 10, it is not necessary to prepare a separate mixing unit.
- the raw material mixed fluid containing an epoxide is supplied to the reactor 1, and by contacting with the catalyst charged in the reactor 1, continuous production is started.
- a fixed bed multistage reactor in which a plurality of adiabatic reactors are connected in series may be used as the reactor.
- an adiabatic reactor is added, at least a portion of the liquid mixed fluid flowing out of the last stage reactor outlet is led to the circulation path 2 returning to the first stage reactor inlet.
- an epoxide is continuously supplied to continuously supply liquid or solution epoxide to at least one flow path among the flow paths connecting the reactors included in the fixed bed multistage reactor, and the epoxide supply step supplies the epoxide. It is preferable to mix the epoxide and the liquid mixed fluid which has flowed into the flow path in the flow path.
- liquid or solution epoxide is continuously supplied in all the channels connecting between each reactor, mixed in all connecting channels connecting between each reactor, and the reactor inlet of the next stage It is more preferable to introduce
- the liquid mixed fluid from the reactor outlet 1a (in the case of a multistage reactor, the outlet of the final stage reactor) mainly contains cyclic carbonate formed in the reactor and unreacted carbon dioxide, and depending on the reaction conditions, unreacted epoxide including. A portion thereof is led to the circulation path 2 as described above, cooled by the heat exchange means 4 and the heat of reaction is removed. The remainder is sent from the discharge path 3 to the next step (separation / purification step) as necessary. The amount of discharge from the discharge path 3 is adjusted by the control valve 15 so that the amount of retained oil in the system becomes constant.
- the liquid mixed fluid is depressurized to separate carbon dioxide and epoxide, and the discharged gas is compressed to recycle carbon dioxide, and crude cyclic carbonate after removing carbon dioxide and epoxide is removed.
- purify by methods, such as distillation, crystallization, adsorption, etc. are applicable.
- Fluorescent X-ray analysis was used for the measurement of the bromine and phosphorus modification amount of a catalyst.
- the analysis conditions are as follows.
- thermogravimetry-differential thermal differential measuring device was used to measure the thermogravimetric weight of the catalyst.
- the analysis conditions are as follows.
- Sample amount 14 mg (the sample ground in a mortar was weighed in an aluminum pan)
- Measurement range temperature rise temperature: room temperature (25 ° C) ⁇ temperature rise at 5 ° C / min ⁇ hold at 50 ° C for 3 hours ⁇ temperature rise at 0.5 ° C / min ⁇ hold at 250 ° C for 3 hours
- Catalyst Synthesis Example 1 Synthesis of tributylphosphonium bromide surface modified silica gel catalyst Beaded silica gel (CARiACT Q-10 (average pore diameter 10 nm, particle diameter 1.2 to 2.4 mm, specific surface area 300 m 2 / g) manufactured by Fuji Silysia Chemical Ltd.) 40 kg and 100 liters of xylene were charged into a 200 liter SUS reaction tank. Azeotropic dehydration of xylene-water was performed for 2 hours under reflux at 140 ° C. to remove water in the silica gel. Next, the inside of the reaction vessel was purged with nitrogen, and then 4.4 kg of 3-bromopropyltrimethoxysilane was dropped.
- CARiACT Q-10 average pore diameter 10 nm, particle diameter 1.2 to 2.4 mm, specific surface area 300 m 2 / g
- the silanization reaction was carried out by heating and refluxing this as it is at 135 ° C. for 9 hours.
- the obtained reaction product was withdrawn from the reaction vessel, and the catalyst precursor (bromopropylated silica gel) in the reaction product was separated by filtration and then washed with 40 L of xylene.
- the bromine modification amount in the catalyst precursor obtained here was 0.39 mmol / g.
- the obtained catalyst precursor and 100 liters of xylene were charged into a reaction vessel, the inside of the reaction vessel was replaced with nitrogen, and then 9.1 kg of tri-n-butylphosphine was dropped. This was directly heated under reflux for 24 hours to carry out quaternary phosphoniumization reaction.
- the reaction product was separated by filtration and washed with 40 L of acetone six times. The reaction product was then dried under reduced pressure overnight at 120 ° C. under a nitrogen stream to obtain 46 kg of the target tributylphosphonium bromide surface-modified silica gel.
- the bromine modification amount in the catalyst was 0.32 mmol / g, and the phosphorus modification amount was 0.33 mmol / g.
- Reference Example 1 Thermogravimetry of Catalyst The thermogravimetry of the catalyst obtained in Catalyst Synthesis Example 1 was carried out. The results are shown in FIG. As shown in FIG. 3, thermal decomposition of the catalyst was observed from a temperature of 146 ° C. or higher, and 1-bromobutane was detected as a decomposition product. From this result, the reactor upper limit temperature in the following example was set to 140 ° C.
- Reference Example 2 Investigation of the influence of reaction pressure on ethylene carbonate yield
- 400 mg of the catalyst obtained in Catalyst Synthesis Example 1 was charged and dried under reduced pressure at 120 ° C. for 1 hour.
- 4 mL (60 mmol) of ethylene oxide was charged.
- carbon dioxide is temporarily filled to 1.5 MPaG, and then the inside of the autoclave is heated to 100 ° C. while being stirred at 800 rpm with a stirrer, and the carbon dioxide is further charged, whereby the internal pressure is 3.0 to 18.3 MPa.
- the reaction was carried out for 1 hour.
- Example 1 Production of ethylene carbonate using a continuous production apparatus In the apparatus shown in FIG. 1, double-tube heat exchangers are used as the heat exchange means 4, 5, raw material supply means 6, 7, 8 and pressure raising means. Production of ethylene carbonate using an apparatus equipped with a pump as 12, a static mixer as mixing means 9 and 10, a gas-liquid separation vessel as gas-liquid separation means 11, and a back pressure valve as pressure control means 13 and 14, respectively. Did.
- Carbon dioxide was then supplied by pump 6 at a flow rate of 53 g / hr. At that time, carbon dioxide was stirred by a static mixer 9 and circulated in a state of being completely mixed with ethylene carbonate, ie, completely dissolved. Excess carbon dioxide which is not dissolved in ethylene carbonate is separated in the gas-liquid separation tank 11, so that uneven flow in the reactor 1 is prevented. Excess carbon dioxide is exhausted from the upper part of the gas-liquid separation tank 11, and the pressure of the gas-liquid separation tank 11 is maintained at 7.5 MPaG by the excess gas and the back pressure valve 14. Subsequently, the pressure of the reactor 1 was adjusted to 8.0 MPaG by the back pressure valve 13.
- the pressure difference between the static mixer 9 and the reactor 1 and the gas-liquid separation tank 11 was set to 0.5 MPa. Further, the liquid after gas-liquid separation was pressurized to 8.0 MPaG by a pump 12 and supplied to the reactor 1. By this operation, carbon dioxide which is completely dissolved in ethylene carbonate and hardly causes gasification is supplied to the reactor 1.
- the saturated solubility of carbon dioxide in ethylene carbonate at a reactor inlet 1b condition (8 MPa, 100 ° C.) is approximately 12% by mass, while the carbon dioxide solubility in circulating fluid after gas-liquid separation is approximately 11% by mass there were.
- the degree of opening of the control valve 15 was adjusted so that the liquid level of the gas-liquid separation tank 11, ie, the amount of retained oil in the system, became constant, and the produced ethylene carbonate was extracted from the discharge path 3.
- the ethylene carbonate flow rate withdrawn was about 88 g / hr.
- ethylene oxide was not detected from the gas exhausted from the upper part of the gas-liquid separation tank 11, so the conversion ratio of ethylene oxide was calculated by the following equation.
- Conversion ratio X ⁇ (feed ethylene oxide flow)-(extracted ethylene oxide flow) ⁇ / (feed ethylene oxide flow) ⁇ 100
- the concentration of ethylene oxide in the extracted ethylene carbonate was 0.29%, and the conversion of ethylene oxide was calculated to be 99.4%.
- the reactor outlet temperature was maintained in the range of 115 to 118 ° C., and no decrease in conversion due to catalyst deactivation was observed. That is, it has been demonstrated that the temperature of the reactor is properly controlled by indirect heat exchange, and catalyst performance can be maintained even in long-term operation.
- Example 2 Reactor Simulation in Group In the embodiment shown in FIG. 1, the relationship between the reactor temperature, the ethylene carbonate circulating amount, and the catalyst amount was simulated under the following conditions. The results are shown in Table 1.
- Simulation software PRO II (Invensis Process Systems Co., Ltd.) physical property estimation method SRK-M Device: In the device shown in FIG. 1, double-pipe heat exchangers as heat exchange means 4 and 5, pumps as raw material supply means 6, 7 and 8 and pressure raising means 12 and static means as mixing means 9 and 10.
- Example 3 Reactor Simulation in Three Groups
- the relationship between the reactor temperature, the ethylene carbonate circulation amount, and the catalyst amount was simulated under the following conditions. The results are shown in Table 1.
- Example 4 Reactor simulation with two units When the number of reactors is two, that is, in the embodiment shown in FIG. 2, the control valve 36, the flow path 32, the reactor 31, the heat exchange means 34 and the mixing means 30.
- the inlet temperature can be controlled by the ethylene carbonate / ethylene oxide circulating ratio at the reactor inlet, and by optimizing these, ethylene carbonate production of 400 to 1000 tons / year can be achieved.
- the reaction can be carried out with a relatively small amount of catalyst of about 500 liters. Therefore, it is possible to carry out the reaction in a compact reactor, and the equipment cost can be reduced.
- the amount of catalyst relative to the amount of cyclic carbonate produced is substantially constant regardless of the number of reactors, so when increasing the production capacity, it is only necessary to increase the number of reactors, heat exchangers and static mixers sequentially. It is possible to boost the ability to economically excel. Therefore, there is no need for disposal of equipment, and double investment in equipment is not required.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polyesters Or Polycarbonates (AREA)
- Epoxy Compounds (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Accessories For Mixers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
しかしながら、このような均一系触媒を使用する場合、通常、反応混合物と触媒との蒸留等による分離操作が必要となり、製造工程が複雑となるばかりでなく、分離工程中の触媒の分解や副生成物の生成といった問題もある。
また、触媒量に比して反応液の通液量が少ないため、(1)反応器内で反応液の偏流が生じる、(2)触媒と反応液との接触、すなわち触媒の濡れが不十分となり、触媒を十分に機能させることができない、という問題がある。更に、系内の偏流等は、ホットスポット(触媒の局所的な過熱)の要因ともなり、触媒劣化を著しく早める。
また、二酸化炭素がガス化しない条件下であっても、二酸化炭素の混合が不十分であると反応液は必ずしも均一相とはならない。例えば、特許文献2ではプロピレンオキシドと超臨界二酸化炭素とを混合して用いているが、非特許文献1に記載のように、生成物であるプロピレンカーボネートは超臨界二酸化炭素と相分離を起こす。そのため、二酸化炭素を反応液に十分溶解させ、反応器内での相分離を抑制するために、完全混合する必要があり、撹拌槽などの大型の付帯設備が必要となる。
しかしながら、ジャケットに熱媒を循環させるジャケット付反応器による除熱は、反応器を大きくすると触媒量に比して除熱面積が小さくなり、また除熱面近傍の固定化触媒しか除熱できないという基本的な問題がある。
上記反応器の出口から流出した液状混合流体の少なくとも一部を上記反応器に戻す循環経路と、
当該循環経路内に液状又は超臨界状態の二酸化炭素を連続的に供給する二酸化炭素供給手段と、
上記循環経路内に液状又は溶液状のエポキシドを連続的に供給するエポキシド供給手段とを備え、
上記循環経路が、
循環流体(循環経路に流入した液状混合流体)を間接熱交換により除熱する熱交換手段と、
上記二酸化炭素供給手段により供給された二酸化酸素と上記循環流体とを経路内で混合する混合手段と、
当該混合手段により得られた二酸化炭素を含む循環流体を減圧し、気液分離処理する気液分離手段と、
気液分離処理後の循環流体を所定の圧力まで昇圧する昇圧手段と、
上記エポキシド供給手段により供給されたエポキシドと上記循環流体とを経路内で混合する混合手段とを具備することを特徴とする、
環状カーボネートの製造装置を提供する。
上記循環経路が、最後段反応器の出口から流出した液状混合流体の少なくとも一部を第1段反応器に戻すようにして設けられている、製造装置を提供する。
循環流体(循環経路に流入した液状混合流体)を間接熱交換により除熱する熱交換工程と、
上記循環経路内に液状又は超臨界状態の二酸化炭素を連続的に供給する二酸化炭素供給工程と、
上記二酸化炭素供給工程により供給された二酸化酸素と上記循環流体とを経路内で混合する混合工程と、
当該混合工程により得られた二酸化炭素を含む循環流体を減圧し、ガス化した余剰の二酸化炭素を気液分離処理する気液分離工程と、
気液分離後の循環流体を所定の圧力まで昇圧する昇圧工程と、
上記循環経路内に液状又は溶液状のエポキシドを連続的に供給するエポキシド供給工程と、
上記エポキシド供給工程により供給されたエポキシドと上記循環流体とを経路内で混合する混合工程を含むことを特徴とする、
環状カーボネートの製造方法を提供する。
上記循環経路が、最後段反応器の出口から流出した液状混合流体の少なくとも一部を第1段反応器に戻すものである、製造方法を提供する。
(エポキシド)
本発明で用いるエポキシドとしては、エポキシ環(炭素原子2つと酸素原子1つからなる3員環)を構造式中に少なくとも1つ含む化合物であれば特に限定されないが、例えば、エチレンオキシド、プロピレンオキシド、ブチレンオキシド、イソブチレンオキシド、ビニルエチレンオキシド、トリフルオロメチルエチレンオキシド、シクロヘキセンオキシド、スチレンオキシド、ブタジエンモノオキシド、ブタジエンジオキシド、2-メチル-3-フェニルブテンオキシド、ピネンオキシド、テトラシアノエチレンオキシド等が挙げられる。
斯様なエポキシドの中でも、下記式(1)で表されるものが好ましく、エチレンオキシド、プロピレンオキシドがより好ましい。
また、上記R1及びR2で示されるアルケニル基、ハロアルケニル基の炭素数は、好ましくは2~4であり、具体的には、ビニル基等が挙げられる。
また、ハロアルキル基及びハロアルケニル基におけるハロゲン原子としては、塩素、臭素、ヨウ素等が挙げられる。
また、上記R1、R2、R3及びR4で示されるアリール基としては、フェニル基が好ましい。
また、R3及びR4としては、水素原子が好ましい。
本発明で用いる不均一系触媒としては、エポキシドと二酸化炭素からの環状カーボネート合成に活性を有する固定化触媒が好ましく、イオン性有機化合物が担体に固定化された固体触媒がより好ましい。
この様なイオン性有機化合物としては、ハロゲン化物アニオンを対イオンとする第四級有機アンモニウム塩及びハロゲン化物アニオンを対イオンとする第四級有機ホスホニウム塩から選ばれる第四級有機オニウム塩が挙げられる。ハロゲン化物アニオンとしては、フッ素アニオン、塩素アニオン、臭素アニオン、ヨウ素アニオンが挙げられる。
第四級有機オニウム塩の好適な具体例としては、テトラアルキルアンモニウムクロリド、テトラアルキルアンモニウムブロミド等のテトラアルキルアンモニウム塩;テトラアルキルホスホニウムクロリド、テトラアルキルホスホニウムブロミド等のテトラアルキルホスホニウム塩が挙げられ、なかでも、テトラアルキルホスホニウム塩が好ましい。
また、上記テトラアルキルアンモニウム塩、テトラアルキルホスホニウム塩中のアルキル基の炭素数は、好ましくは1~8、より好ましくは1~6、更に好ましくは2~4である。例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、シクロへキシル基等が挙げられる。
また、本発明で得られる環状カーボネートは、上記エポキシドのエポキシ環がカーボネート環(O-CO-O結合を有する5員環)に変換された構造を有するものであり、例えば、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、イソブチレンカーボネート、トリフルオロメチルエチレンカーボネート、ビニルエチレンカーボネート、シクロヘキセンカーボネート、スチレンカーボネート、ブタジエンモノカーボネート、ブタジエンジカーボネート、クロロメチルカーボネート、ピネンカーボネート、テトラシアノエチレンカーボネート等が挙げられる。好適な環状カーボネートは、下記式(2)で表されるものである。
<第1実施形態>
本発明の第1の実施形態に係る環状カーボネートの製造装置(第1の製造装置)について説明する。
図1は、本発明の第1実施形態に係る環状カーボネートの製造装置の一例を模式的に示す図である。
図1に示すように、本実施形態の製造装置は、エポキシドと二酸化炭素とを反応させるための不均一系触媒が充填される断熱型の反応器1と、反応器出口1aから流出した液状混合流体の一部を反応器1に戻す循環経路2と、液状混合流体の残部を排出し必要に応じて次工程に送るための排出経路3とを備える。反応器出口1aからの液状混合流体は主として反応器1内で生成した環状カーボネートと未反応の二酸化炭素を含んでおり、反応条件によっては未反応のエポキシドも含まれる。
また、不均一系触媒を反応器1に充填する際は、触媒の前後にガラスビーズ等を充填してもよい。
二酸化炭素供給手段6によって、反応原料である二酸化炭素が液状又は超臨界状態で循環流体に連続的に供給され、エポキシド供給手段8によって、反応原料であるエポキシドが液状又は溶液状の状態で循環流体に連続的に供給される。また、これら構成によって、二酸化炭素とエポキシドの供給量は制御される。
二酸化炭素供給手段6及びエポキシド供給手段8としては、例えば、ポンプが挙げられる。これら手段としてポンプを採用することにより、二酸化炭素やエポキシドの供給量を簡便に制御することができる。また、設備コストを大きく低減させることも可能である。
なお、エポキシド供給手段8において、エポキシドを溶媒に溶解して溶液状で供給する場合、そのエポキシドから合成される環状カーボネートを溶媒とするのが好ましい。具体的には、エチレンオキシドを溶媒に溶解して溶液状で供給する場合、溶媒はエチレンカーボネートが好ましい。
添加剤は連続的に供給してもよく非連続的に供給してもよい。また、添加剤は、ニートで供給してもよいし、溶媒に溶解して溶液状で供給してもよい。溶媒に溶解して供給する場合、溶媒は環状カーボネートが好ましい。
添加剤供給手段7としては、ポンプが挙げられる。
また、添加剤としては、ブロモエタノール、ブロモプロパノールなどのハロゲン化アルコールが挙げられる。ハロゲン化アルコールは、触媒成分の脱離を抑制し、触媒劣化抑制剤として作用する。
循環経路2により、反応器出口1aから流出した液状混合流体の一部が反応器1に循環され、その結果、反応器1内の通液量が大きくなり反応器1内の温度上昇が適正な範囲に抑えられやすくなり、また、反応液の偏流や反応器1内における触媒の濡れ不足を解消することができるため、触媒効率や触媒寿命の低下を抑えることができる。更に、滞留時間を長くすることができるため、触媒量を減らすことができ、反応器1の大きさをコンパクトにすることもできる。
循環経路2は、任意の適切な配管として構成される。配管を構成する材料は特に限定されないが、耐食性に優れる点から、SUSが好ましい。
循環経路2に熱交換手段4を設けることにより、反応熱を容易に除去することができるため、反応器1内の温度を所望の範囲(実質的に反応温度)に容易に制御することができる。熱交換手段4を設けない場合は、反応熱を十分に除去することができないため、反応器1内の温度が上昇し、触媒寿命が極端に短くなることがある。
熱交換手段4としては、当該手段を通過する循環流体の温度を下げて反応熱を除去できる限り、任意の熱交換器を使用できる。具体的には、多管円筒型熱交換器、二重管式熱交換器、プレート式熱交換器、エアクーラー、イリゲーションクーラー、コイル式熱交換器、渦巻き式熱交換器等が挙げられるが、循環液量が比較的に小流量であり且つ高圧力操作であるため、二重管式熱交換器、エアクーラー、イリゲーションクーラーが特に適切であり好ましい。また、これらの熱交換器の総括伝熱係数としては好ましくは約200kcal/(m2hrK)以上である。
また、反応器出口1aと熱交換手段4との間は循環経路2のみから構成されているのが好ましい。斯かる構成により、反応器出口1aから流出した循環流体は速やかに除熱されるようになる。
混合手段9によって、供給された二酸化炭素は他の成分と均一に混合される。
混合手段9としては、スタティックミキサー等のインラインミキサーを用いるのが、装置が簡単であり好ましい。循環経路2にインラインミキサーを設けることにより、二酸化炭素と他の成分とを流路内で効率的に混合することができ、均一な循環流体が得られる。
圧力制御手段13としては、背圧弁が挙げられる。
気液分離手段11によって、ガス化した余剰の二酸化炭素が分離され、その結果として、循環流体のガス化による偏流が抑えられ、反応器1内における不均一系触媒の濡れ不足を解消することができるため、効率的に触媒を活用することができる。
気液分離手段11としては、供給された気液二相流を気体と液体とに分離するとともに、液体の貯留が可能な気液分離槽が挙げられる。気液分離槽を用いることにより、装置の運転開始にあたり、循環流体を気液分離槽に張り込み、これを循環させて反応器1と循環経路2との間の循環を確立することができる。また、運転終了後も循環流体を貯留することができる。
圧力制御手段14としては、背圧弁が挙げられる。
圧力制御手段13及び14を調節することによって、気液分離手段11と混合手段9との間に、所定の圧力差を付与することができ、余剰の二酸化炭素をガス化させ、分離することができる。
昇圧手段12により循環流量を適正に制御でき、所定の圧力(実質的に反応圧力)まで昇圧される。これにより、循環流体は実質的に気相を含まない状態となり、反応器1内での二酸化炭素のガス化を抑制することができる。
昇圧手段12としては循環ポンプ等が挙げられる。
反応器入口1bの温度は、反応器入口1bにおける環状カーボネート/エポキシドの循環比により調節できるが、熱交換手段5によって、反応器入口1bを通過する原料混合流体が予熱され、反応器入口1bの温度をより簡便に調整できる。また、熱交換手段5は、反応開始前(エポキシド導入前)に系内を予熱する場合に使用することができる。
熱交換手段5としては、間接熱交換により温度調節できるものであればよいが、高圧力操作であるため構造が単純で、相応の熱交換効率を有する二重管式熱交換器が好ましい。
また、熱交換手段5は、循環経路内のいずれにあってもよく特に限定されないが、加熱による二酸化炭素の気化を抑制するため、気液分離槽11より下流に設けられているのが好ましい。
混合手段10によって、供給されたエポキシドは他の成分と均一に混合される。
混合手段10としては、スタティックミキサー等のインラインミキサーを用いるのが、装置が簡単であり好ましい。循環経路2にインラインミキサーを設けることにより、エポキシドと他の成分とを流路内で効率的に混合することができ、均一な循環流体が得られる。
混合手段10により均一に混合された循環流体は、原料混合流体として反応器入口1bから触媒が充填された断熱型反応器1に供給され、その結果として、反応器1内で二酸化炭素とエポキシドが反応して環状カーボネートが生成する。
反応器1に導入される原料混合流体の二酸化炭素含有量は、二酸化炭素/エポキシド比(モル比)が、1~20が好ましく、1.1~10がより好ましく、1.2~5が特に好ましい。
また、反応器1に充填される触媒量は、必要とする環状カーボネートの生産量に応じて、上記流通速度を満たす範囲で任意の量を使用することができる。
また、反応器1へ循環される環状カーボネート/エポキシド比(質量比)は、好ましくは1以上、より好ましくは10以上、さらに好ましくは12.5以上、特に好ましくは15以上であり、また、好ましくは100以下、より好ましくは80以下、さらに好ましくは60以下、さらに好ましくは50以下、さらに好ましくは40以下、特に好ましくは30以下である。斯かる比率を調整することにより、反応器入口1bの温度を調整することができる。
また、排出経路3には、制御弁15が設けられている。斯かる制御弁15により、上記の循環経路2に導かれ系内を循環する液量と、排出経路3から排出される液量とを調節できる。
次に、本発明の第2の実施形態に係る環状カーボネートの製造装置(第2の製造装置)について説明する。第2の製造装置における上記第1の製造装置と同一の部分についての説明は省略する。
本発明においては、後述する実施例に示すように、環状カーボネート生産量に対する触媒量が、反応器数によらずほぼ一定となる。このため、本実施形態の製造装置は、反応器を増設することにより、容易に生産能力を増強することができる。
斯様な構成を採用することにより、複数の反応器にエポキシドを分けて供給することができ、第1段反応器に供給されるエポキシドの量を減らして、当該反応器における発熱を低減し、触媒劣化を抑制することができる。また、各反応器間を接続する全ての流路において液状又は溶液状のエポキシドを連続的に供給し、各反応器間を接続する全ての流路内で混合して次段の反応器入口に導入することによって、反応による発熱を全ての反応器に分散させることができるため、斯様な構成を採用するのがより好ましい。
斯様な構成を採用することにより、前段の反応器で発生した反応熱を容易に除去することができ、次段の反応器内の温度を所望の範囲(実質的に反応温度)に容易に制御することができる。また、各反応器間を接続する全ての流路において間接熱交換により冷却して反応熱を除去することによって、さらに効率的に除熱を行うことができるため、斯様な構成を採用するのがより好ましい。
流路22、流路32は、循環経路2と同様に、任意の適切な配管として構成される。配管を構成する材料は特に限定されないが、耐食性に優れる点からSUSが好ましい。
また、反応器21、反応器31に不均一系触媒を充填する際は、触媒の前後にガラスビーズ等を充填してもよい。
斯かる構成によって、反応原料であるエポキシドが液状又は溶液状の状態で、循環経路2、流路22、流路32を流れる液状混合流体に供給される。
また、制御弁16、26、36により、反応器1、21、31に供給されるエポキシドの供給量を各々制御することができる。
なお、制御弁16、26、36を配置する代わりに、各流路に個別にエポキシド供給手段を配置してもよい。この場合、各反応器に供給されるエポキシドの供給量は、個別のエポキシド供給手段により各々制御することができる。
流路22、32に熱交換手段24、34を設けることにより、前段の反応器で発生した反応熱を容易に除去することができ、次段の反応器内の温度を所望の範囲(実質的に反応温度)に容易に制御することができる。
熱交換手段24、34としては、熱交換手段4と同様に、当該手段を通過する液状混合流体の温度を下げて反応熱を除去できる限り、任意の熱交換器を使用できる。具体的には、多管円筒型熱交換器、二重管式熱交換器、プレート式熱交換器、エアクーラー、イリゲーションクーラー、コイル式熱交換器、渦巻き式熱交換器等が挙げられるが、循環液量が比較的に小流量であり且つ高圧力操作であるため、二重管式熱交換器、エアクーラー、イリゲーションクーラーが特に適切であり好ましい。また、これらの熱交換器の総括伝熱係数としては好ましくは約200kcal/(m2hrK)以上である。
混合手段20、30としては、スタティックミキサー等のインラインミキサーを用いるのが、装置が簡単であり好ましい。
このような順番で設けられていることによって、液状混合流体を効率的に除熱し、エポキシドと均一かつ効率的に混合して、次の反応器に供給することができる。
また、このような構成によって、各反応器の出口温度と入口温度との温度差を触媒劣化が起こらない範囲内で大きくすることができ、全ての反応器において高い反応速度で効率的に反応を行うことが可能となる。
また、多段断熱型反応器には各反応器をバイパスする流路を設けることが可能であり、これにより、生産量を適宜調整することが可能であり、更に、生産を継続しながら触媒の入れ替えが可能となる。
更にまた、各反応器間の流路を適宜変更することにより、反応器の接続順序を入れ替えることも可能であり、触媒の劣化状況に応じて最適化された順序で反応させることが可能である。
なお、各断熱性反応器に導入されるエポキシドの供給量、原料混合流体の二酸化炭素含有量、各断熱性反応器に充填される触媒量、各断熱性反応器へ循環される環状カーボネート/エポキシドの比(質量比)は、第1実施形態と同様である。
次に、本発明の環状カーボネートの製造方法について説明する。
本発明の環状カーボネートの製造方法は、上記第1の製造装置や第2の製造装置のような本発明の製造装置を用いて行うことが可能である。また、エポキシドと二酸化炭素とを含む原料混合流体を、不均一系触媒が充填された断熱型反応器に連続的に供給し、反応器出口(固定床多段反応器の場合は、最終段反応器出口)から流出した液状混合流体の少なくとも一部を反応器に戻る循環経路に循環させ、循環経路内で反応熱を除去し、循環流体にエポキシド及び二酸化炭素を連続的に供給し流路内で混合しながら行うものである。
なお、生産量当たりの発熱量は一定(例えば、エチレンオキサイドと二酸化炭素からのエチレンカーボネート合成の場合は、反応熱約100kJ/mol)であるため、断熱型反応器の入口温度と上記温度差はエポキシドと循環させる環状カーボネートとの流量比で調整することができる。
上記の循環を確立させる方法としては、具体的には、予め加熱した環状カーボネートを気液分離手段11に張り込み、これを昇圧手段12により、熱交換手段5、反応器1、循環経路2、熱交換手段4へと送液循環させる方法が挙げられる。また、前ロットの循環流体を気液分離手段11に貯留しておき、これを用いてもよい。いずれの場合も、熱交換手段5にて、反応器入口温度の調整を行うことが好ましい。
環状カーボネートに溶解しない余剰な二酸化炭素は、気液分離手段11にて分離される。
余剰の二酸化炭素は気液分離手段11上部から排気されるが、この余剰ガス及び圧力制御手段14により、気液分離手段11の圧力は反応器1の圧力(したがって、混合手段9の圧力)より低い圧力に制御される。気液分離手段11と反応器1との差圧は、好ましくは0.1MPa以上、より好ましくは0.3MPa以上、さらに好ましくは0.5MPa以上であり、好ましくは1.0MPa以下である。
反応器1の圧力より低い圧力下で余剰のガスを分離することにより、ガス化の起こりにくい環状カーボネート溶解二酸化炭素を反応器1へ供給することができ、反応器1内における偏流が防止される。
この際、固定床多段反応器に含まれる各反応器間を接続する流路のうち少なくとも1つの流路に液状又は溶液状のエポキシドを連続的に供給するエポキシド供給し、当該エポキシド供給工程により供給されたエポキシドと流路に流入した液状混合流体を流路内で混合するのが好ましい。さらに、各反応器間を接続する全ての流路において液状又は溶液状のエポキシドを連続的に供給し、各反応器間を接続する全ての接続流路内で混合して次段の反応器入口に導入するのがより好ましい。
また、固定床多段反応器に含まれる各反応器間を接続する流路のうち少なくとも1つの流路に流入した液状混合流体を間接熱交換により除熱するのが好ましく、各反応器間を接続する全ての流路において間接熱交換により冷却して反応熱を除去するのがより好ましい。
残部は、排出経路3から必要に応じて次工程(分離・精製工程)に送られる。排出経路3からの排出量は、系内の滞油量が一定になるように、制御弁15により調整される。
触媒の臭素及びリン修飾量の測定には、蛍光X線分析を用いた。分析条件は以下のとおりである。
装置:製品名「System3270」(理学電機工業社製)
測定条件:Rh管球、管電圧50kV、管電流50mV、真空雰囲気、検出器:SC、F-PC
触媒の熱重量の測定には、示差熱熱重量同時測定装置を用いた。分析条件は以下のとおりである。
装置:機器名「TG-DTA6200」(エスアイアイ・ナノテクノロジー社製)
試料量:14mg(乳鉢ですりつぶした試料をアルミニウムパンに量り取った)
測定範囲、昇温温度:室温(25℃)→5℃/分で昇温→50℃で3時間保持→0.5℃/分で昇温→250℃で3時間保持
雰囲気:窒素気流下50mL/分
反応液の組成分析には、ガスクロマトグラフィーを用いた。分析条件は以下のとおりである。
装置:製品名「GC-2010Plus」(島津製作所社製)
検出器:FID
INJ温度:150℃
DET温度:260℃
サンプル量:0.3μL
スプリット比:5
カラム:DB-624(60m、0.32mmID、1.8μm、Agilent社製)
カラム温度条件:70℃で3分間保持→5℃/分で昇温→120℃→10℃/分で昇温→250℃で5分間保持(計31分間)
ビーズ状シリカゲル(富士シリシア化学製CARiACT Q-10(平均細孔径10nm、粒子径1.2~2.4mm、比表面積300m2/g))40kgとキシレン100Lとを、200LのSUS製反応槽に仕込んだ。140℃還流下、2時間キシレン-水の共沸脱水を行い、シリカゲル中の水分を除去した。次いで、反応槽内を窒素置換した後、3-ブロモプロピルトリメトキシシラン4.4kgを滴下した。これをそのまま135℃で9時間加熱還流することにより、シラン化反応を行った。得られた反応物を反応槽から抜き出し、反応物中の触媒前駆体(ブロモプロピル化シリカゲル)をろ過により分離したのち、40Lのキシレンで洗浄を行った。ここで得られた触媒前駆体中の臭素修飾量は0.39mmol/gであった。
次いで、得られた触媒前駆体とキシレン100Lを反応槽に仕込み、反応槽内を窒素置換した後、トリ-n-ブチルホスフィン9.1kgを滴下した。これをそのまま還流下、24時間加熱することにより、4級ホスホニウム化反応を行った。
反応後、ろ過により反応物を分離し、40Lのアセトンで6回洗浄を行った。その後反応物を、窒素気流下、120℃で1晩減圧乾燥を行い、目的とするトリブチルホスホニウムブロミド表面修飾シリカゲル46kgを得た。触媒中の臭素修飾量は0.32mmol/gであり、リン修飾量は0.33mmol/gであった。
触媒合成例1にて得られた触媒の熱重量測定を実施した。結果を図3に示す。
図3に示されるように、146℃以上の温度から触媒の熱分解が観察され、分解物として1-ブロモブタンが検出された。この結果から、下記実施例における反応器上限温度を140℃に設定した。
攪拌子を入れた50mLのオートクレーブに、触媒合成例1にて得られた触媒を400mg仕込み、120℃で1時間減圧乾燥を行った。オートクレーブ内を窒素にて大気圧、室温に戻したのち、エチレンオキシド4mL(60mmol)を仕込んだ。次いで、二酸化炭素を1.5MPaGまで仮充填し、その後、オートクレーブ内を攪拌子により800rpmで撹拌しつつ100℃まで加熱し、二酸化炭素をさらに充填することにより、内圧を3.0~18.3MPaの範囲で調整し、1時間反応させた。反応終了後に冷却した後、残存する二酸化炭素を放出し、オートクレーブ内を脱圧した。得られた反応液をガスクロマトグラフにより分析し、エチレンカーボネートの収率を求めた。結果を図4に示す。
図4に示されるように、反応圧力とエチレンカーボネート収率の関係は、二酸化炭素の臨界圧力近傍をピークとした上に凸の関係であることが示された。この結果及び二酸化炭素のガス化抑制の観点から、下記実施例における反応圧力を8MPaに設定した。
図1に示される装置において、熱交換手段4、5として二重管式熱交換器を、原料等供給手段6、7、8及び昇圧手段12としてポンプを、混合手段9、10としてスタティックミキサーを、気液分離手段11として気液分離槽を、圧力制御手段13、14として背圧弁を、それぞれ備えた装置を用いて、エチレンカーボネートの製造を行った。
内径50mm、長さ100cm、容積2000mLの反応器1に、触媒合成例1で得た触媒を530g(1000mL)充填し、更に触媒の前後に粒子径4mmのガラスビーズを合計1560g(1000mL)充填した。
次いで、予め加熱し溶解されたエチレンカーボネート5.0kgを気液分離槽11に初期張りし、これをポンプ12により、熱交換器5、スタティックミキサー10、反応器1、循環経路2、熱交換器4、スタティックミキサー9へと2050g/hrの流量で送液循環させた。その際、熱交換器5にて、反応器入口温度を100℃に調整した。
続いて、反応器1の圧力を背圧弁13によって8.0MPaGに調整した。このようにして、スタティックミキサー9及び反応器1と気液分離槽11との圧力差を0.5MPaとした。また、気液分離後の液をポンプ12にて8.0MPaGまで昇圧し、反応器1に供給した。この操作により、エチレンカーボネートに完全溶解した、ガス化の起こりにくい二酸化炭素が反応器1に供給されるようにした。
なお、反応器入口1b条件(8MPa、100℃)における二酸化炭素のエチレンカーボネートへの飽和溶解度はおよそ12質量%であるところ、気液分離後の循環流体への二酸化炭素溶解度はおよそ11質量%であった。
また、気液分離槽11上部から排気されるガス中からエチレンオキシドは検出されなかったことから、以下の式によりエチレンオキシドの転化率を算出した。
転化率X={(供給エチレンオキシド流量)-(抜出エチレンオキシド流量)}/(供給エチレンオキシド流量)×100
抜き出されたエチレンカーボネート中のエチレンオキシドの濃度は0.29%であり、エチレンオキシドの転化率は、99.4%と算出された。
図1に示した実施形態において、以下の条件にて、反応器温度と、エチレンカーボネート循環量と、触媒量との関係をシミュレーションした。結果を表1に示す。
装置:図1に示される装置において、熱交換手段4、5として二重管式熱交換器を、原料等供給手段6、7、8及び昇圧手段12としてポンプを、混合手段9、10としてスタティックミキサーを、気液分離手段11として気液分離槽を、圧力制御手段13、14として背圧弁を、それぞれ備えた装置
エチレンカーボネート年間(8000時間)生産量:1000トン
エチレンオキシド供給量(ポンプ8):63kg/hr
2-ブロモエタノール供給量(ポンプ7):0.05kg/hr
二酸化炭素供給量(ポンプ6):63kg/hr
エチレンオキシド転化率:99%
反応器数:1基
反応器圧力:8MPa
断熱型反応器入口温度:60℃、70℃、80℃、90℃、100℃、110℃、120℃、130℃、及び135℃
断熱型反応器上限温度(断熱型反応器出口温度):140℃
ΔT:反応器出口1aと反応器入口1bとの温度差
EC/EO循環希釈比:反応器入口1bでのエチレンカーボネート流量をエチレンオキシド供給量(63kg/hr)で除したもの
図2に示した実施形態において、以下の条件にて、反応器温度と、エチレンカーボネート循環量と、触媒量との関係をシミュレーションした。結果を表1に示す。
装置:図2に示される装置において、熱交換手段4、5、24、34として二重管式熱交換器を、原料等供給手段6、7、8及び昇圧手段12としてポンプを、混合手段9、10、20、30としてスタティックミキサーを、気液分離手段11として気液分離槽を、圧力制御手段13、14として背圧弁を、それぞれ備えた装置
エチレンカーボネート年間(8000時間)生産量:1000トン
エチレンオキシド供給量(制御弁16):21kg/hr
(制御弁26):21kg/hr
(制御弁36):21kg/hr
2-ブロモエタノール供給量(ポンプ7):0.05kg/hr
二酸化炭素供給量(ポンプ6):64kg/hr
エチレンオキシド転化率:99%
反応器数:3基
反応器圧力:8MPa
断熱型反応器入口温度:110℃、120℃、130℃及び135℃
断熱型反応器上限温度(断熱型反応器出口温度):140℃
ΔT:反応器出口1aと反応器入口1bとの温度差
EC/EO循環希釈比:反応器入口1bでのエチレンカーボネート流量をエチレンオキシド供給量の総和(63kg/hr)で除したもの
反応器数を2つにした場合、すなわち図2に示す実施形態において、制御弁36、流路32、反応器31、熱交換手段34及び混合手段30を除いた実施形態での反応器シミュレーションを行った。
具体的には以下の条件にて、反応器温度と、エチレンカーボネート循環量と、触媒量との関係をシミュレーションした。結果を表1に示す。
装置:実施例2の装置において、制御弁36、流路32、反応器31、二重管式熱交換器34及びスタティックミキサー30を除いた装置
エチレンカーボネート年間(8000時間)生産量:1000トン
エチレンオキシド供給量(制御弁16):31.5kg/hr
(制御弁26):31.5kg/hr
2-ブロモエタノール供給量(ポンプ7):0.05kg/hr
二酸化炭素供給量(ポンプ6):64kg/hr
エチレンオキシド転化率:99%
反応器数:2基
反応器圧力:8MPa
断熱型反応器入口温度:90℃、100℃、110℃、120℃、130℃、及び135℃
断熱型反応器上限温度(断熱型反応器出口温度):140℃
ΔT:反応器出口1aと反応器入口1bとの温度差
EC/EO循環希釈比:反応器入口1bでのエチレンカーボネート流量をエチレンオキシド供給量の総和(63kg/hr)で除したもの
また、本発明においては、環状カーボネート生産量に対する触媒量が、反応器数によらずほぼ一定となるので、生産能力を増強する場合は、反応器、熱交換器、スタティックミキサーを順次増加させるだけでよく、経済的に優れた能力増強が可能である。したがって、設備廃棄の必要がなく、設備への二重投資が不要となる。
1a、21a、31a:反応器出口
1b、21b、31b:反応器入口
2:循環経路
3:排出経路
4、5、24、34:熱交換手段
6:二酸化炭素供給手段
7:添加剤供給手段
8:エポキシド供給手段
9、10、20、30:混合手段
11:気液分離手段
12:昇圧手段
13、14:圧力制御手段
15、16、26、36:制御弁
22、32:反応器間の流路
Claims (10)
- エポキシドと二酸化炭素とを反応させるための不均一系触媒が充填される断熱型の反応器と、
前記反応器の出口から流出した液状混合流体の少なくとも一部を前記反応器に戻す循環経路と、
当該循環経路内に液状又は超臨界状態の二酸化炭素を連続的に供給する二酸化炭素供給手段と、
前記循環経路内に液状又は溶液状のエポキシドを連続的に供給するエポキシド供給手段とを備え、
前記循環経路が、
循環流体を間接熱交換により除熱する熱交換手段と、
前記二酸化炭素供給手段により供給された二酸化酸素と前記循環流体とを経路内で混合する混合手段と、
当該混合手段により得られた二酸化炭素を含む循環流体を減圧し、気液分離処理する気液分離手段と、
気液分離処理後の循環流体を所定の圧力まで昇圧する昇圧手段と、
前記エポキシド供給手段により供給されたエポキシドと前記循環流体とを経路内で混合する混合手段とを具備することを特徴とする、
環状カーボネートの製造装置。 - 前記反応器が、2基以上の断熱型反応器が直列に接続された固定床多段反応器として構成されており、
前記循環経路が、最後段反応器の出口から流出した液状混合流体の少なくとも一部を第1段反応器に戻すようにして設けられている、
請求項1に記載の環状カーボネートの製造装置。 - 前記固定床多段反応器に含まれる各反応器間を接続する流路のうち少なくとも1つの流路に液状又は溶液状のエポキシドを連続的に供給するエポキシド供給手段と、
当該エポキシド供給手段により供給されたエポキシドと流路に流入した液状混合流体を流路内で混合する混合手段とを更に備える、
請求項2に記載の環状カーボネートの製造装置。 - 前記固定床多段反応器に含まれる各反応器間を接続する流路のうち少なくとも1つの流路が、流路に流入した液状混合流体を間接熱交換により除熱する熱交換手段を具備する、
請求項2又は3に記載の環状カーボネートの製造装置。 - 前記各混合手段がインラインミキサーである、
請求項1~4のいずれか1項に記載の環状カーボネートの製造装置。 - エポキシドと二酸化炭素とを含む原料混合流体を不均一系触媒が充填された断熱型反応器に連続的に供給し、前記反応器の出口から流出した液状混合流体の少なくとも一部を循環経路に導き前記反応器に戻す環状カーボネートの製造方法であって、
循環流体を間接熱交換により除熱する熱交換工程と、
前記循環経路内に液状又は超臨界状態の二酸化炭素を連続的に供給する二酸化炭素供給工程と、
前記二酸化炭素供給工程により供給された二酸化酸素と前記循環流体とを経路内で混合する混合工程と、
当該混合工程により得られた二酸化炭素を含む循環流体を減圧し、ガス化した余剰の二酸化炭素を気液分離処理する気液分離工程と、
気液分離後の循環流体を所定の圧力まで昇圧する昇圧工程と、
前記循環経路内に液状又は溶液状のエポキシドを連続的に供給するエポキシド供給工程と、
前記エポキシド供給工程により供給されたエポキシドと前記循環流体とを経路内で混合する混合工程を含むことを特徴とする、
環状カーボネートの製造方法。 - 前記反応器が、2基以上の断熱型反応器が直列に接続された固定床多段反応器として構成されており、
前記循環経路が、最後段反応器の出口から流出した液状混合流体の少なくとも一部を第1段反応器に戻すものである、
請求項6に記載の環状カーボネートの製造方法。 - 前記固定床多段反応器に含まれる各反応器間を接続する流路のうち少なくとも1つの流路に液状又は溶液状のエポキシドを連続的に供給するエポキシド供給工程と、
当該エポキシド供給工程により供給されたエポキシドと流路に流入した液状混合流体を流路内で混合する混合工程とを更に含む、
請求項7に記載の環状カーボネートの製造方法。 - 前記固定床多段反応器に含まれる各反応器間を接続する流路のうち少なくとも1つの流路に流入した液状混合流体を間接熱交換により除熱する熱交換工程を含む、
請求項7又は8に記載の環状カーボネートの製造方法。 - 前記各混合工程を、インラインミキサーを用いて行う、
請求項6~9のいずれか1項に記載の環状カーボネートの製造方法。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP15800528.0A EP3150588B1 (en) | 2014-05-30 | 2015-05-29 | Apparatus and method for producing cyclic carbonate |
CN201580026857.3A CN106414422B (zh) | 2014-05-30 | 2015-05-29 | 环状碳酸酯的制造装置及制造方法 |
US15/314,804 US10106520B2 (en) | 2014-05-30 | 2015-05-29 | Apparatus and method for producing cyclic carbonate |
ES15800528T ES2735400T3 (es) | 2014-05-30 | 2015-05-29 | Aparato y método para producir carbonato cíclico |
JP2016523568A JP6515097B2 (ja) | 2014-05-30 | 2015-05-29 | 環状カーボネートの製造装置及び製造方法 |
KR1020167030948A KR102440432B1 (ko) | 2014-05-30 | 2015-05-29 | 고리형 카보네이트의 제조 장치 및 제조 방법 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014-112219 | 2014-05-30 | ||
JP2014112219 | 2014-05-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015182732A1 true WO2015182732A1 (ja) | 2015-12-03 |
Family
ID=54699053
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/065492 WO2015182732A1 (ja) | 2014-05-30 | 2015-05-29 | 環状カーボネートの製造装置及び製造方法 |
Country Status (7)
Country | Link |
---|---|
US (1) | US10106520B2 (ja) |
EP (1) | EP3150588B1 (ja) |
JP (1) | JP6515097B2 (ja) |
KR (1) | KR102440432B1 (ja) |
CN (1) | CN106414422B (ja) |
ES (1) | ES2735400T3 (ja) |
WO (1) | WO2015182732A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114761390A (zh) * | 2019-11-15 | 2022-07-15 | 新绿色世界有限公司 | 连续制备环状碳酸酯的方法 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018154588A (ja) * | 2017-03-17 | 2018-10-04 | 東レ・ファインケミカル株式会社 | N−(シクロヘキシルチオ)フタルイミドの製造方法および製造装置 |
CN110028483A (zh) * | 2019-04-30 | 2019-07-19 | 大连理工大学 | 一种外循环喷雾式气液接触工艺制备环状碳酸酯的方法 |
CN110684005A (zh) * | 2019-10-31 | 2020-01-14 | 大连理工大学 | 一种制备环状碳酸酯的循环喷射式连续反应工艺 |
JPWO2020230491A1 (ja) * | 2019-05-16 | 2020-11-19 | ||
NL2024243B1 (en) * | 2019-11-15 | 2021-07-29 | New Green World B V | Process to continuously prepare a cyclic carbonate |
CN112058191A (zh) * | 2020-08-25 | 2020-12-11 | 南京延长反应技术研究院有限公司 | 一种环状碳酸酯的微界面制备系统及方法 |
JP2023549793A (ja) * | 2020-11-12 | 2023-11-29 | ニュー・グリーン・ワールド・ベー・フェー | 環状炭酸塩を調製する方法 |
CN114940670B (zh) * | 2022-06-14 | 2024-05-10 | 天津科技大学 | 一种生产锂电池高纯碳酸酯溶剂的工艺系统 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62117623A (ja) * | 1985-11-18 | 1987-05-29 | Inoue Seisakusho:Kk | インラインミキサ− |
JPH11335372A (ja) * | 1998-05-25 | 1999-12-07 | Agency Of Ind Science & Technol | カーボネート化合物の製造方法 |
WO2004108696A1 (ja) * | 2003-06-04 | 2004-12-16 | Asahi Kasei Chemicals Corporation | アルキレンカーボネートの製造方法 |
JP2008229505A (ja) * | 2007-03-20 | 2008-10-02 | Mitsubishi Chemicals Corp | 反応装置および芳香族ポリカーボネートの製造方法 |
WO2013130147A1 (en) * | 2012-02-28 | 2013-09-06 | Saudi Basic Industries Corporation | Process for preparing carbonate and diol products |
WO2015008854A1 (ja) * | 2013-07-19 | 2015-01-22 | 独立行政法人産業技術総合研究所 | 環状カーボネートの製造方法 |
WO2015008853A1 (ja) * | 2013-07-19 | 2015-01-22 | 丸善石油化学株式会社 | 環状カーボネートの連続的製造方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4314945A (en) * | 1977-12-22 | 1982-02-09 | Union Carbide Corporation | Alkylene carbonate process |
JPS6317072A (ja) | 1986-07-08 | 1988-01-25 | Sharp Corp | 熱転写プリンタにおける印字消去方法 |
JP4370777B2 (ja) * | 2002-12-19 | 2009-11-25 | 三菱化学株式会社 | アルキレンカーボネートの製造方法 |
US20080214386A1 (en) | 2004-03-01 | 2008-09-04 | Toshikazu Takahashi | Catalyst for Cyclic Carbonate Synthesis |
JP4930992B2 (ja) | 2004-03-04 | 2012-05-16 | 独立行政法人産業技術総合研究所 | 環状カーボネート製造用触媒 |
-
2015
- 2015-05-29 CN CN201580026857.3A patent/CN106414422B/zh active Active
- 2015-05-29 EP EP15800528.0A patent/EP3150588B1/en active Active
- 2015-05-29 WO PCT/JP2015/065492 patent/WO2015182732A1/ja active Application Filing
- 2015-05-29 ES ES15800528T patent/ES2735400T3/es active Active
- 2015-05-29 KR KR1020167030948A patent/KR102440432B1/ko active IP Right Grant
- 2015-05-29 US US15/314,804 patent/US10106520B2/en active Active
- 2015-05-29 JP JP2016523568A patent/JP6515097B2/ja active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62117623A (ja) * | 1985-11-18 | 1987-05-29 | Inoue Seisakusho:Kk | インラインミキサ− |
JPH11335372A (ja) * | 1998-05-25 | 1999-12-07 | Agency Of Ind Science & Technol | カーボネート化合物の製造方法 |
WO2004108696A1 (ja) * | 2003-06-04 | 2004-12-16 | Asahi Kasei Chemicals Corporation | アルキレンカーボネートの製造方法 |
JP2008229505A (ja) * | 2007-03-20 | 2008-10-02 | Mitsubishi Chemicals Corp | 反応装置および芳香族ポリカーボネートの製造方法 |
WO2013130147A1 (en) * | 2012-02-28 | 2013-09-06 | Saudi Basic Industries Corporation | Process for preparing carbonate and diol products |
WO2015008854A1 (ja) * | 2013-07-19 | 2015-01-22 | 独立行政法人産業技術総合研究所 | 環状カーボネートの製造方法 |
WO2015008853A1 (ja) * | 2013-07-19 | 2015-01-22 | 丸善石油化学株式会社 | 環状カーボネートの連続的製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3150588A4 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114761390A (zh) * | 2019-11-15 | 2022-07-15 | 新绿色世界有限公司 | 连续制备环状碳酸酯的方法 |
Also Published As
Publication number | Publication date |
---|---|
CN106414422B (zh) | 2019-01-08 |
EP3150588A1 (en) | 2017-04-05 |
US20170197931A1 (en) | 2017-07-13 |
KR20170012217A (ko) | 2017-02-02 |
US10106520B2 (en) | 2018-10-23 |
EP3150588B1 (en) | 2019-07-03 |
ES2735400T3 (es) | 2019-12-18 |
JP6515097B2 (ja) | 2019-05-15 |
EP3150588A4 (en) | 2018-01-17 |
KR102440432B1 (ko) | 2022-09-05 |
JPWO2015182732A1 (ja) | 2017-04-20 |
CN106414422A (zh) | 2017-02-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6515097B2 (ja) | 環状カーボネートの製造装置及び製造方法 | |
JP2019512585A (ja) | 高吸収性ポリマーを生成するためのシステムおよび方法 | |
AU2017304582B2 (en) | Oxidative dehydrogenation (ODH) of ethane | |
AU2017304583B2 (en) | Oxidative dehydrogenation (ODH) of ethane | |
JP3656030B2 (ja) | 第3級ブチルアルコールの製造方法 | |
TWI663158B (zh) | 環狀碳酸酯之製造裝置及製造方法 | |
JP2019501914A (ja) | ハロゲン化アルカンを調製するための改善されたプロセス | |
JPWO2018047773A1 (ja) | イソブチレンの分離精製方法およびイソブチレンの製造方法 | |
CN113105414A (zh) | 一种制备1,2-环氧戊烷的方法 | |
US20150336886A1 (en) | Method for phase transfer synthesis of organic peroxides | |
JP4673028B2 (ja) | エチレンカーボネートの精製方法 | |
KR20120115561A (ko) | 디메틸 에테르의 제조 방법 | |
JP5290937B2 (ja) | アルコールの製造方法 | |
WO2023243671A1 (ja) | アルキレンカーボネートの製造方法、及びアルキレンカーボネートの製造装置 | |
RU2472786C1 (ru) | Способ получения оксида пропилена | |
WO2023190038A1 (ja) | 第三級ブチルアルコールの製造方法 | |
JP2010077055A (ja) | イソプロパノールの製造方法 | |
KR20230063763A (ko) | 폴리아민계 불균일계 촉매를 이용한 알킬렌 카보네이트 제조 방법 및 장치 | |
JP2012519586A (ja) | 液相反応用の方法及び集成装置 | |
JP2012180242A (ja) | 塩素の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15800528 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016523568 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20167030948 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15314804 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2015800528 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2015800528 Country of ref document: EP |