WO2017159814A1 - アルカノールアミン類の製造方法 - Google Patents
アルカノールアミン類の製造方法 Download PDFInfo
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- WO2017159814A1 WO2017159814A1 PCT/JP2017/010762 JP2017010762W WO2017159814A1 WO 2017159814 A1 WO2017159814 A1 WO 2017159814A1 JP 2017010762 W JP2017010762 W JP 2017010762W WO 2017159814 A1 WO2017159814 A1 WO 2017159814A1
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- trialkanolamine
- dialkanolamine
- ammonia
- alkylene oxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/22—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of other functional groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/10—Separation; Purification; Stabilisation; Use of additives
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- 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
- Y02P20/10—Process efficiency
Definitions
- the present invention relates to a method for producing alkanolamines.
- water serves as a catalyst, and by changing the ratio of ethylene oxide to ammonia (EO / NH 3 molar ratio), monoethanolamine (MEA), diethanolamine (DEA), and triethanolamine (TEA) ) Production ratio can be changed.
- EO / NH 3 molar ratio monoethanolamine
- DEA diethanolamine
- TEA triethanolamine
- the DEA production ratio does not vary greatly from 30 to 35% by weight. There was a problem that it was difficult to change greatly.
- the present invention has been made in view of the above circumstances, and provides a method for producing ethanolamines having high purity, which can suppress the production ratio of dialkanolamine to be low (for example, less than 30% by weight).
- the purpose is to do.
- Another object of the present invention is to provide ethanolamine having a high purity capable of controlling the production ratio of dialkanolamine low (for example, less than 30% by weight) while appropriately controlling the production ratio of monoalkanolamine or trialkanolamine. It is to provide a manufacturing method of the kind.
- the present inventor has conducted intensive research to solve the above problems. As a result, in producing alkanolamines, the inventors found that the above-mentioned problems can be solved by recycling a specific proportion of dialkanolamine to the reaction, and completed the present invention.
- the above-mentioned objects are obtained by reacting alkylene oxide and ammonia to obtain a reaction product containing monoalkanolamine, dialkanolamine and trialkanolamine; separating dialkanolamine from the reaction product; Recycling at least a portion of the alkanolamine to a reaction of the alkylene oxide and ammonia, wherein in the recycling step, the dialkanolamine is converted to alkylene oxide (moles) relative to the total amount (moles) of ammonia and dialkanolamine. ) Can be achieved by the method for producing alkanolamines to be supplied so that the molar ratio is 0.08 or more and less than 0.26.
- an alkylene oxide and ammonia are reacted to obtain a reaction product containing a monoalkanolamine, a dialkanolamine and a trialkanolamine (step (1)); Separating the dialkanolamine from (reaction (2)); recycling at least a portion of the dialkanolamine to the reaction of alkylene oxide and ammonia (reaction (3)), wherein the recycling step ( In step (3)), the dialkanolamine is supplied so that the molar ratio of alkylene oxide (mole) to the total amount (mole) of ammonia and dialkanolamine is 0.08 or more and less than 0.26.
- the production ratio of dialkanolamine can be kept low, and the production ratio of monoalkanolamine or trialkanolamine can be controlled appropriately.
- the alkanolamine (especially trialkanolamine) obtained by the said method has high purity.
- a part of dialkanolamine separated (purified) in the purification step is not obtained as a product, but recycled to a reaction system of alkylene oxide and ammonia, that is, a part of dialkanolamine is recycled. It is characterized in that it is fed to the reactor together with alkylene oxide and ammonia (ammonia water in the case of the safe water method).
- alkylene oxide and ammonia ammonia water in the case of the safe water method.
- the production ratio of monoalkanolamine and trialkanolamine can be controlled within an appropriate range according to demand.
- dialkanolamine is recycled to the reaction system, alkylene oxide is excessively added to this dialkanolamine, or alkylene oxide is added to trialkanolamine formed during the reaction, thereby forming a by-product of trialkanolamine 1 alkylene oxide adduct.
- the amount increases. For this reason, the amount of impurities, particularly the trialkanolamine 1 alkylene oxide adduct, is mixed in the trialkanolamine, and the purity of trialkanolamine, which is one of the final products, tends to decrease.
- the content of the trialkanolamine 1 alkylene oxide adduct in the trialkanolamine obtained by the method of the present invention can be reduced (for example, to 0.6% by weight or less). Therefore, according to the method of the present invention, a highly pure trialkanolamine can be produced.
- the production ratio of dialkanolamine can be controlled low (for example, less than 30% by weight) while appropriately controlling the production ratio of monoalkanolamine or trialkanolamine. Further, the ethanolamines obtained (particularly trialkanolamine) have high purity.
- X to Y indicating a range includes X and Y, and means “X or more and Y or less”. Unless otherwise specified, measurements such as operation and physical properties are performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.
- step (1) an alkylene oxide and ammonia are reacted to obtain a reaction product containing a monoalkanolamine, a dialkanolamine and a trialkanolamine (step (1)); Separating the dialkanolamine from (step (2)); recycling at least a portion of the dialkanolamine to the reaction of alkylene oxide and ammonia (step (3)).
- step (3) the dialkanolamine has a molar ratio of alkylene oxide (mol) to the total amount (mol) of ammonia and dialkanolamine of 0.08 or more and less than 0.26. As you feed.
- the production ratio of monoalkanolamine and / or trialkanolamine can be increased and the production ratio of dialkanolamine can be kept low (particularly less than 30% by weight). Further, the content of the trialkanolamine 1 alkylene oxide adduct in the trialkanolamine can be reduced (for example, to 0.6% by weight or less).
- the “molar ratio of alkylene oxide (mole) to the total amount (mole) of ammonia and dialkanolamine” is also simply referred to as “alkylene oxide molar ratio”.
- the “molar ratio of ethylene oxide (mole) to the total amount (mole) of ammonia and diethanolamine” is also simply referred to as “ethylene oxide molar ratio” or [EO (mole) / (NH 3 + DEA (total mole))].
- MEA monoethanolamine
- DEA diethanolamine
- TEA triethanolamine
- EO ethylene oxide
- the alkanolamines only need to have at least one alkanol group, and include all primary, secondary, and tertiary alkanolamines.
- the other substituent bonded to the nitrogen atom includes an alkyl group (for example, linear or branched having 1 to 5 carbon atoms). Chain alkyl group), aryl group and the like.
- examples include amine, triethanolamine, triisopropanolamine, N-phenyldiethanolamine and the like.
- ethanolamines (monoethanolamine, diethanolamine, triethanolamine) are phospholipid-rich head structures and are found in biological membranes.
- Monoethanolamine is a partial structure such as diphenhydramine, phenyltroxamine or doxylamine, and is linked to phenylmethane in the common structure of antihistamines.
- Triethanolamine exhibits water solubility and chelating ability, and is useful as a raw material for chelating agents. For this reason, the method of the present invention is particularly suitable for the production of ethanolamines because of its high industrial utility.
- ethylene oxide and ammonia are reacted to obtain a reaction product containing monoethanolamine, diethanolamine and triethanolamine; diethanolamine is separated from the reaction product; at least of the diethanolamine
- a molar ratio of ethylene oxide (mole) to diethanolamine in a total amount (mole) of ammonia and diethanolamine is 0.08 or more.
- a method for producing ethanolamines to be supplied so as to be less than 0.26 is provided.
- the above reaction is not particularly limited, but a known method such as an aqueous solution method or a catalyst method can be used.
- the above-described method is an industrial production method of alkanolamine (particularly ethanolamine).
- the methods described in JP-A-2005-8536 and JP-A-2004-238290 are modified in the same manner or appropriately. Can be applied.
- the water-absorbing method alkylene oxide and aqueous ammonia are reacted.
- the catalytic method alkylene oxide and liquid ammonia are reacted in the presence of a zeolite catalyst.
- the alkylene oxide is not particularly limited and is selected according to the desired structure of the alkanolamine. Specific examples include ethylene oxide (ethylene oxide) and propylene oxide. Of these, ethylene oxide (ethylene oxide) is preferred.
- ammonia concentration of ammonia water used in the low water method is not particularly limited, but is preferably about 30 to 50% by weight in consideration of the reaction efficiency with alkylene oxide, production efficiency, and the like.
- the reaction is performed using ammonia water and alkylene oxide as raw materials in a liquid phase state using a reactor.
- the mixing ratio of alkylene oxide and ammonia is not particularly limited, but alkylene oxide is usually preferably in the range of 0.1 to 1.0 mole, and preferably 0.15 to 0.005 moles per mole of ammonia (NH 3 ). A range of 50 is more preferred.
- ammonia is used in excess of the theoretical amount of reaction with alkylene oxide, it is usually preferable to separate and recover unreacted ammonia from the reaction product and supply it again to the reactor.
- the alkanolamine obtained by reaction is a mixture containing a monoalkanolamine, a dialkanolamine, and a trialkanolamine.
- the reactor is a multi-tubular reactor, and the reaction liquid is usually allowed to flow up-flow. Furthermore, the reactor is preferably a raw material split feed reactor from the viewpoint of reaction efficiency.
- the reaction conditions are not particularly limited as long as the reaction between the alkylene oxide and ammonia proceeds.
- the reaction temperature is preferably from room temperature (25 ° C.) to about 150 ° C., more preferably from 50 to 135 ° C., and even more preferably from 80 to 120 ° C.
- the reaction pressure is preferably from ordinary pressure (standard atmospheric pressure (101 kPa)) to about 16 MPa, more preferably from 1 to 10 MPa, and even more preferably from 3 to 5 MPa.
- ammonia water is supplied from the ammonia water tank 3 to the raw material alkylene oxide tank (ethylene oxide tank in FIG. 1) 2.
- the alkylene oxide is sent to the reactor 4.
- the production ratio of the mono-, di-, and tri-alkanolamine obtained varies depending on the mixing ratio of ammonia and alkylene oxide to be used, and can be set as appropriate according to the purpose.
- the reaction liquid containing monoalkanolamine, dialkanolamine and trialkanolamine, and further ammonia and water is sent to the ammonia diffusion tower 5.
- water and ammonia are diffused from the top of the tower in the ammonia stripping tower 5 and are collected in the ammonia water tank 3 through a cooler (not shown).
- the ammonia water is diluted and used as a reaction raw material for the low water method. Reused.
- water and ammonia emission conditions in the ammonia diffusion tower are preferably distilled under pressure, but are not particularly limited as long as water and ammonia can be distilled.
- the removal temperature is preferably adjusted so that the temperature of the bottom liquid (column bottom liquid) of the ammonia diffusion tower exceeds 100 ° C. and is about 150 ° C. or less (preferably 120 to 145 ° C.).
- the removal time is usually preferably about 0.5 to 36 hours, more preferably 1 to 6 hours.
- the removal pressure is preferably about 0.1 to 3 MPa, more preferably 0.15 to 1 MPa. Under such conditions, water and ammonia can be distilled off efficiently.
- the ammonia that has come out from the top of the ammonia diffusion tower is cooled by a cooler (the refrigerant is usually cooling water) and collected in an ammonia water tank.
- a plate tower, a packed tower, a wet wall tower, and a spray tower can be used for distillation. The distillation may be performed continuously or batchwise.
- the water-safe method and the catalyst method may be applied singly or in combination (that is, the alkanolamines obtained by the safe-water method and the alkanolamines obtained by the catalytic method may be combined.
- the reaction product may be obtained by mixing).
- the method of the present invention is particularly effective in the case of the low water method. is there.
- the bottom liquid (column bottom liquid) of the ammonia stripping tower 5 is water and alkanolamines (monoalkanolamine, dialkanolamine). , Trialkanolamine, etc.).
- alkanolamines monoalkanolamine, dialkanolamine, Trialkanolamine, etc.
- this invention is not limited to the following form.
- the bottom liquid (column bottom liquid) of the ammonia diffusion tower 5 is put into the dehydration tower 6.
- the bottom liquid (column bottom liquid) of a dehydration tower contains alkanolamines (monoalkanolamine, dialkanolamine, trialkanolamine, etc.).
- the water removal conditions in the dehydration tower are not particularly limited as long as water can be removed, but distillation under reduced pressure is preferable.
- the removal temperature is preferably adjusted such that the temperature of the bottom liquid (column bottom liquid) of the dehydration tower is about 55 to 180 ° C.
- the removal time is usually preferably about 0.5 to 36 hours, more preferably 1 to 6 hours.
- the removal pressure is preferably about 1 to 200 hPa, more preferably 50 to 150 hPa. Under such conditions, water can be distilled off efficiently.
- a plate tower, a packed tower, a wet wall tower, and a spray tower can be used for distillation. The distillation may be performed continuously or batchwise.
- the bottom liquid (column bottom liquid) of the dehydration tower 6 is charged into a monoalkanolamine rectification tower (MEA rectification tower in FIG. 1) 7.
- the monoalkanolamine rectifying column 7 the monoalkanolamine is rectified to obtain purified monoalkanolamine from the top of the column.
- the bottom liquid (column bottom liquid) of the monoalkanolamine rectification column contains dialkanolamine, trialkanolamine, and the like.
- the rectification conditions of the monoalkanolamine in the monoalkanolamine rectification column are not particularly limited as long as the monoalkanolamine can be rectified, but distillation under reduced pressure is preferable.
- the rectification temperature is preferably adjusted so that the temperature of the bottom liquid (column bottom liquid) of the monoalkanolamine rectification column is about 55 to 180 ° C. (preferably 100 to 160 ° C.).
- the removal time is usually preferably about 0.5 to 36 hours, more preferably 2 to 6 hours.
- the removal pressure (reduced pressure condition) is preferably about 1 to 200 hPa, more preferably 5 to 50 hPa, and even more preferably 10 to 30 hPa. Under such conditions, monoalkanolamine (particularly MEA) can be rectified efficiently.
- a plate tower, a packed tower, a wet wall tower, and a spray tower can be used for distillation. The distillation may be performed continuously or batchwise.
- the bottom liquid (column bottom liquid) of the monoalkanolamine rectification tower 7 is charged into a dialkanolamine rectification tower (DEA rectification tower in FIG. 1) 8.
- the dialkanolamine rectifying column 8 the dialkanolamine is rectified to obtain purified dialkanolamine from the top of the column.
- the bottom liquid (column bottom liquid) of the dialkanolamine rectification column contains trialkanolamine and the like.
- the rectifying conditions for dialkanolamine in the dialkanolamine rectifying column are not particularly limited as long as dialkanolamine can be rectified, but distillation under reduced pressure is preferable.
- the rectification temperature is preferably adjusted so that the temperature of the bottom liquid (column bottom liquid) of the dialkanolamine rectification column is about 55 to 180 ° C. (preferably 120 to 180 ° C.).
- the removal time is usually preferably about 0.5 to 36 hours, more preferably 1 to 6 hours.
- the removal pressure (reduced pressure condition) is preferably about 1 to 200 hPa, more preferably 3 to 50 hPa. Under such conditions, dialkanolamine (particularly DEA) can be rectified efficiently.
- a plate tower, a packed tower, a wet wall tower, and a spray tower can be used for distillation. The distillation may be performed continuously or batchwise.
- the embodiment in this step is not particularly limited, and may be a form in which at least a part of the dialkanolamine separated in the step (2) is directly circulated and supplied to the reactor in the step (1).
- it may be separately supplied without being circulated directly to the reactor of the above step (1). That is, for example, in FIG. 1, a part of DEA distilled from the DEA rectification column 8 is directly circulated and supplied to the reactor 4 through the DEA recycling line 11, but this is directly circulated to the reactor 4. It may be stored in a tank without being supplied, taken out from the tank and supplied to the reactor 4.
- this step is preferably in a form in which at least a part of the dialkanolamine separated in the step (2) is directly circulated and supplied to the reactor in the step (1).
- the dialkanolamine has a molar ratio (alkylene oxide molar ratio) of alkylene oxide (mol) to the total amount (mol) of ammonia and dialkanolamine of 0.08 or more and 0.26.
- Supply (recycle) to the reactor so that it is less.
- the production ratio of trialkanolamine can be further increased. Further, the content of the trialkanolamine 1 alkylene oxide adduct in the trialkanolamine can be reduced (for example, to 0.6% by weight or less). For this reason, the trialkanolamine obtained has high purity.
- the alkylene oxide molar ratio is less than 0.08, the supply (recycle) amount of dialkanolamine to the reaction is not sufficient, so the production rate of dialkanolamine is not effectively reduced, and monoalkanolamine And / or improvement in the production ratio of trialkanolamine is not observed.
- the alkylene oxide molar ratio is 0.26 or more, the production ratio of dialkanolamine is low, but the amount of impurities (particularly trialkanolamine 1 alkylene oxide adduct) in trialkanolamine as the final product. Increases and the purity of trialkanolamine decreases (for example, see Comparative Examples 1 and 2 below). For this reason, it is necessary to separately perform a trialkanolamine purification step.
- the alkylene oxide is ethylene oxide (EO)
- TEA-1EO triethanolamine 1 alkylene oxide adduct
- the molar ratio of alkylene oxide (mole) to the total amount (mole) of ammonia and dialkanolamine (moleic oxide molar ratio) is preferably 0.10 to 0.25, more preferably 0.15 to 0.23, especially It is preferably 0.18 to 0.22.
- dialkanolamine When dialkanolamine is not recycled as in the prior art, monoalkanolamine is produced on the reactor inlet side by the reaction of alkylene oxide and ammonia, and this monoalkanolamine and alkylene oxide react to produce dialkanolamine.
- the dialkanolamine and alkylene oxide further react to produce trialkanolamine, the trialkanolamine is produced at a large proportion on the outlet side of the reactor, and this reacts with alkylene oxide to give trialkanolamine 1 alkylene. It is speculated that an oxide adduct (for example, TEA-1EO described above) is by-produced.
- an oxide adduct for example, TEA-1EO described above
- the dialkanolamine recycled at the reactor inlet side reacts with the alkylene oxide to produce a trialkanolamine. Since the residence time of the alkanolamine in the reactor becomes longer and the reaction between the trialkanolamine and the alkylene oxide tends to occur, the amount of the trialkanolamine 1 alkylene oxide adduct produced is smaller than when the dialkanolamine is not recycled. Will increase. However, the present inventors appropriately control the supply amount (recycle amount) of dialkanolamine with respect to ammonia in the reactor, thereby mixing the amount of trialkanolamine 1 alkylene oxide adduct in trialkanolamine. It was found that can be further reduced.
- the ratio (weight ratio) of dialkanolamine to ammonia is preferably 0.05 or more and less than 0.18, more preferably 0.06 to 0.17, and 0.07 to Particularly preferred is 0.16. That is, in a preferred embodiment of the present invention, in the recycling step (step (3)), the dialkanolamine is supplied at a ratio (weight ratio) of dialkanolamine to ammonia of 0.05 or more and less than 0.18. .
- the amount of impurities in trialkanolamine which is one of the final products, especially the amount of trialkanolamine 1 alkylene oxide adduct added is further increased.
- the purity of trialkanolamine can be further improved.
- the production ratio of a monoalkanolamine and a trialkanolamine can be controlled to a more suitable range according to a demand, suppressing the production ratio of dialkanolamine further low.
- alkanolamines can be produced, but trialkanolamine may be further purified.
- the method of the invention further comprises the step of purifying the trialkanolamine.
- the purification method of trialkanolamine is not particularly limited, and a known method can be applied in the same manner or appropriately modified. Although the preferable form of the purification method of the trialkanolamine of this invention is demonstrated below, this invention is not limited to the following form.
- the bottom liquid (column bottom liquid) of dialkanolamine rectifying column 8 obtained above contains trialkanolamine and impurities (for example, trialkanolamine 1 alkylene oxide adduct, deuterated component).
- the bottom liquid of the dialkanolamine rectifying column 8 is charged into a trialkanolamine distillation column (TEA distillation column in FIG. 1) 9.
- TAA distillation column in FIG. 1 a trialkanolamine distillation column
- high boiling point components are removed.
- the distillation conditions in the trialkanolamine distillation column are not particularly limited as long as the impurities can be removed, but distillation under reduced pressure is preferable.
- the distillation temperature is adjusted so that the temperature of the bottom liquid (column bottom liquid) of the trialkanolamine distillation column is about 55 to 180 ° C. (preferably 130 to 180 ° C., more preferably 130 to 175 ° C.). It is preferable.
- the removal time is usually preferably about 0.5 to 36 hours, more preferably 6 to 12 hours.
- the removal pressure (reduced pressure condition) is preferably about 1 to 200 hPa, more preferably 1 to 5 hPa. Under such conditions, the impurities can be efficiently removed (trialkanolamine, particularly TEA can be rectified efficiently).
- a plate tower, a packed tower, a wet wall tower, and a spray tower can be used for distillation. The distillation may be performed continuously or batchwise.
- the bottom liquid (column bottom liquid) of the trialkanolamine distillation tower 9 obtained above is charged into a trialkanolamine rectification tower (TEA rectification tower in FIG. 1) 10 and from the top of the tower. Purified trialkanolamine is obtained.
- the trialkanolamine rectification tower 10 rectifies trialkanolamine. According to a preferred embodiment, a part (for example, about 95%) of the bottom liquid (column bottom liquid) of the trialkanolamine distillation tower 9 is distilled from the top of the trialkanolamine rectification tower 10 (the rest is the rest).
- the method of the present invention further comprises separating trialkanolamine from the reaction product, wherein the trialkanolamine 1 alkylene oxide adduct is based on said trialkanolamine isolate. It is contained in an amount of 0.6% by weight or less.
- the separation conditions may be such that the content of the trialkanolamine 1 alkylene oxide adduct in the trialkanolamine is 0.6% by weight or less, but the trialkanolamine in the trialkanolamine The conditions are such that the content of 1 alkylene oxide adduct is preferably 0.58% by weight or less, particularly preferably 0.50% by weight or less.
- a trialkanolamine with high purity can be obtained from the top of the trialkanolamine rectification column 10.
- the rectifying conditions of the trialkanolamine in the trialkanolamine rectification column are not particularly limited as long as the trialkanolamine having a desired purity can be rectified, but distillation under reduced pressure is preferable.
- the temperature of the bottom liquid (column bottom liquid) of the trialkanolamine rectification column is about 55 to 180 ° C. (preferably 130 to 180 ° C., more preferably 130 to 175 ° C.). It is preferable to adjust.
- the removal time is usually preferably about 0.5 to 36 hours, more preferably 12 to 24 hours.
- the removal pressure (reduced pressure condition) is preferably about 1 to 200 hPa, more preferably 1 to 5 hPa. Under such conditions, the trialkanolamine (particularly TEA) can be rectified more efficiently (so that the content of the trialkanolamine 1 alkylene oxide adduct in the trialkanolamine is as described above).
- a plate tower, a packed tower, a wet wall tower, and a spray tower can be used for distillation. The distillation may be performed continuously or batchwise.
- Alkanolamines are produced as described above.
- the production ratio of dialkanolamine is low, and accordingly, the production ratio of monoalkanolamine and trialkanolamine is high.
- the production ratio of dialkanolamine in the alkanolamines is preferably lower than the production ratio in general industrial production (for example, 30 to 35% by weight in DEA). Accordingly, in a preferred form of the invention, the dialkanolamine production ratio is less than 30% by weight.
- the production ratio of dialkanolamine in the alkanolamines is more preferably 29% by weight or less, particularly preferably 27% by weight or less.
- the lower limit of the dialkanolamine production ratio in the alkanolamines is not particularly limited, but is usually 10% by weight or more, preferably 15% by weight or more.
- the production ratio of monoalkanolamine and trialkanolamine in alkanolamines can be appropriately adjusted according to demand.
- the production ratio of monoalkanolamine in alkanolamines is preferably 35 to 70% by weight, more preferably 45 to 60% by weight.
- the production ratio of trialkanolamine in the alkanolamines is preferably 10 to 45% by weight, more preferably 20 to 35% by weight.
- the production ratio of each alkanolamine in alkanolamines is measured according to the method described in the following Example.
- the content of the trialkanolamine 1 alkylene oxide adduct in the trialkanolamine can be reduced.
- the content of the trialkanolamine 1 alkylene oxide adduct in the trialkanolamine is preferably 0.6% by weight or less, more preferably 0.58% by weight or less, and particularly preferably 0.50% by weight. It is as follows.
- the minimum of content of trialkanolamine 1 alkylene oxide adduct in trialkanolamine is so preferable that it is low, it is 0.
- content of trialkanolamine 1 alkylene oxide adduct in trialkanolamine is measured according to the method as described in the following Example.
- Example 1 According to the flow shown in FIG. 1 (ethanolamine production plant), ethanolamines were produced by the water-absorbing method.
- ethylene oxide (EO) and 38 wt% ammonia water are respectively supplied from the ethylene oxide tank 2 and the ammonia water tank 3 to a molar ratio of ammonia to ethylene oxide (NH 3 / EO (molar ratio)).
- the multi-tubular reactor 4 was continuously charged so as to be 0.20, and the first reaction was performed under the conditions of a reaction temperature of 80 to 110 ° C. and a reaction pressure of 3.7 MPa, and monoethanolamine (MEA), diethanolamine ( A first reaction solution containing DEA) and triethanolamine (TEA) was obtained.
- MEA monoethanolamine
- MEA monoethanolamine
- diethanolamine A first reaction solution containing DEA
- TEA triethanolamine
- the first reaction liquid obtained as described above is first fed to an ammonia stripping tower (removal pressure 0.2 MPa, bottom temperature 140 ° C.) 5 and continuously distilled for 1 hour. Unreacted ammonia and water are removed from the top of the tower. Removed. The bottom liquid of the ammonia diffusion tower 5 was fed to a dehydration tower (removal pressure 150 hPa, bottom temperature 145 ° C.) 6 and continuously distilled for 1 hour to distill the remaining water from the top of the tower.
- the bottom liquid of the dehydration tower 6 is continuously distilled for 2 hours in the MEA rectification tower (removal pressure 12 hPa, bottom temperature 145 ° C.) 7 to distill the MEA, and the bottom liquid of the MEA rectification tower 7 is further subjected to DEA rectification.
- DEA was distilled by continuous distillation for 1 hour in a tower (removal pressure: 4 hPa, bottom temperature: 170 ° C.) 8 to obtain a raw material TEA as a bottom liquid.
- the bottom liquid (raw material TEA) obtained here was fed to the TEA distillation column 9.
- a portion of the DEA distilled in this way was divided into a molar ratio of EO to the total amount of ammonia and DEA [EO (mol) / (NH 3 + DEA (total mole))] of 0.21, and DEA to ammonia. in proportions such as supply amount ratio (weight ratio) (DEA / NH 3) becomes 0.076 in, to the reactor 4 is supplied (recycled) through DEA recycle line 11, the reaction temperature 80 ⁇ 110 ° C., a reaction pressure The second reaction was performed under the condition of 3.7 MPa.
- the second reaction liquid obtained above was fed to an ammonia stripping tower (removal pressure 0.2 MPa, bottom temperature 140 ° C.) 5 and continuously distilled for 1 hour to remove unreacted ammonia and water from the top of the tower. It was.
- the bottom liquid of the ammonia stripping tower 5 is fed to a dehydration tower (removal pressure 150 hPa, bottom temperature 145 ° C.) 6 and continuously distilled for 1 hour to distill the remaining water from the top of the tower.
- a mixture of DEA and TEA) was obtained.
- this bottom liquid is fed to the MEA rectification tower (removal pressure 12 hPa, bottom temperature 145 ° C.) 7 and continuously distilled for 2 hours to distill the MEA from the top of the tower, and the bottom liquid (mixed liquid of DEA and TEA) )
- This bottom liquid was fed to a DEA rectification tower (removal pressure 4 hPa, bottom temperature 170 ° C.) 8 and continuously distilled for 1 hour to distill DEA from the top of the tower to obtain a bottom liquid (raw material TEA).
- the bottom liquid (raw material TEA) obtained here was fed to the TEA distillation column 9.
- a part of the DEA obtained above was supplied (recycled) to the reactor 4 under the same conditions as described above.
- the bottom liquid (raw material TEA) fed to the TEA distillation tower 9 (removal pressure 4 hPa, bottom temperature 175 ° C.) 9 is continuously distilled for 12 hours to remove high-boiling components from the bottom, and the crude TEA is distilled from the top of the tower. I made it come out.
- This crude TEA was fed to a TEA rectification column (removal pressure 4 hPa, bottom temperature 175 ° C.) 10 and distilled for 24 hours to distill purified TEA from the top of the column. In the batch distillation, about 95% of the charged amount of the crude TEA was distilled from the top of the TEA rectification column 10 and a part of the fraction from the top was returned to the DEA rectification column 8.
- MEA distilled above (“MEA” in FIG. 1), DEA (DEA after being supplied to the reactor 4; “DEA” in FIG. 1) and TEA (“purified TEA” in FIG. 1)
- Quantitative analysis was performed by the following method, and the ratio of each ethanolamine (production ratio; weight ratio) was calculated.
- the ratio (production ratio) of ethanolamine obtained was MEA 50% by weight, DEA 27% by weight, and TEA 23% by weight.
- the content (% by weight) of triethanolamine 1EO adduct (TEA-1EO) in the purified TEA distilled as described above was 0.46% by weight as measured by the following method.
- Example 2 Comparative Examples 1 to 3
- the molar ratio of EO to the total amount of ammonia and DEA [EO (mol) / (NH 3 + DEA (total mol))]]
- the supply amount ratio of DEA to ammonia weight ratio
- Example 3 Comparative Examples 1 to 3
- a part of DEA was supplied (recycled) to the reactor 4 through the DEA recycling line 11 so that the ratios shown in Table 1 below were obtained.
- Example 1 The MEA, DEA, and TEA thus distilled were subjected to quantitative analysis in the same manner as in Example 1, and the ratio of each ethanolamine (production ratio; weight ratio) was calculated. Further, the content (wt%) of triethanolamine 1EO adduct (TEA-1EO) in the distilled TEA was measured in the same manner as in Example 1. The results are shown in Table 1 below.
- the molar ratio of EO to the total amount of ammonia and DEA is “EO / (NH 3 + DEA) (molar ratio)”, and the supply amount ratio (weight ratio) of DEA to ammonia is “DEA”.
- / NH 3 (weight ratio) ”and the content of triethanolamine 1EO adduct (TEA-1EO) in TEA are shown as“ TEA-1EO in TEA (% by weight) ”, respectively.
- the production ratio of diethanolamine (DEA) can be lowered and the production ratio of monoethanolamine (MEA) and triethanolamine (TEA) can be increased by the method of the present invention. Further, according to the method of the present invention, the content of triethanolamine 1 ethylene oxide adduct (TEA-1EO), which is an impurity of triethanolamine (TEA), which is the final product, can be reduced.
- DEA diethanolamine
- MEA monoethanolamine
- TEA triethanolamine
- TEA-1EO triethanolamine 1 ethylene oxide adduct
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Abstract
Description
本発明のアルカノールアミン類の製造方法は、アルキレンオキシドとアンモニアとを反応させて、モノアルカノールアミン、ジアルカノールアミンおよびトリアルカノールアミンを含む反応生成物を得(工程(1));前記反応生成物からジアルカノールアミンを分離し(工程(2));前記ジアルカノールアミンの少なくとも一部を、アルキレンオキシドとアンモニアとの反応にリサイクルする(工程(3))、ことを有する。ここで、上記リサイクル工程(工程(3))において、ジアルカノールアミンを、アンモニアおよびジアルカノールアミンの合計量(モル)に対するアルキレンオキシド(モル)のモル比が0.08以上0.26未満となるように、供給する。当該方法により、モノアルカノールアミンおよび/またはトリアルカノールアミンの生産比率を上げ、ジアルカノールアミンの生産比率を低く(特に30重量%未満)抑えることができる。また、トリアルカノールアミン中のトリアルカノールアミン1アルキレンオキシド付加物の含有量を(例えば、0.6重量%以下にまで)低減できる。
本工程では、アルキレンオキシドとアンモニアとを反応させて、モノアルカノールアミン、ジアルカノールアミンおよびトリアルカノールアミンを含む反応生成物を得る。例えば、アルキレンオキシドがエチレンオキシド(EO)である場合には、下記反応が起こる。
本工程では、上記工程(1)で得られた反応生成物からジアルカノールアミンを分離する。
本工程では、上記工程(2)で分離したジアルカノールアミンの少なくとも一部を、アルキレンオキシドとアンモニアとの反応にリサイクルする。本工程の実施形態は特に制限されず、上記工程(2)で分離したジアルカノールアミンの少なくとも一部を、上記工程(1)の反応器に直接的に循環供給する形態であってもよいし、上記工程(1)の反応器に直接的に循環させずに別途供給する形態であってもよい。すなわち、たとえば図1では、DEA精留塔8から留出したDEAの一部についてDEAリサイクルライン11を通じて反応器4に直接的に循環供給しているが、これを反応器4へ直接的に循環供給せずにタンクに貯留し、当該タンクから取り出して反応器4に供給してもよい。ただし、本工程は、図1に示すように、上記工程(2)で分離したジアルカノールアミンの少なくとも一部を上記工程(1)の反応器に直接的に循環供給する形態であることが好ましい。
図1に示されるフロー(エタノールアミン製造プラント)に従って、エタノールアミン類を安水法で製造した。
各エタノールアミン(MEA、DEA、TEA)の定量分析およびTEA-1EOの含有量の測定は、微極性キャピラリーカラム(SPELCO製 PTA-5)を取付けた水素炎イオン化検出器を備えたガスクロマトグラフ((株)島津製作所製、GC-2010)で、内部標準法を用いて分析する。
実施例1において、アンモニアおよびDEAとの合計量に対するEOのモル比[EO(モル)/(NH3+DEA(合計モル))]、ならびにアンモニアに対するDEAの供給量比(重量比)(DEA/NH3)がそれぞれ下記表1に示される割合になるように、DEAの一部をDEAリサイクルライン11を通じて反応器4に供給(リサイクル)した以外は、実施例1と同様の操作を行った。
2…エチレンオキシドタンク、
3…アンモニア水タンク、
4…多管式反応器、
5…アンモニア放散塔、
6…脱水塔、
7…MEA精留塔、
8…DEA精留塔、
9…TEA蒸留塔、
10…TEA精留塔
11…DEAリサイクルライン。
Claims (4)
- アルキレンオキシドとアンモニアとを反応させて、モノアルカノールアミン、ジアルカノールアミンおよびトリアルカノールアミンを含む反応生成物を得;前記反応生成物からジアルカノールアミンを分離し;前記ジアルカノールアミンの少なくとも一部を、アルキレンオキシドとアンモニアとの反応にリサイクルする、ことを有し、
前記リサイクル工程において、ジアルカノールアミンを、アンモニアおよびジアルカノールアミンの合計量(モル)に対するアルキレンオキシド(モル)のモル比が0.08以上0.26未満となるように、供給する、アルカノールアミン類の製造方法。 - 前記リサイクル工程において、ジアルカノールアミンを、前記アンモニアに対する前記ジアルカノールアミンの割合(重量比)が、0.05以上0.18未満の割合で供給する、請求項1に記載の方法。
- 前記反応生成物からトリアルカノールアミンを分離することをさらに有し、トリアルカノールアミン1アルキレンオキシド付加物が前記トリアルカノールアミン分離物に対して0.6重量%以下の量で含まれる、請求項1または2に記載の方法。
- 前記ジアルカノールアミンの生産比率が30重量%未満である、請求項1~3のいずれか1項に記載の方法。
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EP17766809.2A EP3431463B1 (en) | 2016-03-18 | 2017-03-16 | Method for producing alkanolamines |
CN201780011689.XA CN108698979B (zh) | 2016-03-18 | 2017-03-16 | 烷醇胺类的制造方法 |
US16/075,930 US10538483B2 (en) | 2016-03-18 | 2017-03-16 | Process for producing alkanolamine |
MYPI2018702537A MY190173A (en) | 2016-03-18 | 2017-03-16 | Process for producing alkanolamine |
JP2018506020A JP6620219B2 (ja) | 2016-03-18 | 2017-03-16 | アルカノールアミン類の製造方法 |
SA518392381A SA518392381B1 (ar) | 2016-03-18 | 2018-09-10 | عملية لإنتاج ألكانول أمين |
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