METHODS AND SYSTEMS FOR THE TREATMENT OF ETHYLENE OXIDE

专利摘要:
methods for treating a stream of ethylene oxide suitable for use in carbonylation reactions are disclosed. this treatment uses an inorganic solid to remove water from the ethylene oxide stream. systems for carrying out the methods described herein are also disclosed.
公开号:BR112019014870A2
申请号:R112019014870-1
申请日:2018-01-18
公开日:2020-02-27
发明作者:A. Pokrovski Konstantin；B. Ruhl John；Tseitlin Alexander；Sherry Kyle
申请人:Novomer, Inc.；
IPC主号:

专利说明:

METHODS AND SYSTEMS FOR THE TREATMENT OF ETHYLENE OXIDE CROSS REFERENCE TO RELATED APPLICATIONS [001] This application claims priority to US Provisional Patent Application No. 62 / 448,337, filed on January 19, 2017, which is incorporated here by reference in its entirety.
FIELD [002] The present description generally refers to the treatment of ethylene oxide, and more specifically to methods and systems for the treatment of ethylene oxide for use in carbonylation reactions.
BACKGROUND [003] Ethylene oxide can be combined with carbon monoxide, in the presence of a carbonylation catalyst, to form beta-propiolactone or succinic anhydride. These products can be converted to C3 and C4 commodity chemicals, such as glacial acrylic acid, tetrahydrofuran (THF) and 1,4-butanediol. Access to these products depends, in part, on ethylene oxide carbonylation on a commercial scale. Several challenges are known in the art regarding the handling of ethylene oxide on a commercial scale. Thus, what is desired in the art are methods of treating ethylene oxide suitable for use in carbonylation reactions.
BRIEF SUMMARY [004] Here are provided methods and systems that involve the treatment of an ethylene oxide feed suitable for use in carbonylation reactions. In some ways, a method of treating ethylene oxide is provided, which includes:
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2/30 wet a water-removing solid with organic solvent, or ethylene oxide, or a combination thereof; and continuously contacting the wet water-removing solid with an ethylene oxide feed to produce a treated ethylene oxide stream, wherein the ethylene oxide feed includes ethylene oxide and has an initial water content, the current of treated ethylene oxide includes ethylene oxide and has a water content, and the water content of the treated ethylene oxide stream is lower than the initial water content; and contact of the wet water removal solid with the ethylene oxide feed produces heat, where the heat produced is less than that produced by contacting a non-wet water removal solid with an ethylene oxide feed.
[005] In some ways, a method of continuously supplying ethylene oxide to a carbonylation zone is provided, which includes:
wetting an inorganic water-removing solid with organic solvent, ethylene oxide or a combination thereof;
continuously contacting the wet inorganic water-removing solid with an ethylene oxide feed to produce a treated ethylene oxide stream;
feeding the treated ethylene oxide stream to a carbonylation zone; and contact the stream of ethylene oxide treated with carbon monoxide, in the presence of a catalyst of
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3/30 carbonylation, in the carbonylation zone, where the ethylene oxide feed has an initial water content, the treated ethylene oxide stream has a water content, and the water content of the treated ethylene oxide stream it is lower than the initial water content; and the contact produces heat, where the heat produced is less than that produced when contacting an inorganic non-wetting water solid with an ethylene oxide feed.
[006] In some variations, contacting the stream of ethylene oxide treated with carbon monoxide in the presence of a carbonylation catalyst in the carbonylation zone produces a carbonylation product that may include betapropiolactone, succinic anhydride or a mixture thereof.
[007] In yet another aspect, a system for the treatment of ethylene oxide is provided here, which includes: an ethylene oxide source configured to provide an ethylene oxide feed; and a water removal unit comprising an inlet configured to receive the ethylene oxide feed, an outlet configured to produce a treated ethylene oxide stream, and a wet water removal solid, in which the water removal unit it is configured to contact the ethylene oxide feed with the wet water removal solid;
the wet water removal solid is wetted with organic solvent, ethylene oxide or a mixture thereof;
the ethylene oxide feed comprises oxide
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4/30 ethylene and has an initial water content, the treated ethylene oxide stream comprises ethylene oxide and has a water content, and the water content of the treated ethylene oxide stream is lower than the content of initial water; and the contact produces heat, where the heat produced is less than that produced when contacting a non-wet water-removing solid with an ethylene oxide feed.
[008] In yet another aspect, a system is provided here for the continuous supply of ethylene oxide to a carbonylation zone, which includes:
an ethylene oxide source configured to provide an ethylene oxide feed;
a water removal unit comprising an inlet configured to receive the ethylene oxide feed, an outlet configured to produce a treated ethylene oxide stream and a wet water removal solid, in which the water removal unit is configured to contact the ethylene oxide feed with the wet water-removing solid;
the wet water removal solid is wetted with organic solvent, ethylene oxide or a mixture thereof;
the ethylene oxide feed comprises ethylene oxide and has an initial water content, the treated ethylene oxide stream comprises ethylene oxide and has a water content, and the water content of the treated ethylene oxide stream is more lower than the initial water content; and
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5/30 the contact produces heat, in which the heat produced is less than that produced when contacting a non-wet water-removing solid with an ethylene oxide feed; and a carbonylation zone comprising an inlet configured to receive the treated ethylene oxide stream, wherein the carbonylation zone is configured to contact the ethylene oxide stream treated with carbon monoxide, in the presence of a carbonylation catalyst.
[009] In some variations, contact of the ethylene oxide stream treated with carbon monoxide, in the presence of a carbonylation catalyst, produces a carbonylation product that may include beta-propiolactone, succinic anhydride or a combination thereof.
[0010] In some variations of the foregoing methods, the treated ethylene oxide stream has a water content at least 50% lower than the initial water content. In other variations, the initial water content is above 5 ppm, or the water content of the treated ethylene oxide stream is less than 2 ppm, or both. In certain variations, contacting the wet water-removing solid with the ethylene oxide feed results in less than 10% by weight of ethylene oxide polymerization, or less than 10% by weight of the ethylene oxide being converted ethylene glycol. In certain variations, the organic solvent includes an ether, such as tetrahydrofuran.
DETAILED DESCRIPTION [0011] Here are provided methods of treating a
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6/30 ethylene oxide feed suitable for use in carbonylation reactions. The presence of water in ethylene oxide can lead to a variety of negative effects in continuous carbonylation processes. Methods of removing water from ethylene oxide may include using a water-removing solid, such as molecular sieves, to remove traces of water. However, contacting water removal solids with ethylene oxide can be exothermic, producing heat that can lead to the homopolymerization of ethylene oxide and / or to the reaction of ethylene oxide with water. These side reactions can reduce carbonylation yields, and side products can impact the efficient operation of continuous commercial scale processes. Thus, methods for removing additional water from ethylene oxide are provided here when controlling such side reactions.
[0012] In some respects, methods are provided here for treating an ethylene oxide feed with a water-removing solid to produce a treated ethylene oxide feed. In certain embodiments, contacting ethylene oxide with a water-removing solid, such as molecular sieves, can lead to the conversion of ethylene oxide to side products, such as polyethylene glycol and / or ethylene glycol. Without wishing to be bound by any theory, an increase in temperature during the initial contact of ethylene oxide with a water-removing solid can lead to localized heating, which can promote side reactions that include, for example, the polymerization of ethylene oxide to produce polyethylene glycol and / or ethylene oxide reaction with water.
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7/30 [0013] In some variations, the methods include controlling the contact conditions between an ethylene oxide feed and a water-removing solid, such that, compared to if the conditions are not controlled, the amount of heat generated is decreased, a lower temperature of the ethylene oxide feed is achieved, or there is a reduction in undesirable side reactions, or all combinations thereof.
[0014] In certain respects, methods are provided here for wetting a water removal solid and then contacting an ethylene oxide feed with the wet water removal solid to produce a treated ethylene oxide stream. In other respects, contacting an ethylene oxide feed with a wet water-removing solid produces less heat, maintains a lower ethylene oxide temperature, and / or reduces ethylene oxide side reactions, compared to contacting a feed of ethylene oxide. ethylene oxide with a non-wet water-removing solid. The treated ethylene oxide stream can undergo additional processes, such as carbonylation to produce beta-propiolactone and / or succinic anhydride.
[0015] In other respects, systems are provided for contacting an ethylene oxide feed with a wet water-removing solid to produce a treated ethylene oxide stream. These methods and systems are described in further detail below.
Methods of Treating Ethylene Oxide Feed [0016] As described above, in some respects, the methods described here include controlling the conditions of contact between the ethylene oxide feed and the solid
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8/30 water removal, such that the amount of heat generated is decreased, a lower temperature of ethylene oxide is achieved and / or there is a reduction in undesirable side reactions, compared to if the conditions are not controlled. As used herein, ethylene oxide can also be referred to as OE.
[0017] In certain embodiments, the methods described here include controlling the contact conditions between an ethylene oxide feed and a water-removing solid, such that the temperature of the ethylene oxide in the feed remains within a certain range. In some variations, the ethylene oxide feed is contacted by a water removal solid in an adsorbent or drying bed, and control of the contact conditions between the ethylene oxide feed and the water removal solids results in temperature of the ethylene oxide in the adsorbent or drying bed to remain within a certain range. In some embodiments, controlling the contact conditions between an ethylene oxide feed and a water-removing solid reduces unwanted side reactions, such as, for example, polymerization of ethylene oxide and / or reaction of ethylene oxide with water to produce ethylene glycol. Water Removal Solid Wetting [0018] Methods of controlling contact conditions may include, for example, wetting the water removing solid prior to contact with the ethylene oxide feed. The water-removing solid can be wetted with, for example, a solvent, ethylene oxide or a combination thereof, prior to contact with the ethylene oxide feed. In certain modalities, the methods are
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9/30 characterized by the ethylene oxide feed not being brought into contact with the dry water removal solid.
[0019] It should be understood that the solvent, ethylene oxide or a combination thereof used to wet the water-removing solid may, in some modalities, contain no water, or contain only trace amounts of water. Thus, the water-removing solid can be wetted with a non-aqueous solvent, a non-aqueous ethylene oxide, or a non-aqueous combination thereof.
[0020] Without being limited by any theory, wetting the water-removing solid with a solvent before contacting the ethylene oxide feed or before establishing a continuous ethylene oxide feed can reduce the amount of heat generated by the contact, the temperature of the ethylene oxide feed, and / or the amount of undesirable side products produced in relation to the use of the non-wet water-removing solid. Thus, the use of the wet water removal solid may, in some embodiments, allow water to be removed from the ethylene oxide feed while controlling the heat and / or the side products generated. This can increase the carbonylation yield in optional downstream processes, such as carbonylation of ethylene oxide to produce succinic anhydride, beta-propiolactone or a combination thereof.
[0021] Wetting the water-removing solid may include contacting the water-removing solid with a solvent, ethylene oxide, or a combination thereof, until the surface of the solid is saturated with a solvent, ethylene oxide or combination of the same.
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10/30 [0022] In some variations, wetting the water-removing solid comprises saturating the outer surfaces of the water-removing solid with the solvent, ethylene oxide, or a combination thereof. In some variations, the water-removing solid comprises pores, and wetting the water-removing solid comprises saturation of the surfaces within the pores. In still other variations, the water-removing solid comprises particles and pores, and in some embodiments wetting the water-removing solid comprises having the solvent, ethylene oxide, or a combination thereof, present between the particles, within the pores or a combination of them.
[0023] In some embodiments, the additional solvent is removed before contacting the wet water-removing solid with the ethylene oxide feed or before establishing a continuous ethylene oxide feed, when in other embodiments the additional solvent is not removed. It should be understood that when the additional solvent is removed, the solvent may still be present on the outer surfaces, surfaces within the pores (if present), between particles (if present), and within the pores (if present) of the removal solid of water.
[0024] In some embodiments, the water removal solid is wetted with ethylene oxide. This can be done gradually by introducing ethylene oxide to the water removal solid while maintaining the temperature of the ethylene oxide within a specified range. In some embodiments, ethylene oxide is gaseous, while in other embodiments, ethylene oxide is liquid. In some embodiments, ethylene oxide is introduced to the water-removing solid as
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11/30 a mixture, for example as a combination of ethylene oxide and inert gas, or a combination of ethylene oxide and a solvent.
[0025] In certain embodiments, contacting an ethylene oxide feed with a wet water-removing solid leads to at least 99% lower, at least 90% lower, at least 80% lower, at least 70% more low, at least 60% lower, at least 50% lower, at least 40% lower, at least 30% lower, at least 20% lower, at least 10% lower, at least 5% lower , at least 1% lower, between 1% and 99% lower, between 10% and 90% lower, between 10% and 50% lower, between 1% and 10% lower, or between 1% polymerization and 20% lower ethylene oxide than if the ethylene oxide feed has been contacted with a water-removing solid that is not wet.
[0026] In certain embodiments, contacting an ethylene oxide feed with a wet water-removing solid leads to at least 99% lower, at least 90% lower, at least 80% lower, at least 70% more low, at least 60% lower, at least 50% lower, at least 40% lower, at least 30% lower, at least 20% lower, at least 10% lower, at least 5% lower at least 1% lower, between 1% and 99% lower, between 10% and 90% lower, between 10% and 50% lower, between 1% and 10% lower, or between a conversion of 1 % and 20% lower ethylene oxide to ethylene glycol than if the ethylene oxide feed was contacted with a water-removing solid that was not wet.
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12/30 [0027] In certain embodiments, contacting an ethylene oxide feed with a wet water-removing solid produces at least 99% less, at least 90% less, at least 80% less, at least 70% less, at least 60% less, at least 50% less, at least 40% less, at least 30% less, at least 20% less or at least 10% less heat than is produced by contacting a non-wet water-removing solid with an ethylene oxide feed.
[0028] In certain embodiments, contacting a feed of ethylene oxide with wet water removal solids results in less than 15% by weight, less than 10% by weight, less than 5% by weight, less than 1% by weight , less than 0.5% by weight, or less than 0.1% by weight of the polymerization of ethylene oxide.
[0029] In certain modalities, contacting a feed of ethylene oxide with wet water removal solids results in less than 15% by weight, less than 10% by weight, less than 5% by weight, less than 1% by weight , less than 0.5% by weight or less than 0.1% by weight of the ethylene oxide being converted to ethylene glycol.
[0030] Appropriate solvents for wetting the water-removing solid may include, for example, hydrocarbons, ethers, esters, nitriles or sulfones, or any mixtures thereof. In certain embodiments, the water-removing solid is wetted with a solvent that comprises an ether. In certain embodiments, the ether is selected from the group consisting of tetrahydrofuran, 1,4-dioxane, glyme, diglyme, triglyme, tetraglyme, diethyl ether, diphenyl ether, methyl-t-butyl ether, and any combinations thereof. In certain embodiments, the ether comprises
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13/30 tetrahydrofuran. In certain embodiments, the ether comprises 1,4-dioxane. In certain embodiments, the ether comprises diglyme. In certain embodiments, the solvent used to wet the water-removing solid is the same solvent used in one or more downstream processes, such as the optional carbonylation of the treated ethylene oxide stream. In other embodiments, the ethylene oxide feed that contacts the water removal solid comprises a solvent, where the solvent is the same solvent used to wet the water removal solid.
Contact Temperature [0031] In some embodiments, controlling the contact conditions between the ethylene oxide feed and the water removal solid includes contacting the ethylene oxide feed with the water removal solid at a temperature that does not lead to polymerization, or lead to lower polymerization than contact at a different temperature. In one embodiment, the ethylene oxide feed is contacted with a water-removing solid at a temperature of less than 100 ° C, less than 70 ° C, or less than 50 ° C. In certain embodiments, contacting the ethylene oxide feed with a water-removing solid at a temperature of less than 100 ° C, less than 70 ° C, or less than 50 ° C leads to at least 99% lower, at least at least 90% lower, at least 80% lower, at least 70% lower, at least 60% lower, at least 50% lower, at least 40% lower, at least 30% lower, at least least 20% lower, at least 10% lower, at least 5% lower, at least 1% lower, between 1% and 99% lower, between 10% and 90% lower, between 10% and 50 % more
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14/30 low, between 1% and 10% lower, or between 1% and 20% lower polymerization of ethylene oxide than if the ethylene oxide feed was contacted with the water removal solid at a higher temperature.
[0032] In certain embodiments, the step of contacting the ethylene oxide feed with the water-removing solid is kept within the range of about -20 ° C to about 70 ° C, about -15 ° C at about 40 ° C, from about -10 ° C to about 30 ° C, from about -10 ° C to about 20 ° C, from about -20 ° C to about 0 ° C, from about 10 ° C to about 20 ° C or about 10 ° C to about 50 ° C.
[0033] In other modalities, the methods and processes described here include controlling the conditions of contact between the ethylene oxide stream and the water removal solid, such that contacting the ethylene oxide stream with the removal solid of water increases the temperature of the ethylene oxide stream by less than 10 ° C, 5 ° C, less than 4 ° C, less than 3 ° C, less than 2 ° C, less than 1 ° C, less than 0, 5 ° C, or less than 0.1 ° C.
Water Removal Solid [0034] In certain embodiments, the water removal solid adsorbs water. In some embodiments, the water removal solid is an inorganic solid. In some embodiments, the water-removing solid is a zeolite, a composition of porous glass, a clay, or silica. In some embodiments, the water-removing solid comprises a molecular sieve.
[0035] In certain embodiments, the water-removing solid comprises a molecular sieve that has a pore size too small to effectively admit molecules of
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15/30 ethylene oxide. In some embodiments, the pore size is less than 4.2 Å.
[0036] In certain embodiments, the water-removing solid is a molecular sieve, where the molecular sieve has a pore size of less than 4.2 Å, less than
4.0 Â, less than 3.8 Â, less than 3.6 Â, less than
3.4 Â, less than 3.2 Â or less than 3.0 Â. In certain embodiments, the water-removing solid is a molecular sieve, where the molecular sieve has a pore size of 3 Â or 4 Â. In certain embodiments, the water-removing solid comprises a molecular sieve, where the molecular sieve has a mixture of pore sizes. In certain embodiments, the molecular sieve comprises a microporous inorganic solid. In certain embodiments, the molecular sieve comprises a zeolite.
[0037] In other variations, any combinations of the water removal solids described here can be used.
Ethylene Oxide Feed [0038] The ethylene oxide feed comprises ethylene oxide and can be liquid, gaseous, or a combination thereof. In certain embodiments, the ethylene oxide feed comprises an initial water content, and contacting the ethylene oxide feed with a water-removing solid produces a stream of treated ethylene oxide that has a lower water content than the initial water content of the ethylene oxide feed.
Water Content [0039] In certain modalities, the ethylene oxide feed has an initial water content above 20
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16/30 ppm, above 10 ppm, above 5 ppm or above 1 ppm. In some embodiments, the water content of the treated ethylene oxide stream is less than 20 ppm, less than 15 ppm, less than 10 ppm, less than 5 ppm, less than 4 ppm, less than 3 ppm, less than 2 ppm or less than 1 ppm. In certain embodiments, the water content of the treated ethylene oxide stream is less than 0.5 ppm, less than 0.4 ppm, less than 0.25 ppm, less than 0.1 ppm, less than than 0.05 ppm or less than 0.01 ppm.
[0040] In certain modalities, the ethylene oxide feed has an initial water content above 20 ppm, and the treated ethylene oxide stream has a water content less than 10 ppm. In certain embodiments, the ethylene oxide feed has an initial water content above 10 ppm, and the treated ethylene oxide stream has a water content less than 5 ppm.
[0041] In certain embodiments, the ethylene oxide feed has an initial water content between about 100 ppm and about 500 ppm, between about 20 ppm and about 200 ppm, between about 4 ppm and about 200 ppm, between about 20 ppm and about 100 ppm, between about 4 ppm and about 100 ppm, and the water content of the treated ethylene oxide stream is less than 10 ppm, less than 5 ppm, less than 2 ppm, or less than about 1 ppm.
[0042] In some embodiments, the treated ethylene oxide stream has a water content at least 50% lower, at least 40% lower, at least 30% lower, at least 20% lower or at least 10 % lower than the initial water content of the ethylene oxide stream. Food Composition
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17/30 [0043] In some modalities, the ethylene oxide feed comprises between 1% and 99% by weight of ethylene oxide, between 2% and 90% by weight of ethylene oxide, between 5% and 80% in weight of ethylene oxide, between 5% and 70% by weight of ethylene oxide, between 5% and 75% by weight of ethylene oxide, between 10% and 90% by weight of ethylene oxide, between 20% and 80 % by weight of ethylene oxide, between 20% and 70% by weight of ethylene oxide, between 30% and 40% by weight of ethylene oxide, or between 40% and 75% by weight of ethylene oxide.
[0044] In certain embodiments, the ethylene oxide feed comprises a solvent. Suitable solvents can include, for example, hydrocarbons, ethers, esters, nitriles or sulfones, or any mixtures thereof. In certain embodiments, the ethylene oxide feed comprises ethylene oxide and an ether. In some embodiments, the ether is selected from the group consisting of tetrahydrofuran, 1,4-dioxane, glyme, diglyme, triglyme, tetraglyme, diethyl ether, diphenyl ether, methyl-t-butyl ether and any mixtures thereof. In certain embodiments, the ether comprises tetrahydrofuran. In certain embodiments, the ether comprises 1,4-dioxane. In certain embodiments, the ether comprises diglyme.
Contact the Ethylene Oxide Feed with Water Removal Solid [0045] In certain embodiments, the step of contacting the ethylene oxide feed with a water removal solid comprises continuously passing the ethylene oxide feed through a fixed bed comprising the water-removing solid. In certain modalities, the
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18/30 Contacting the ethylene oxide feed with a water-removing solid comprises continuously passing the ethylene oxide feed through one or more containers containing a suspension of the water-removing solid. In certain embodiments, the ethylene oxide feed is in contact with the water-removing solid for about 0.5 and about 240 minutes. In certain embodiments, the time that the ethylene oxide feed is in contact with the water-removing solid is sufficient for the initial water content in the ethylene oxide feed to be reduced by at least 50%, at least 75%, at least 85%, at least 95%, at least 95%, at least 98% or at least 99%. In certain embodiments, the time that the ethylene oxide feed is in contact with the water-removing solid is sufficient for the initial water content in the ethylene oxide feed to be reduced by at least 5%, at least 10%, at least 20%, at least 30% or at least 40%.
[0046] In certain embodiments, the methods or systems described herein comprise two or more columns (or suspension beds) of the water-removing solid. This can allow, for example, the gaseous or liquid feed of ethylene oxide to be run through a first column comprising the water removal solid for a first interval, then the flow can be diverted to a second column comprising the solid water removal for a second interval. The flow can be diverted again to subsequent columns, for example in a system or method using three, four, five, six or more columns (or suspension beds). In certain embodiments, a column comprising the water-removing solid is contacted
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19/30 by the ethylene oxide stream for a period of time, the ethylene oxide stream is diverted to one or more subsequent columns, the water-removing solid in the first column is regenerated, and the regenerated column is contacted again by the ethylene oxide stream. Regeneration of the water removal solid may include draining the liquid from the water removal solid, displacing any residual ethylene oxide with ambient nitrogen, and then heating the water removal solid to a temperature of 150 ° C to 250 ° C, under reduced pressure (for example, a vacuum), or under a flow of inert gas (for example, nitrogen).
[0047] In certain embodiments, the method includes determining the efficiency of water removal to determine when to switch the ethylene oxide feed to a subsequent column. This may include, for example, analyzing the water content of the treated ethylene oxide stream leaving one or more columns and diverting the stream to one or more subsequent columns when the water content of the ethylene oxide stream treaty exceeds a certain threshold. In other embodiments, determining the water removal efficiency may include determining the amount of water absorbed by a column (or group of columns) and comparing this value to a certain starting point for the absorption capacity of that column (or group columns). For example, the water content of the treated ethylene oxide stream can be determined and compared to the water content of the ethylene oxide feed, and the amount of water absorbed by the column calculated by totalizing the flow of ethylene oxide over time. .
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20/30
Systems for the Treatment of Ethylene Oxide [0048] In another aspect, systems are provided here for the treatment of an ethylene oxide feed. In some embodiments, the system includes an ethylene oxide source configured to provide an ethylene oxide feed; and a water removal unit comprising an inlet configured to receive the ethylene oxide feed, an outlet configured to produce a treated ethylene oxide stream, and a wet water removal solid. In some variations, the system also comprises a monitoring unit configured to monitor the water content of the treated ethylene oxide stream.
[0049] It should be understood that any variations described above for the methods provided apply to the systems described here. For example, the systems described here are configured to receive and use variations of the water-removing solid and the ethylene oxide feed, and treat the ethylene oxide feed.
[0050] In certain embodiments, the water removal unit is configured to contact the ethylene oxide feed with the wet water removal solid. In other embodiments, the wet water-removing solid is wetted with organic solvent, ethylene oxide or a mixture thereof. The ethylene oxide feed comprises ethylene oxide and has an initial water content, and the treated ethylene oxide stream comprises ethylene oxide and has a water content. In some embodiments, the water content of the treated ethylene oxide stream is lower than the initial water content. As described above, contacting the ethylene oxide feed produces heat, and in some
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21/30 modalities, the systems described here are configured so that the heat produced is less than that produced when contacting a non-wet water removal solid with an ethylene oxide feed.
[0051] In certain embodiments, the ethylene oxide source is configured to continuously supply an ethylene oxide supply to the inlet of the water removal unit.
[0052] In some embodiments, the ethylene oxide feed that enters the water removal unit is at a temperature that does not conduct, or minimize, the homopolymerization of ethylene oxide through contact with the water removal solid. In one embodiment, the ethylene oxide feed enters the water removal unit at a temperature less than 100 ° C, less than 70 ° C or less than 50 ° C.
[0053] In certain embodiments, the temperature of the water removal unit is between about -20 ° C to about 70 ° C, about -15 ° C to about 40 ° C, about 10 ° C at about 30 ° C, from about -10 ° C to about 20 ° C, about -20 ° C to about 0 ° C, about 10 ° C to about 20 ° C or about from 10 ° C to about 50 ° C.
[0054] As described above, the ethylene oxide feed comprises ethylene oxide and, optionally, a solvent. In some embodiments, the solvent comprises an ether. In certain embodiments, the ether is selected from the group consisting of tetrahydrofuran, 1,4dioxane, glyme, diglyme, triglyme, tetraglyme, diethyl ether, diphenyl ether, methyl-t-butyl ether and any combinations thereof. In certain embodiments, the ether comprises tetrahydrofuran. In
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22/30 certain embodiments, the ether comprises 1,4-dioxane. In certain embodiments, ether comprises diglyme. In certain embodiments, the ethylene oxide feed comprises a solvent, where the same solvent is used in one or more downstream processes, such as the carbonylation of ethylene oxide to produce beta-propiolactone, succinic anhydride or a combination thereof.
[0055] The ethylene oxide feed that enters the entrance to the water removal unit may comprise between 10% by weight and 90% by weight of ethylene oxide, between 20% by weight and 80% by weight of ethylene oxide , between 20% by weight and 70% by weight of ethylene oxide, between 30% by weight and 40% by weight of ethylene oxide, or between 40% by weight and 75% by weight of ethylene oxide. In certain embodiments, the weight percentage of ethylene oxide in the ethylene oxide feed is between 1% by weight and 99% by weight, between 2% by weight and 90% by weight, between 5% by weight and 80% by weight. between 5% by weight and 70% by weight or between 5% by weight and 75% by weight.
[0056] In certain modalities, the water removal unit is configured to continuously pass the ethylene oxide feed through a contact zone, where it contacts the wet water removal solid. In certain embodiments, the water removal unit comprises one or more fixed beds or one or more suspension beds which comprise the water removing solid. In certain embodiments, the average time between the ethylene oxide feed entering the removal unit and water from the ethylene oxide source and the treated ethylene oxide stream leaving the water removal is between about 0.5 and fence
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23/30 of 240 minutes. In certain embodiments, the time that the ethylene oxide feed is in contact with the water-removing solid is sufficient for the initial water content in the incoming ethylene oxide feed to be reduced by at least 50%, at least 75 %, at least 85%, at least 95%, at least 95%, at least 98% or at least 99%.
[0057] In certain modalities, the water removal unit comprises two or more parallel treatment zones, and are configured to exchange the flow of ethylene oxide feed from a first treatment zone (or group of treatment zones) to another parallel treatment zone (or group of treatment zones). It should be understood that each treatment zone can comprise one or more columns or reactors (or combinations of columns and reactors). Where two or more columns or reactors are present in a treatment zone, they can be placed in parallel, in series or any combination of parallel and series.
[0058] In certain modalities, the system also includes a monitoring unit. In some variations, the monitoring unit is configured to monitor the water content of the treated ethylene oxide stream, the initial water content of the ethylene oxide feed, or a combination thereof. This may include, for example, monitoring the water content of the treated ethylene oxide stream leaving one or more columns in a water removal unit.
[0059] In some variations, the monitoring unit is configured to monitor the amount of water removed by the water removal unit, or to monitor the
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24/30 water removal unit efficiency.
[0060] In some modalities, the water content, amount of water or efficiency monitored by the monitoring unit are compared to a starting point value. In some embodiments, the starting point value is 5 ppm of water, 3 ppm of water, 10% by weight of water or 5% by weight of water. For example, in some modalities a monitoring instrument monitors the amount of water removed by the water removal unit, and this amount is compared to a threshold value of 10% by weight of water or 5% by weight of water. In some modalities, a monitoring instrument monitors the water content of the treated ethylene oxide stream, and this index is compared to a threshold value of 5 ppm of water, or 3 ppm of water.
[0061] In some embodiments, when the water content of the treated ethylene oxide stream, the amount of water removed by the water removal unit, or the efficiency of the water removal unit approaches a threshold value, the feed of ethylene oxide is exchanged from a first treatment zone to a parallel treatment zone. Thus, in some embodiments, the system also comprises an instrument for exchanging the ethylene oxide feed from a first treatment zone to another parallel treatment zone. The water content of the treated ethylene oxide stream or amount of water removed by the water removal unit can be kept below some threshold value, or the efficiency of the water removal unit can be maintained above some threshold value. starting point, through monitoring with the monitoring unit as described above and changing the power supply
Petition 870190068300, of 07/18/2019, p. 37/50
25/30 ethylene oxide from a first treatment zone to a parallel treatment zone, when approaching the starting point value.
[0062] For example, in some modalities, the system comprises a monitoring unit to measure the efficiency of the water removal unit and an instrument to exchange the ethylene oxide feed from a first treatment zone to another treatment zone parallel, such that the efficiency of the water removal phase can be maintained above a desired starting point value.
[0063] In certain modalities, the system also comprises a regeneration unit to regenerate one or more treatment zones when another parallel treatment zone is in use. In certain embodiments, the system comprises an instrument for removing an ethylene oxide treatment zone prior to regeneration of the water-removing solid. Removing may be desirable to prevent residual ethylene oxide reactions during regeneration and mitigate the dangers associated with heating ethylene oxide vapor. In certain embodiments, the removal instrument includes a vacuum source that can be attached to the treatment area to be regenerated. In some embodiments, the removal instrument includes a source of inert gas, such as nitrogen or argon, which can be attached to the treatment zone to be regenerated and, optionally, an outlet for the inert gas to leave the treatment zone that is being regenerated. In certain embodiments, the removal instrument comprises a vacuum source, an inert gas source and a distributor to affect the alternative coupling of each to the
Petition 870190068300, of 07/18/2019, p. 38/50
26/30 treatment to be regenerated. In certain modalities, the system comprises a scrubbing instrument for capturing or destroying the ethylene oxide purged from the treatment area by operating the removal instrument. In certain embodiments, the scrubbing instruments are coupled to the exhaust of the vacuum source and / or an inert gas outlet of the removal instrument. The scrubbing instrument may include, for example, aqueous scrubbing baths, reactive resins, thermal oxidizers, spinners or combinations thereof. The regeneration of the treatment zones can include, for example, application of heat and / or vacuum and / or flow of an inert gas or liquid through the treatment zone.
[0064] In some embodiments, the system also comprises a carbonylation zone that comprises an entrance configured to receive the treated ethylene oxide stream. This carbonylation zone, in certain modalities, is configured to contact the stream of ethylene oxide treated with carbon monoxide, in the presence of a carbonylation catalyst. In some embodiments, contacting the ethylene oxide stream treated with carbon monoxide, in the presence of a carbonylation catalyst, produces a carbonylation product that comprises betapropiolactone, succinic anhydride or a combination thereof.
EXAMPLES [0065] The following examples are illustrative only and are not meant to limit any aspect of the present disclosure in any way.
Example 1
Continuous drying of an OE feed stream for an OE carbonylation process using online measurement
Petition 870190068300, of 07/18/2019, p. 39/50
27/30 water for control [0066] An ethylene oxide inlet is provided through the piping of a colocalized ethylene oxidation unit, where the ethylene oxide stream has an average water content between 10 ppm and 40 ppm . Before entering a reactor downstream of OE carbonylation, the ethylene oxide feed is pumped in a water removal phase comprising six parallel packed and coated bed columns, each containing 10,000 kg of 3 µm molecular sieves. based on zeolite. Before departure, each of the columns is filled with anhydrous tetrahydrofuran and then the tetrahydrofuran is drained from the columns. At startup, two of the parallel columns are fed with liquid OE from the pipeline at a total flow of 10 metric tons / h, while the active column liners are connected to a flow of chilled water at 10 ° C. The water content of the outlet of each of the two columns is monitored by the Karl Fischer titration. The water concentration in the two columns is monitored over time.
[0067] Once the water content of column 1 is found to exceed a predetermined threshold of 3 ppm, the OE feed to column 1 can be diverted to a new column that has recently been regenerated. Column 1 is purged by alternative evacuation and flushed with nitrogen until an OE detector at the outlets records less than 50 ppm OE in the nitrogen stream that exits the column during washing. At this time, the coating is drained from the cooling liquid and a flow of steam at 180 ° C is introduced and maintained for 6 hours. The column is then cooled with the help of tempered water to the coating, and the
Petition 870190068300, of 07/18/2019, p. 40/50
28/30 Dry tetrahydrofuran (THF) is flowed into the column from a THF feed tank that is part of the downstream carbonylation reactor. Once the column is filled with THF, it is maintained in this circumstance until it is necessary to replace another exhausted column. This cycle is repeated continuously between the six columns to maintain a constant OE feed stream, having less than 3 ppm of water to the downstream carbonylation reactor. Example 2
Continuous drying of an OE feed stream for an OE carbonylation process using 4 ulares molecular sieves [0068] This example follows the procedure described in Example 1, except that the drying columns contain 4 Å molecular sieves.
Example 3
Continuous drying of an OE feed stream for an OE carbonylation process using higher column temperatures [0069] This example follows the procedure described in Example 1, except that the drying columns are maintained at a temperature of 40- 50 ° C during operation.
Example 4
Continuous drying of an OE feed stream for an OE carbonylation process using OE solution as feed [0070] This example follows the procedure described in Example 1, except that the drying liquid OE stream fed to the OE inlet is a 50% by weight solution of OE in tetrahydrofuran.
Petition 870190068300, of 07/18/2019, p. 41/50
29/30
Example 5
Continuous drying of an OE feed stream for an OE carbonylation process using an alternative water measuring instrument
[0071] This example follow the procedure described at the Example 1, except that the content water chain in power supply OE that get out of columns is monitored per
mass spectroscopy.
Example 6
Drying of an OE feed stream for an OE carbonylation process using pre-oiled molecular sieves [0072] An OE drying column was manufactured from a 50 mL stainless steel cylinder with welded 7-micron filters, valves 41G series ball bearings and appropriate fittings, all from Swagelok. The cylinder was packed with UOP EPG-2 molecular sieves (3 Â, 1/16 (0.1587 cm) rods) that were subsequently activated in a nitrogen flow (T = 240 ° C). The column with activated sieves was brought into a glove box and treated with dry THF (1 mL), to control heating by adding OE. The activated and treated sieve column was then connected to an OE cylinder and a scrubbing system. Pre- and post-column OE samples were collected in a cylinder (3 (7.62 cm) in length of tubing equipped with a Swagelok cap, a reducer and a 41G ball valve). Before each collection, the sample cylinder was connected to a Schlenk line and evacuated to <100 mTorr (0.0133 kPa) when heated to 100 ° C. After collection, a needle was connected to the sample cylinder valve while purged with
Petition 870190068300, of 07/18/2019, p. 42/50
30/30 nitrogen. The cylinder / needle unit was quickly transferred from the nitrogen source to the inlet of a Karl-Fisher titrator (Mettler-Toledo C30) inlet, the needle introduced through the septum and the valve opened slowly to allow the sample in the titrator. After each sample was titrated, the electrolyte (Fluka Hydranal Coulomat AG) was discarded, the cell washed with two 50 mL portions and filled with 100 mL of fresh electrolyte. The results are summarized in Table 1 below.
Table 1. Water concentration of the OE sample taken before and after drying.
Sample H2O concentration in the sample (ppm) Before drying 20, 9 After drying 10.5
Petition 870190068300, of 07/18/2019, p. 43/50

权利要求:
Claims (24)
[1]
1. Ethylene oxide treatment method, FEATURED for understanding:
wetting a water-removing solid with organic solvent, or ethylene oxide or a combination thereof; and continuously contacting the wet water-removing solid with an ethylene oxide feed to produce a treated ethylene oxide stream, wherein the ethylene oxide feed comprises ethylene oxide and has an initial water content, the Treated ethylene oxide comprises ethylene oxide and has a water content, and the water content of the treated ethylene oxide stream is lower than the initial water content.
[2]
Method according to claim 1, CHARACTERIZED in that the treated ethylene oxide stream has a water content at least 50% lower than the initial water content.
[3]
3. Method according to claim 1 or 2, CHARACTERIZED by:
(i) the initial water content is above 5 ppm; or (ii) the water content of the treated ethylene oxide stream is less than 2 ppm;
or both (i) and (ii).
[4]
4. Method according to any one of claims 1 to 3, characterized in that contacting the wet water-removing solid with the ethylene oxide feed results in less than 10% by weight of the ethylene oxide polymerization.
Petition 870190068300, of 07/18/2019, p. 44/50
2/6
[5]
Method according to any one of claims 1 to 4, CHARACTERIZED that contacting the wetted water-removing solid with the ethylene oxide feed results in less than 10% by weight of the ethylene oxide being converted to ethylene glycol.
[6]
Method according to any one of claims 1 to 5, CHARACTERIZED in that the water-removing solid is a zeolite, clay or silica, or any combination thereof.
[7]
Method according to any one of claims 1 to 6, characterized in that the water-removing solid is a molecular sieve.
[8]
Method according to any one of claims 1 to 7, characterized in that contacting the water-removing solid with ethylene oxide comprises introducing ethylene oxide to the water-removing solid maintaining the temperature of the ethylene oxide within a specified scale.
[9]
Method according to any one of claims 1 to 8, CHARACTERIZED in that the organic solvent comprises an ether.
[10]
Method according to any one of claims 1 to 7 and 9, CHARACTERIZED that the organic solvent comprises tetrahydrofuran, 1,4-dioxane, glyme, diglyme, triglyme, tetraglyme, diethyl ether, diphenyl ether or methyl-t- ether butyl, or any combination thereof.
[11]
Method according to any one of claims 1 to 9, characterized in that the organic solvent comprises tetrahydrofuran.
Petition 870190068300, of 07/18/2019, p. 45/50
3/6
[12]
Method according to any one of claims 1 to 11, characterized in that the ethylene oxide feed is gaseous or liquid.
[13]
13. Method according to any one of claims 1 to 12, CHARACTERIZED that the contact of the wet water-removing solid with the ethylene oxide feed produces heat, in which the heat produced is less than that produced when contacting a non-wet water removal solid with an ethylene oxide feed.
[14]
14. Method of continuous supply of ethylene oxide to a carbonylation zone, CHARACTERIZED because it comprises:
wetting an inorganic water-removing solid with organic solvent, ethylene oxide or a combination thereof;
continuously contacting the wet inorganic water-removing solid with an ethylene oxide feed to produce a treated ethylene oxide stream;
feeding the treated ethylene oxide stream to a carbonylation zone; and contacting the ethylene oxide stream treated with carbon monoxide in the presence of a carbonylation catalyst in the carbonylation zone, where the ethylene oxide feed has an initial water content, the treated ethylene oxide stream has a content of water, and the water content of the treated ethylene oxide stream is lower than the initial water content.
[15]
15. Method, according to claim 14, CHARACTERIZED by contacting the ethylene oxide stream
Petition 870190068300, of 07/18/2019, p. 46/50
4/6 treated with carbon monoxide in the presence of a carbonylation catalyst in the carbonylation zone to produce a carbonylation product comprising beta-propiolactone, succinic anhydride or a mixture thereof.
[16]
16. Method according to claim 14 or 15, CHARACTERIZED that the contact produces heat, wherein the heat produced is less than that produced by contacting a non-wet inorganic water-removing solid with an ethylene oxide feed .
[17]
17. System for the treatment of ethylene oxide, FEATURED for comprising:
an ethylene oxide source configured to provide an ethylene oxide feed; and a water removal unit comprising an inlet configured to receive the ethylene oxide feed, an outlet configured to produce a stream of treated ethylene oxide and a wet water removal solid, wherein the water removal unit is configured to contact the ethylene oxide feed with the wet water removal solid;
the wet water removal solid is wetted with organic solvent, ethylene oxide or a mixture thereof;
the ethylene oxide feed comprises ethylene oxide and has an initial water content, the treated ethylene oxide stream comprises ethylene oxide and has a water content, and the water content of the treated ethylene oxide stream it is lower than the initial water content.
[18]
18. System according to claim 17,
Petition 870190068300, of 07/18/2019, p. 47/50
5/6
CHARACTERIZED for also comprising a monitoring unit configured to monitor the water content of the treated ethylene oxide stream.
[19]
19. System, according to claim 18, CHARACTERIZED by the fact that the monitoring unit is configured to monitor the initial water content of the ethylene oxide feed.
[20]
20. System for continuous supply of ethylene oxide to a carbonylation zone, FEATURED for understanding:
an ethylene oxide source configured to provide an ethylene oxide feed;
a water removal unit comprising an inlet configured to receive the ethylene oxide feed, an outlet configured to produce a treated ethylene oxide stream and a wet water removal solid, in which the water removal unit is configured to contact the ethylene oxide feed with the wet water-removing solid;
the wet water removal solid is wetted with organic solvent, ethylene oxide or a mixture thereof;
the ethylene oxide feed comprises ethylene oxide and has an initial water content, the treated ethylene oxide stream comprises ethylene oxide and has a water content, and the water content of the treated ethylene oxide stream is more lower than the initial water content;
a carbonylation zone comprising an entrance configured to receive the ethylene oxide stream
Petition 870190068300, of 07/18/2019, p. 48/50 treated, in which the carbonylation zone is configured to contact the stream of ethylene oxide treated with carbon monoxide in the presence of a carbonylation catalyst.
[21]
21. The system of claim 20, characterized in that the contact of the ethylene oxide stream treated with carbon monoxide in the presence of a carbonylation catalyst produces a carbonylation product comprising beta-propiolactone, succinic anhydride or a combination thereof.
[22]
22. System, according to claim 21, CHARACTERIZED because it also includes a monitoring unit configured to monitor the water content of the treated ethylene oxide stream.
[23]
23. System, according to claim 22, CHARACTERIZED by the fact that the monitoring unit is configured to monitor the initial water content of the ethylene oxide feed.
[24]
24. System according to any of claims 17 to 23, CHARACTERIZED by the fact that the contact produces heat, in which the heat produced is less than that produced when contacting an inorganic water-removing solid not soaked with an ethylene oxide feed .

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法律状态:
2021-04-20| B08F| Application dismissed because of non-payment of annual fees [chapter 8.6 patent gazette]|Free format text: REFERENTE A 3A ANUIDADE. |

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2021-08-10| B08K| Patent lapsed as no evidence of payment of the annual fee has been furnished to inpi [chapter 8.11 patent gazette]|Free format text: REFERENTE AO DESPACHO 8.6 PUBLICADO NA RPI 2624 DE 20/04/2021. |

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2021-10-13| B350| Update of information on the portal [chapter 15.35 patent gazette]|

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